TW201741372A - Imide crosslinked resin, transparent film and surface protective film - Google Patents

Imide crosslinked resin, transparent film and surface protective film Download PDF

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TW201741372A
TW201741372A TW106115287A TW106115287A TW201741372A TW 201741372 A TW201741372 A TW 201741372A TW 106115287 A TW106115287 A TW 106115287A TW 106115287 A TW106115287 A TW 106115287A TW 201741372 A TW201741372 A TW 201741372A
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Taiwan
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group
copolymer
diamine
transparent film
crosslinked resin
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TW106115287A
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Chinese (zh)
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須賀健雄
西出宏之
小松伸一
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學校法人早稻田大學
Ｊｘｔｇ能源股份有限公司
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Publication of TW201741372A publication Critical patent/TW201741372A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

An imide crosslinked resin that is obtained by crosslinking a copolymer, which contains a cyclic olefin unit and an unsaturated dicarboxylic acid anhydride unit, by means of a diamine.

Description

醯亞胺交聯型樹脂、透明膜及表面保護膜Yttrium imide crosslinked resin, transparent film and surface protective film

本發明係關於一種醯亞胺交聯型樹脂、透明膜及表面保護膜。The present invention relates to a quinone imine crosslinked resin, a transparent film, and a surface protective film.

近年來，因攜帶型資訊終端等之普及，保護顯示器表面之表面保護膜之需求增加。例如，於專利文獻1中揭示有一種於偏光板或觸控面板上配置有覆蓋窗之有機電場發光顯示裝置。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2010-232162號公報In recent years, the demand for protecting the surface protective film on the surface of a display has increased due to the spread of portable information terminals and the like. For example, Patent Document 1 discloses an organic electric field light-emitting display device in which a cover window is disposed on a polarizing plate or a touch panel. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-232162

[發明所欲解決之問題] 表面保護膜係例如於膜基材之一個面上蒸鍍鋁等金屬而製造，但此時，對於膜基材，需求充分之耐熱性。 本發明之目的在於提供一種具有良好之耐熱性，且可較佳地用作表面保護膜用之樹脂材料之醯亞胺交聯型樹脂。又，本發明之目的在於提供一種包含醯亞胺交聯型樹脂，且可較佳地用作表面保護膜用之膜基材之透明膜。進而，本發明之目的在於提供一種具備該透明膜之表面保護膜。 [解決問題之技術手段] 本發明之一態樣係關於一種利用二胺將具有環狀烯烴單元及不飽和二羧酸酐單元之共聚物交聯而成之醯亞胺交聯型樹脂。 於一態樣中，環狀烯烴單元可具有降𦯉烷骨架。 於一態樣中，不飽和二羧酸酐單元可包含順丁烯二酸酐單元。 本發明之另一態樣係關於一種包含醯亞胺交聯型樹脂之透明膜。 本發明之又一態樣係關於一種具備透明膜、及設置於透明膜之至少一個面上之金屬蒸鍍層之表面保護膜。 [發明之效果] 根據本發明，提供一種具有良好之耐熱性，且可較佳地用作表面保護膜用之樹脂材料之醯亞胺交聯型樹脂。又，根據本發明，提供一種包含上述醯亞胺交聯型樹脂且作為表面保護膜用之膜基材較佳之透明膜、及具備該透明膜之表面保護膜。[Problems to be Solved by the Invention] The surface protective film is produced by, for example, vapor-depositing a metal such as aluminum on one surface of a film substrate. However, in this case, sufficient heat resistance is required for the film substrate. An object of the present invention is to provide a ruthenium imide crosslinked resin which has good heat resistance and can be preferably used as a resin material for a surface protective film. Further, an object of the present invention is to provide a transparent film comprising a ruthenium imide crosslinked resin which can be preferably used as a film substrate for a surface protective film. Further, an object of the present invention is to provide a surface protective film comprising the transparent film. [Technical means for solving the problem] An aspect of the present invention relates to an yttrium imide crosslinked resin obtained by crosslinking a copolymer having a cyclic olefin unit and an unsaturated dicarboxylic anhydride unit with a diamine. In one aspect, the cyclic olefin unit may have a reduced 𦯉 alkane skeleton. In one aspect, the unsaturated dicarboxylic anhydride unit can comprise a maleic anhydride unit. Another aspect of the invention relates to a transparent film comprising a ruthenium imide crosslinked resin. Still another aspect of the present invention relates to a surface protective film comprising a transparent film and a metal deposition layer provided on at least one surface of the transparent film. [Effect of the Invention] According to the present invention, there is provided a ruthenium imide crosslinked resin which has good heat resistance and can be preferably used as a resin material for a surface protective film. Moreover, according to the present invention, there is provided a transparent film which is preferably a film substrate for a surface protective film comprising the above-described quinone imine crosslinked resin, and a surface protective film comprising the transparent film.

以下，對本發明之較佳之實施形態進行說明。 (醯亞胺交聯型樹脂) 本實施形態之醯亞胺交聯型樹脂係利用二胺將具有環狀烯烴單元及不飽和二羧酸酐單元之共聚物交聯而成之交聯體。 於本說明書中，環狀烯烴單元係指來自環狀烯烴之結構單元，不飽和二羧酸酐單元係指來自不飽和二羧酸酐之結構單元。即，共聚物可謂係具有來自環狀烯烴之結構單元及來自不飽和二羧酸酐之結構單元之共聚物，亦可謂係包含環狀烯烴及不飽和二羧酸酐之單體成分之共聚物。 本實施形態之醯亞胺交聯型樹脂具有藉由共聚物中之酸酐與二胺中之胺基之反應而形成之醯亞胺鍵。本實施形態之醯亞胺交聯型樹脂藉由在分子內具備來自環狀烯烴之環結構及經由醯亞胺鍵之交聯結構，而顯示出充分之透光性及良好之耐熱性。因此，本實施形態之醯亞胺交聯型樹脂可較佳地用作表面保護膜用之樹脂材料。 ＜共聚物＞ 本實施形態中之共聚物係具有環狀烯烴單元及不飽和二羧酸酐單元，且可藉由二胺而交聯之聚合物。 於共聚物中，不飽和二羧酸酐單元之含量C2 (mol)及下述順丁烯二醯亞胺系單元之含量C3 (mol)之合計量C2 ＋C3 (mol)相對於環狀烯烴單元之含量C1 (mol)之比(C2 ＋C3 )/C1 例如可為0.5～2.0，較佳為0.95～1.05。 不飽和二羧酸酐單元之含量C2 相對於上述合計量C2 ＋C3 之比C2 /(C2 ＋C3 )例如可為0.01以上，較佳為0.5以上，亦可為1(即，順丁烯二醯亞胺系單元之含量為0)。 共聚物之數量平均分子量Mn例如可為190以上，較佳為1000以上，亦可為3000以上。藉由增大共聚物之數量平均分子量Mn，而有醯亞胺交聯型樹脂之耐熱性進一步提高之傾向。又，共聚物之數量平均分子量Mn例如可為500000以下，較佳為10000以下，亦可為7000以下。藉由減小共聚物之數量平均分子量Mn，而有利用二胺之交聯反應之反應率提高之傾向。 於共聚物中，重量平均分子量Mw相對於數量平均分子量Mn之比即分子量分佈Mw/Mn例如可為10以下，較佳為5以下。若Mw/Mn較小，則有醯亞胺交聯型樹脂之耐熱性進一步提高，並且醯亞胺交聯型樹脂中之揮發分量降低之傾向。 再者，於本說明書中，共聚物之數量平均分子量Mn及重量平均分子量Mw表示藉由GPC(Gel Permeation Chromatography，凝膠層析法)測定法而於以下之條件下測得之值。 機器：島津製作所製造之「RID-10A/CBM-20A/DGU-20A3、 LC-20AD/DPD-M20A/CTO-20A」 管柱：東曹公司製造之「TSKgel superHM-N」 檢測器：示差折射率檢測器(RI檢測器/內置) 溶劑：氯仿 溫度：40℃ 流速：0.3 mL/min 注入量：20 μL 濃度：0.1重量% 校準試樣：單分散聚苯乙烯 校準法：聚苯乙烯 (i)環狀烯烴單元 環狀烯烴單元係來自環狀烯烴之結構單元。環狀烯烴係具有環結構、及包含構成環結構之碳原子之碳-碳雙鍵，且可與不飽和二羧酸酐進行聚合之化合物。 環狀烯烴例如可為包含在環內至少具有1個碳-碳雙鍵之環結構之化合物。此種環狀烯烴易於進行與不飽和二羧酸酐之聚合反應。又，根據此種環狀烯烴，由於在共聚物之主鏈中併入有環結構，故而有主鏈之形狀及移動性受到限制，從而可獲得耐熱性及光學特性更優異之醯亞胺交聯型樹脂之傾向。 環狀烯烴所具有之環結構可為單環系，亦可為多環系。作為單環系之環結構，例如，可列舉：環烯烴骨架、環二烯骨架、環三烯骨架等。作為該等環結構，例如，可列舉下述式(1-1)～(1-5)所表示之環結構。 [化1]作為多環系之環結構，可列舉縮合環、橋接環等。作為多環系之環結構，例如，可列舉：降&#158665;烯骨架、降&#158665;二烯骨架、雙環[2.2.2]-2-辛烯骨架、雙環[2.2.2]-2,5-辛二烯骨架、二環戊二烯骨架、二氫二環戊二烯骨架、苊烯骨架、茚骨架、四氫茚骨架、四環[6.2.1.13,6 .02,7 ]-4-十二烯骨架等。作為該等環結構，例如，可列舉下述式(2-1)～(2-11)所表示之環結構。 [化2]環狀烯烴所具有之環結構可具有取代基。又，環結構可與其他環進行縮合，亦可與其他環形成螺環。 作為環狀烯烴，例如，可列舉具有下述式(3-1)～(3-34)所表示之結構之化合物。 [化3]該等環狀烯烴可具有取代基。取代基只要為不阻礙聚合反應之範圍，則並無特別限制。取代基例如可為鹵素原子、烷基、鹵代烷基、烷氧基、芳基、芳烷基、矽烷基、羧基、羥基、胺基、烷氧羰基等。又，亦可進而經其他取代基取代為該等取代基。 作為鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子，其等之中，較佳為氟原子、氯原子或溴原子，更佳為氟原子。 烷基可為直鏈狀、支鏈狀或環狀。烷基之碳數例如可為1～30，較佳為1～10。作為烷基之具體例，可列舉：甲基、乙基、異丙基、第三丁基等。 鹵代烷基係烷基所具有之氫原子之一部分或全部取代為鹵素原子而成之基。作為烷基及鹵素原子，可列舉與上述相同之例。作為鹵代烷基，例如，可列舉：三氟甲基、氯甲基、溴甲基等。 烷氧基係-OR(R表示烷基)所表示之基，作為R之烷基，可列舉與上述相同之例。作為烷氧基，例如，可列舉：甲氧基、乙氧基、異丙氧基、正丙氧基、第三丁氧基等。 芳基係具有自芳香族烴去除一個氫原子而成之結構之基。作為芳基，例如，可列舉：苯基、萘基、蒽基等。 芳烷基係烷基之氫原子之一部分或全部(較佳為1個)取代為芳基而成之基。作為烷基及芳基，可列舉與上述相同之例。作為芳烷基，例如，可列舉：苄基、苯乙基、苯丙基等。 矽烷基係-Si(R')3 (R'表示烷基、芳基或芳烷基)所表示之基，作為R'之烷基、芳基及芳烷基，可列舉與上述相同之例。作為矽烷基，例如，可列舉：三甲基矽烷基、二甲基苯基矽烷基、三乙基矽烷基、二乙基苯基矽烷基等。 烷氧羰基係-COOR(R表示烷基)所表示之基，作為R之烷基，可列舉與上述相同之例。作為烷氧基羰基，例如，可列舉：甲氧基羰基、乙氧基羰基、異丙氧基羰基、第三丁氧基羰基等。 環狀烯烴較佳為不包含除氧、氮及硫以外之雜原子之化合物，更佳為不包含雜原子之烴。 作為環狀烯烴之具體例，例如，可列舉：苊烯、5-乙醯基-2-降&#158665;烯雙環[3.2.1]-2-辛烯、[雙環[2.2.1]-5-庚烯-2-基]三乙氧基矽烷、第三丁基-5-降&#158665;烯-2-羧酸酯、二環戊二烯、5,6-二氫二環戊二烯、5-亞乙基-2-降&#158665;烯、羥基二環戊二烯、2-降&#158665;烯、5-降&#158665;烯-2,3-二羧酸酐、2,5-降&#158665;二烯、5-降&#158665;烯-2,2-二甲醇、5-降&#158665;烯-2-羧酸甲酯、5-降&#158665;烯-2-羧酸酯、5-降&#158665;烯-2,3-二甲醇、順-5-降&#158665;烯-外-2,3-二羧酸酐、5-降&#158665;烯-2-內,3-內-二甲醇、5-降&#158665;烯-2-外,3-外-二甲醇、5-降&#158665;烯-2-基 乙酸酯、5-降&#158665;烯-2-腈、5-降&#158665;烯-2,3-二羧醯亞胺、5-降&#158665;烯-2-甲胺、5-降&#158665;烯-2-甲醇、N-(2-乙基己基)-5-降&#158665;烯-2,3-二羧醯亞胺、3a,4,7,7a-四氫茚、四環[6.2.1.13,6.02,7]-4-十二烯、4-乙烯基-1-環己烯、5-乙烯基雙環[2.2.1]-2-庚烯、三環戊二烯、二甲橋苯并茚、二甲橋茀、α-蒎烯、β-蒎烯、檸檬烯等。 環狀烯烴具有2個以上之碳-碳雙鍵時，碳-碳雙鍵之一部分或全部可藉由聚合反應而發生反應。即，環狀烯烴單元可為環狀烯烴所具有之碳-碳雙鍵之一部分或全部藉由聚合反應發生反應而成之結構單元，亦可為具有將環狀烯烴所具有之碳-碳雙鍵之一部分或全部取代為單鍵而成之結構之結構單元。 環狀烯烴單元較佳為環結構之至少一部分構成共聚物之主鏈。藉此，共聚物之主鏈之形狀及移動性藉由環狀烯烴單元之環結構而被控制，從而可獲得耐熱性及光學特性更優異之醯亞胺交聯型樹脂。 (ii)不飽和二羧酸酐單元 不飽和二羧酸酐單元係來自不飽和二羧酸酐之結構單元。不飽和二羧酸酐係具有碳-碳雙鍵及2個羧基之不飽和二羧酸藉由分子內脫水而形成酸酐而成之化合物。 作為不飽和二羧酸酐，例如，可列舉：順丁烯二酸酐、甲基順丁烯二酸酐、亞甲基丁二酸酐、2,3-二甲基順丁烯二酸酐、2-(2-羧基乙基)-3-甲基順丁烯二酸酐、3,4,5,6-四氫鄰苯二甲酸酐、苯基順丁烯二酸酐、2,3-二苯基順丁烯二酸酐、烯丙基丁二酸酐、(2-甲基-2-丙烯基)丁二酸酐、2-丁烯-1-基丁二酸酐、順-4-環己烯-1,2-二羧酸酐、5-降&#158665;烯-2,3-二羧酸酐、雙環[2.2.2]-5-辛烯-2,3-二羧酸酐等。 不飽和二羧酸酐例如可為具有下述式(4-1)所表示之結構之化合物。 [化4]式中，R1 表示氫原子、鹵素原子、烷基、鹵代烷基或芳基，2個R1 可相互相同，亦可相互不同。 若不飽和二羧酸酐為具有式(4-1)所表示之結構之化合物，則共聚物之主鏈之形狀及移動性藉由來自不飽和二羧酸酐之環結構而被控制，故而可獲得耐熱性及光學特性更優異之醯亞胺交聯型樹脂。 作為R1 之鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子。鹵素原子較佳為氟原子、氯原子或溴原子，更佳為氟原子。 R1 之烷基可為直鏈狀、支鏈狀或環狀。烷基之碳數例如可為1～30，較佳為1～10。作為烷基之具體例，可列舉：甲基、乙基、異丙基、第三丁基等。 R1 之鹵代烷基係烷基所具有之氫原子之一部分或全部取代為鹵素原子而成之基。作為烷基及鹵素原子，可列舉與上述相同之例。作為鹵代烷基，例如，可列舉：三氟甲基、氯甲基、溴甲基等。 作為R1 之芳基，例如，可列舉：苯基、萘基、蒽基等。 R1 較佳為氫原子、烷基或鹵代烷基，更佳為氫原子或烷基。又，就與環狀烯烴之反應性優異，且共聚物之製造變得容易之觀點而言，較佳為R1 之中至少1個為氫原子。 不飽和二羧酸酐單元例如可具有丁二酸酐所具有之除氫原子之一部分或全部以外之結構。 不飽和二羧酸酐為具有式(4-1)所表示之結構之化合物時，不飽和二羧酸酐單元可為具有下述式(4-2)所表示之結構之結構單元。再者，式中，R1 與上述為同義。 [化5](iii)順丁烯二醯亞胺系單元 本實施形態中之共聚物亦可進而具有來自順丁烯二醯亞胺系化合物之結構單元(順丁烯二醯亞胺系單元)。順丁烯二醯亞胺系化合物係例如具有下述式(5-1)所表示之結構之化合物，順丁烯二醯亞胺系單元係例如具有下述式(5-2)所表示之結構之結構單元。 [化6][化7]式中，R2 表示氫原子、鹵素原子、烷基、鹵代烷基或芳基，2個R2 可相互相同，亦可相互不同。R3 表示一價之基。 作為R2 之鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子。鹵素原子較佳為氟原子、氯原子或溴原子，更佳為氟原子。 R2 之烷基可為直鏈狀、支鏈狀或環狀。烷基之碳數例如可為1～30，較佳為1～10。作為烷基之具體例，可列舉：甲基、乙基、異丙基、第三丁基等。 R2 之鹵代烷基係烷基所具有之氫原子之一部分或全部取代為鹵素原子而成之基。作為烷基及鹵素原子，可列舉與上述相同之例。作為鹵代烷基，例如，可列舉：三氟甲基、氯甲基、溴甲基等。 作為R2 之芳基，例如，可列舉：苯基、萘基、蒽基等。 R2 較佳為氫原子、烷基或鹵代烷基，更佳為氫原子或烷基。又，就與環狀烯烴及不飽和二羧酸酐之反應性優異，且共聚物之製造變得容易之觀點而言，較佳為R2 之中至少1個為氫原子。 R3 之一價之基只要為不阻礙與環狀烯烴之聚合反應之範圍，則並無特別限制。作為R3 之一價之基，例如，可列舉：烷基、鹵代烷基、芳基、烷氧基羰基、芳烷基、矽烷基等。一價之基亦可進而具有取代基，作為該取代基，例如，可列舉：鹵素原子、烷基、芳基、胺基、烷氧基、芳氧基、烷硫基、芳硫基、矽烷基等。 作為烷基、鹵代烷基、芳基、芳烷基、烷氧基、烷氧基羰基及矽烷基，可列舉與上述相同之例。 烷硫基係-SR(R表示烷基)所表示之基，作為R之烷基，可列舉與上述相同之例。作為烷硫基，例如，可列舉：甲硫基、乙硫基、丙硫基等。 芳氧基及芳硫基分別係-OR"及-SR"(R"表示芳基)所表示之基，作為R"之芳基，可列舉與上述相同之例。作為芳氧基，例如，可列舉：苯氧基、萘氧基等，作為芳硫基，例如，可列舉：苯硫基、萘硫基等。 (iv)其他結構單元 本實施形態中之共聚物亦可進而具有除上述以外之結構單元。例如，共聚物亦可進而具有來自具有2個順丁烯二醯亞胺基之雙順丁烯二醯亞胺系化合物之結構單元。 作為雙順丁烯二醯亞胺系化合物，例如，可列舉：4,4'-雙順丁烯二醯亞胺二苯甲烷、1,6-雙(順丁烯二醯亞胺)己烷、雙(3-乙基-5-甲基-4-順丁烯二醯亞胺苯基)甲烷、1,4-雙(順丁烯二醯亞胺)丁烷、2,2-雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]丙烷、1,2-雙(順丁烯二醯亞胺)乙烷、N,N'-1,4-伸苯基二順丁烯二醯亞胺、N,N'-1,3-伸苯基二順丁烯二醯亞胺等。 又，共聚物亦可進而具有來自可與不飽和二羧酸酐或順丁烯二醯亞胺系化合物交替共聚之烯烴化合物之結構單元。 作為烯烴化合物，例如，可列舉：苯乙烯、茚、α-甲基苯乙烯、對甲基苯乙烯等苯乙烯衍生物；乙基乙烯醚、正丙基乙烯醚、異丙基乙烯醚、正丁基乙烯醚、異丁基乙烯醚、2-乙基己基乙烯醚、環己基乙烯醚等烷基單乙烯醚衍生物等。 本實施形態中之共聚物例如可藉由包含環狀烯烴及不飽和二羧酸酐之單體成分之聚合反應而獲得。單體成分可進而包含順丁烯二醯亞胺系化合物，亦可進而包含其他單體。 聚合反應之形態並無特別限定，例如可為自由基聚合。 聚合反應為自由基聚合時，作為聚合起始劑，可使用公知之自由基聚合起始劑。作為自由基聚合起始劑，例如，可列舉：偶氮二異丁腈(AIBN，azobisisobutyronitrile)、二第三丁基過氧化物、第三丁基過氧化氫、過氧化苯甲醯(BPO，Benzoyl peroxide)、甲基乙基酮過氧化物、氧化還原起始劑(過氧化氫與鐵(II)鹽、過硫酸鹽與亞硫酸氫鈉等)、三乙基硼烷(Et3 B)、二乙基鋅(Et2 Zn)等。又，亦可使用原子轉移自由基聚合(ATRP，Atom Transfer Radical Polymerization)、可逆加成-裂解鏈轉移聚合(RAFT，Reversible Addition-Fragmentation Chain Transfer Polymerization)、經由氮氧化物之聚合(NMP，Nitroxide Mediated Polymerization)等活性自由基聚合、精密自由基聚合等方法。 關於自由基聚合起始劑之使用量，例如，以單體成分之總量為基準，可為0.1～10 mol%，較佳為1～5 mol%。 聚合反應較佳為於溶劑中實施。作為溶劑，例如，可較佳地使用四氫呋喃(THF、tetrahydrofuran)、二㗁烷、二氧雜環戊烷、丙酮、氯仿、甲苯、二甲基甲醯胺(DMF，dimethylformamide)、二甲基乙醯胺(DMAc，dimethyl acetamide)、N-甲基吡咯啶酮(NMP，N-Methylpyrrolidone)、二甲基亞碸(DMSO，dimethyl sulfoxide)、γ-丁內酯、環戊酮、環己酮、四甲脲、1,3-二甲基-2-咪唑啶酮、二乙二醇二甲醚等乙二醇二甲醚系溶劑、乙基溶纖劑等溶纖劑系溶劑、丙二醇單甲醚乙酸酯等二醇酯系溶劑、丙二醇單甲醚等二醇醚系溶劑等。 聚合反應之條件並無特別限定，例如反應溫度可為-20～200℃，反應時間可為0.1～100小時。 ＜交聯體＞ 本實施形態之醯亞胺交聯型樹脂係利用二胺將上述共聚物交聯而成之交聯體，其具有藉由共聚物中之酸酐與二胺之反應而形成之醯亞胺鍵。 於本實施形態中，共聚物中之不飽和二羧酸酐單元之中一部分或全部可與二胺發生反應而形成醯亞胺鍵。以共聚物中之不飽和二羧酸酐單元之總量為基準，殘留於醯亞胺交聯型樹脂中之不飽和二羧酸酐單元之量較佳為90 mol%以下，更佳為70 mol%以下，進而較佳為50 mol%以下。 二胺只要為具有2個可與共聚物中之酸酐發生反應而形成醯亞胺鍵之胺基之化合物即可。 作為二胺，可列舉：芳香族二胺、脂肪族二胺等。於本說明書中，芳香族二胺表示具有2個鍵結於芳香環之胺基之化合物，脂肪族二胺表示具有2個鍵結於sp3 碳之胺基之化合物。又，二胺亦可為具有鍵結於芳香環之胺基及鍵結於sp3 碳之胺基之化合物。 作為芳香族二胺，例如，可列舉具有下述式(6-1)～(6-4)所表示之結構之化合物。 [化8]式中，Q1 表示二價之基。 該等芳香族二胺亦可具有取代基。取代基只要為不阻礙交聯反應之範圍，則並無特別限制。取代基例如可為鹵素原子、烷基、鹵代烷基、芳基、磺基、烷氧基、芳氧基、矽烷基、羥基、硫醇基、烷硫基、芳硫基、腈基、酮基、羧基等。又，亦可進而經其他取代基取代為該等取代基。 作為鹵素原子、烷基、鹵代烷基、芳基、烷氧基、芳氧基、矽烷基、烷硫基、芳硫基，可列舉與上述相同之例。 酮基係-COR'(R'表示烷基、芳基或芳烷基)所表示之基，作為R'之烷基、芳基及芳烷基，可列舉與上述相同之例。作為酮基，例如，可列舉：甲基羰基、苯基羰基、苄基羰基等。 Q1 中之二價之基只要為不阻礙交聯反應之範圍，則並無特別限制。作為二價之基之具體例，可列舉：-O-、-S-、-CH2 -、-SO2 -、-CO-、-O-C6 H4 -O-、-NHCO-、-O-C6 H4 -C(Me)2 -C6 H4 -O-、-O-C6 H4 -C(CF3 )2 -C6 H4 -O-、-C(Me)2 -C6 H4 -C(Me)2 -、-O-C6 H4 -C6 H4 -O-、-O-C6 H4 -SO2 -C6 H4 -O-、-C6 H4 -、-NHCO-C6 H4 -CONH-、-CONH-C6 H4 -NHCO-、-(Si(OMe)2 -O)n -、-(Si(OEt)2 -O)n -、-(Si(OPh)2 -O)x -等。再者，x表示1以上之整數，較佳為1～100之整數。 作為脂肪族二胺，例如，可列舉具有下述式(7-1)～(7-7)所表示之結構之化合物。 [化9]式中，Q2 表示二價之基。 該等脂肪族二胺亦可具有取代基。取代基只要為不阻礙交聯反應之範圍，則並無特別限制。取代基例如可為鹵素原子、烷基、鹵代烷基、芳基、磺基、烷氧基、芳氧基、矽烷基、羥基、硫醇基、烷硫基、芳硫基、腈基、酮基、羧基等。又，亦可進而經其他取代基取代為該等取代基。作為該等基之例，可列舉與上述相同之例。 Q2 中之二價之基只要為不阻礙交聯反應之範圍，則並無特別限制。作為二價之基之具體例，可列舉：-O-、-S-、-CH2 -、-SO2 -、-CO-、-O-C6 H4 -O-、-NHCO-、-O-C6 H4 -C(Me)2 -C6 H4 -O-、-O-C6 H4 -C(CF3 )2 -C6 H4 -O-、-C(Me)2 -C6 H4 -C(Me)2 -、-O-C6 H4 -C6 H4 -O-、-O-C6 H4 -SO2 -C6 H4 -O-、-C6 H4 -、-NHCO-C6 H4 -CONH-、-CONH-C6 H4 -NHCO-、-(Si(OMe)2 -O)n -、-(Si(OEt)2 -O)n -、-(Si(OPh)2 -O)x -、9,9-亞茀基等。再者，x表示1以上之整數，較佳為1～100之整數。 又，二胺例如可為將胺基導入至聚矽氧烷之末端或側鏈而成之聚矽氧烷系二胺。聚矽氧烷系二胺之分子量例如可為100～100000，亦可為200～50000。 作為二胺之具體例，可列舉：1,4-苯二胺、1,3-苯二胺、1,2-苯二胺、4,4'-伸乙基二苯胺、2,2'-伸乙基二苯胺、3,3'-二胺基二苯乙烷、4,4'-二胺基聯苯、3,3'-二胺基聯苯、2,2'-二胺基聯苯、3,4'-二胺基聯苯、4,4'-二胺基-2,2'-二甲基聯苯、4,4'-二胺基-3,3'-二甲基聯苯、4,4'-二胺基八氟聯苯、2,5-二甲基-1,4-苯二胺、2,3,5,6-四氟-1,4-苯二胺、2,3,5,6-四甲基-1,4-苯二胺、2,4,5,6-四氟-1,3-苯二胺、1,3,5-三(4-胺基苯基)苯、2,5-二氯-1,4-苯二胺、2,6-二溴-1,4-苯二胺、2,7-二胺基茀、1,5-二胺基萘、1,4-二胺基萘、2,6-二胺基萘、1,3-二胺基芘、1,6-二胺基芘、1,8-二胺基芘、3,3'-二胺基二苯甲烷、3,4'-二胺基二苯甲烷、4,4'-二胺基二苯甲烷、4,4'-二胺基-3,3'-二甲基二苯甲烷、4,4'-亞甲基雙(2-氯苯胺)、4,4'-亞甲基雙(2-乙基-6-甲基苯胺)、4,4'-亞甲基雙(2,6-二乙基苯胺)、4,4"-二胺基-對聯三苯、α,α'-雙(4-胺基苯基)-1,4-二異丙基苯、1,1-雙(4-胺基苯基)環己烷、1,3-雙[2-(4-胺基苯基)-2-丙基]苯、4,4'-二胺基-2,2'-二甲基聯苄、鄰聯甲苯胺、間聯甲苯胺、3,3'-二乙基聯苯胺、3,3',5,5'-四甲基聯苯胺、2,2',5,5'-四氯聯苯胺、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、3,3'-二羥基聯苯胺、1,5-雙(4-胺基苯氧基)戊烷、3,3'-二胺基聯苯胺、鄰二甲氧苯胺、9,9-雙(4-胺基苯基)茀、9,9-雙(4-胺基-3-氯苯基)茀、9,9-雙(4-胺基-3-氟苯基)茀、9,9-雙(4-胺基-3-甲基苯基)茀、9,9-雙(3-胺基-4-羥基苯基)茀、2,7-二胺基-9,9-二正辛基茀、2,2-雙(3-胺基-4-羥基苯基)丙烷、4,6-二胺基間苯二酚、2,5-二胺基-1,4-苯二硫醇、4,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲酮、3,3'-二胺基二苯醚、3,4'-二胺基二苯醚、4,4'-二胺基二苯醚、1,4-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-[1,3-伸苯基雙(1-甲基-亞乙基)]雙苯胺、4,4'-[1,4-伸苯基雙(1-甲基-亞乙基)]雙苯胺、4,4'-雙(4-胺基苯氧基)聯苯、1,4-雙(4-胺基-2-三氟甲基苯氧基)苯、4,4'-二胺基二苯胺、4,4'-二胺基苯甲醯苯胺、3,4'-二胺基苯甲醯苯胺、雙(2-胺基苯基)硫醚、雙(4-胺基苯基)硫醚、4,4'-二硫代二苯胺、2,2'-二硫代二苯胺、3,3'-二胺基二苯基碸、4,4'-二胺基二苯基碸、2,2'-聯苯胺二磺酸、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸、雙(3-胺基-4-羥基苯基)碸、3,7-二胺基-2,8-二甲基二苯并噻吩碸、2,2-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙(3-胺基苯基)六氟丙烷、2,2-雙(3-胺基-4-羥基苯基)六氟丙烷、2,2'-雙(三氟甲基)聯苯胺、4,4'-二胺基二苯乙烯、3,6-二胺基咔唑、2,6-二胺基蒽醌、3,9-雙[2-(3,5-二胺基-2,4,6-三氮雜苯基)乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、苯胍胺、2,4-二胺基-6-甲基-1,3,5-三&#134116;、2,4-二胺基-6-二甲基胺基-1,3,5-三&#134116;、2,4-二胺基-6-[2-(2-甲基-1-咪唑)乙基]-1,3,5-三&#134116;、2,4-二胺基-6-[2-(2-十一烷基-1-咪唑)乙基]-1,3,5-三&#134116;、2,2'-二胺基-4,4'-聯噻唑、乙二胺、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷、2-甲基-1,3-丙二胺、2,2-二甲基-1,3-丙二胺、1,2-二胺基-2-甲基丙烷、2,3-二甲基-2,3-丁二胺、2-甲基-1,5-二胺基戊烷、2,2'-氧基雙(乙基胺)、1,2-雙(2-胺基乙氧基)乙烷、1,4-丁二醇雙(3-胺基丙基)醚、二乙二醇雙(3-胺基丙基)醚、1,14-二胺基-3,6,9,12-四氧雜十四烷、二伸乙基三胺、三伸乙基四胺、3,3'-二胺基二丙基胺、2,2'-二胺基-N-甲基二乙基胺、3,3'-二胺基-N-甲基二丙基胺、N,N'-雙(2-胺基乙基)-1,3-丙二胺、N,N'-雙(3-胺基丙基)乙二胺、N,N'-雙(3-胺基丙基)-1,4-丁二胺、2,2'-硫代雙(乙基胺)、間苯二甲胺、對苯二甲胺、順-1,3-雙(胺基甲基)環己烷、1,3-雙(3-胺基丙基)四甲基二矽氧烷、信越化學製造之胺基改性聚矽氧油(例如，X-22-1660B-3(Mw：4400)、X-22-161B(Mw：3000)、X-22-161A(Mw：1600)、X-22-9409(Mw：1340)等)、Gelest公司製造之二甲基矽氧烷型二胺(例如，DMS-A11、DMS-A12、DMS-A15、DMS-A21、DMS-A31、DMS-A32、DMS-A35等)、1,3-環己二胺、1,4-環己二胺、順-1,3-環己二胺、反-1,3-環己二胺、順-1,4-環己二胺、反-1,4-環己二胺、4,4'-亞甲基雙(2-甲基環己基胺)、1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、4,4'-亞甲基雙(環己基胺)、雙(胺基甲基)降&#158665;烷、異佛爾酮二胺、3(4),8(9)-雙(胺基甲基)三環[5.2.1.02,6 ]癸烷、3-胺基苄胺、4-胺基苄胺等。 共聚物與二胺之交聯反應例如可藉由使共聚物與二胺發生反應而形成聚醯胺酸之第一步驟、及利用聚醯胺酸之脫水反應形成醯亞胺鍵之第二步驟而實施。 第一步驟例如可為使共聚物與二胺於溶劑中發生反應而獲得聚醯胺酸之步驟。反應溫度例如可為-20～200℃，反應時間例如可為0.1～100小時。 第一步驟中所使用之溶劑只要為可將共聚物及二胺溶解之溶劑即可。又，溶劑較佳為可將所生成之聚醯胺酸溶解之溶劑。作為溶劑，例如，可較佳地使用二甲基乙醯胺(DMAc)、N-甲基吡咯啶酮(NMP)、γ-丁內酯、N,N-二甲基甲醯胺(DMF)、二甲基亞碸(DMSO)、四氫呋喃(THF)、四甲脲、1,3-二甲基-2-咪唑啶酮、苯酚、對氯酚、吡啶、環戊酮、環己酮等。 關於與共聚物發生反應之二胺之量，例如，以共聚物中之不飽和二羧酸酐單元之含量為基準，可為0.05當量以上，更佳為0.5當量以上。又，關於二胺之量，例如，以共聚物中之不飽和二羧酸酐單元之含量為基準，可為1.5當量以下，更佳為1.0當量以下。 於第一步驟中，可獲得包含聚醯胺酸之反應液。於一態樣中，可將聚醯胺酸自該反應液回收，並將所回收之聚醯胺酸供第二步驟使用。又，於另一態樣中，可將該反應液塗佈於基板上而形成聚醯胺酸之塗膜之後，實施第二步驟。 於第二步驟中，藉由聚醯胺酸之脫水反應而形成醯亞胺鍵，從而獲得醯亞胺交聯型樹脂。 脫水反應例如可藉由對聚醯胺酸進行加熱而實施。脫水反應之反應溫度例如可為100～400℃，反應時間例如可為0.1～100小時。 再者，交聯反應之態樣並不限定於如上所述者。例如，交聯反應可為使用脫水觸媒使共聚物與二胺發生反應，而於一階段形成醯亞胺鍵之反應。作為脫水觸媒，例如，可列舉：吡啶、2-羥基吡啶、三乙胺、咪唑、N-甲基哌啶等。又，交聯反應可在將所產生之水捕獲之脫水劑之存在下進行，作為脫水劑，例如，可列舉：乙酸酐、丙酸酐、三氟乙酸酐等。 本實施形態之醯亞胺交聯型樹脂具有藉由共聚物中之酸酐與二胺中之胺基之反應而形成之醯亞胺鍵。本實施形態之醯亞胺交聯型樹脂藉由在分子內具備來自環狀烯烴之環結構及經由醯亞胺鍵之交聯結構，而具有充分之透光性及良好之耐熱性。因此，本實施形態之醯亞胺交聯型樹脂可較佳地用作表面保護膜用之樹脂材料。 (透明膜) 本實施形態之透明膜包含上述醯亞胺交聯型樹脂。本實施形態之透明膜例如可較佳地用作表面保護膜用之膜基材。再者，於本說明書中，透明膜係表示可見光透過率(T450 nm )為60%以上之膜。 透明膜之可見光透過率(T450 nm )較佳為80%以上，更佳為85%以上。 透明膜之厚度並無特別限定，例如可為1 μm以上，亦可為10 μm以上，可為500 μm以下，亦可為1000 μm以下。 透明膜亦可進而含有除醯亞胺交聯型樹脂以外之成分。例如，透明膜亦可進而含有抗氧化劑、光穩定劑、抗靜電劑、潤滑劑、阻燃劑、塑化劑、透明化劑、成核劑、填充劑等。 以下，對透明膜之製造方法之較佳之一態樣進行說明。 本態樣之透明膜之製造方法可具備：準備步驟，其係準備含有作為共聚物與二胺之反應物之聚醯胺酸之塗佈液者；塗佈步驟，其係將塗佈液塗佈於基板上，而形成含有聚醯胺酸之塗膜者；及加熱步驟，其係對塗膜進行加熱，而獲得含有醯亞胺交聯型樹脂之透明膜者。 於準備步驟中，例如，可使共聚物與二胺於溶劑中發生反應，而獲得含有聚醯胺酸之反應液，並將該反應液作為塗佈液。又，亦可將聚醯胺酸自反應液回收，並使所回收之聚醯胺酸溶解於溶劑中而獲得塗佈液。 於塗佈步驟中，將塗佈液塗佈於基板上而形成塗膜。塗佈方法並無特別限定，可使用公知之塗佈方法(例如，旋轉塗佈法、棒式塗佈法、狹縫法、模嘴塗佈法等)。 於塗佈步驟中，可於塗佈液之塗佈後將溶劑去除。溶劑之去除方法並無特別限定，可使用公知之去除方法(例如，減壓下之加熱、常壓下之加熱、利用加熱板之加熱、熱氣流下之加熱、氣流下之乾燥、遠紅外線加熱等)。 基板並無特別限定，只要為具有可形成具有所需之形狀之塗膜之表面者即可。作為基板，例如，可較佳地使用：玻璃基板；銅、鋁等金屬箔基板；鋼、不鏽鋼等金屬帶基板；聚四氟乙烯、PPS(Polyphenylene Sulfite，聚苯硫)、PET(Polyethylene Terephthalate，聚對苯二甲酸乙二酯)、丙烯酸樹脂、聚乙烯、聚丙烯、聚苯乙烯等樹脂片材基板等。 於加熱步驟中，對塗膜進行加熱而使聚醯胺酸之脫水反應進行，從而獲得含有醯亞胺交聯型樹脂之透明膜。加熱溫度只要為聚醯胺酸之脫水反應進行之溫度即可，例如可為100～400℃，較佳為200～300℃。加熱時間例如可為0.1～100小時，較佳為1～10小時。 (表面保護膜) 本實施形態之表面保護膜具備：上述透明膜；及金屬蒸鍍層，其設置於透明膜之至少一個面上。上述透明膜含有醯亞胺交聯型樹脂，耐熱性優異。因此，於本實施形態中，獲得即便於使金屬於透明膜上蒸鍍之情形時亦充分地抑制由透明膜之熱所導致之膨脹、變形等，且具有良好之透光性之表面保護膜。 金屬蒸鍍層係於透明膜上藉由蒸鍍而形成之金屬薄層。金屬例如可為鋁、矽等，亦可為其等之金屬氧化物。蒸鍍方法並無特別限定，可使用公知之蒸鍍方法。 金屬蒸鍍層之厚度例如可為1～1000 nm，亦可為100～500 nm。 本實施形態之表面保護膜例如可為了攜帶型資訊終端之顯示器、觸控面板、電腦用顯示器、電視用顯示器、數位標牌等之表面保護而較佳地使用。 以上，對本發明之較佳之實施形態進行了說明，但本發明並不受到上述實施形態限定。 [實施例] 以下，藉由實施例而對本發明更具體地進行說明，但本發明並不受到實施例限定。 [實施例1] (1)共聚物(A-1)之合成 藉由降&#158665;烯與順丁烯二酸酐之交替共聚，而獲得共聚物(A-1)。降&#158665;烯與順丁烯二酸酐之添加比係設為1：1(莫耳比)，聚合反應係於四氫呋喃(THF)中，將偶氮二異丁腈(AIBN)作為自由基聚合起始劑，於室溫、24小時之條件下進行。關於AIBN之使用量，相對於單體成分之總量，設為1.9 mol%。 [化10]更具體而言，將降&#158665;烯2000 mg及順丁烯二酸酐2080 mg溶解於3 mL之THF中，並添加60 mg之AIBN作為自由基聚合起始劑，於60℃進行24小時之反應。經過對二乙醚之再沈澱精製，而以白色粉末之形式獲得2650 mg之共聚物(A-1)。 所獲得之共聚物(A-1)之數量平均分子量Mn為4.8×103 ，分子量分佈Mw/Mn為1.7。再者，數量平均分子量Mn及分子量分佈Mw/Mn係利用以下之方法進行測定。 ＜數量平均分子量Mn及重量平均分子量Mw之測定＞ 藉由GPC測定法，於以下之條件下測定數量平均分子量Mn及重量平均分子量Mw。 機器：島津製作所製造之「RID-10A/CBM-20A/DGU-20A3、 LC-20AD/DPD-M20A/CTO-20A」 管柱：東曹公司製造之「TSKgel superHM-N」 檢測器：示差折射率檢測器(RI檢測器/內置) 溶劑：氯仿 溫度：40℃ 流速：0.3 mL/min 注入量：20 μL 濃度：0.1重量% 校準試樣：單分散聚苯乙烯 校準法：聚苯乙烯 (2)醯亞胺交聯型樹脂(A-1-1)之製造 於共聚物(A-1)之二甲基乙醯胺溶液(濃度100 mg/mL)1 mL中添加二胺之二甲基乙醯胺溶液(濃度25 mg/mL)1 mL，並於室溫攪拌20小時而使其發生反應，從而獲得含有聚醯胺酸之塗佈液。作為二胺，使用4,4'-二胺基二苯醚，關於二胺之添加量，相對於共聚物中之順丁烯二酸酐單元，設為1當量(即，相對於順丁烯二酸酐單元1莫耳，二胺為0.5莫耳)。 繼而，將所獲得之塗佈液500 μL滴注至250 mm見方之玻璃基板，並於100℃使其乾燥1小時而獲得獨立膜。藉由於1 mmHg之真空下，於200℃將所獲得之獨立膜加熱24小時，而使聚醯胺酸醯亞胺化，從而獲得包含醯亞胺交聯型樹脂(A-1-1)之透明膜。 對於所獲得之醯亞胺交聯型樹脂(A-1-1)，利用以下之方法測定10%重量損失溫度(T10 )。其結果為，T10 為386℃，確認到較高之耐熱性。又，利用以下之方法對透明膜之可見光透過率(T450 nm )進行測定之結果為，T450 nm 為82%。進而，利用以下之方法對鉛筆硬度進行測定之結果為，所獲得之透明膜之鉛筆硬度為2H。 ＜10%重量損失溫度之測定方法＞ 利用熱重量分析裝置(股份有限公司RIGAKU製造之「Thermo plus Evo TG8120」)測定10%重量損失溫度。其係藉由如下方法而求出：一面於氮氣氛圍下使氮氣流動，一面將掃描溫度設定為30℃～500℃，於升溫速度10℃/min之條件下進行加熱，並測定所使用之試樣之重量損失10%之溫度。 ＜透光率之測定方法＞ 利用分光光度計Jasco V-670 spectrophotometer作為測定裝置，測定對於波長280～800 nm之光之試樣之透過率，求出對於波長450 nm之光之透過率。 ＜鉛筆硬度試驗＞ 使用HEIDON新東科學股份有限公司製造之連續負荷式表面性測定機TRIBOGEAR TYPE-22作為測定裝置而進行自動測定。 [實施例2] (1)醯亞胺交聯型樹脂(A-1-2)之製造 除了使用2,2'-雙(三氟甲基)聯苯胺之DMAc溶液(濃度25 mg/mL)1.6 mL作為二胺以外，利用與實施例1同樣之方法製造包含醯亞胺交聯型樹脂(A-1-2)之透明膜。 醯亞胺交聯型樹脂(A-1-2)之T10 為379℃，透明膜之T450 nm 為74%。 [實施例3] (1)醯亞胺交聯型樹脂(A-1-3)之製造 除了使用3(4),8(9)-雙(胺基甲基)三環[5.2.1.02,6 ]癸烷之DMAc溶液(濃度25 mg/mL)1 mL作為二胺以外，利用與實施例1同樣之方法製造包含醯亞胺交聯型樹脂(A-1-3)之透明膜。 關於醯亞胺交聯型樹脂(A-1-3)之T10 及透明膜之T450 nm ，均表示與實施例2大致同等之值。 [實施例4] (1)醯亞胺交聯型樹脂(A-1-4)之製造 於共聚物(A-1)之THF溶液(濃度100 mg/mL)1 mL中添加Gelest公司製造之DMS-A12(胺基丙基末端二甲基矽氧烷，分子量900～1000)之THF溶液(濃度37 mg/mL)1 mL，並於室溫攪拌20小時而使其發生反應，從而獲得含有聚醯胺酸之塗佈液。再者，二胺之添加量係設為約0.45當量。 繼而，將所獲得之塗佈液1 mL滴注至底面為2 cm見方之鐵氟龍(註冊商標)盤中，並於室溫使其乾燥1小時而獲得獨立膜。藉由於1 mmHg之真空下，於200℃將所獲得之獨立膜加熱24小時，而使聚醯胺酸醯亞胺化，從而獲得包含醯亞胺交聯型樹脂(A-1-4)之透明膜。 醯亞胺交聯型樹脂(A-1-4)之T10 為352℃，透明膜之T450 nm 為97%。又，對鉛筆硬度進行測定結果為F～H。 [實施例5] (1)醯亞胺交聯型樹脂(A-1-5)之製造 於共聚物(A-1)之THF溶液(濃度100 mg/mL)1 mL中添加信越化學工業之胺基改性聚矽氧油 X-22-9409(胺基苯基末端二甲基矽氧烷，分子量1340)之THF溶液(濃度57 mg/mL)1 mL，並於室溫攪拌20小時而使其發生反應，從而獲得含有聚醯胺酸之塗佈液。再者，二胺之添加量係設為約0.3當量。 繼而，將所獲得之塗佈液1 mL滴注至底面為2 cm見方之鐵氟龍(註冊商標)盤中，並於室溫使其乾燥1小時而獲得獨立膜。藉由於1 mmHg之真空下，於200℃將所獲得之獨立膜加熱24小時，而使聚醯胺酸醯亞胺化，從而獲得包含醯亞胺交聯型樹脂(A-1-5)之透明膜。 醯亞胺交聯型樹脂(A-1-5)之T10 為359℃，透明膜之T450 nm 為84%。 [實施例6] (1)共聚物(A-2)之合成 藉由降&#158665;烯、順丁烯二酸酐、及N-乙基順丁烯二醯亞胺之共聚合，而獲得共聚物(A-2)。降&#158665;烯、順丁烯二酸酐、N-乙基順丁烯二醯亞胺之添加比係設為3：1：2。聚合反應係於THF中，將AIBN作為自由基聚合起始劑，於室溫、24小時之條件下進行。關於AIBN之使用量，相對於單體成分之總量，設為1.6 mol%。 [化11]更具體而言，將降&#158665;烯2000 mg、順丁烯二酸酐710 mg、及N-乙基順丁烯二醯亞胺1780 mg溶解於3 mL之THF中，並添加60 mg之AIBN作為自由基聚合起始劑，於60℃進行24小時之反應。經過對二乙醚之再沈澱精製，而以白色粉末之形式獲得3340 mg之共聚物(A-2)。 所獲得之共聚物(A-2)之數量平均分子量Mn為4.7×103 ，分子量分佈Mw/Mn為1.7。 (2)醯亞胺交聯型樹脂(A-2-1)之製造 於共聚物(A-2)之γ-丁內酯溶液(濃度100 mg/mL)1 mL中添加二胺之γ-丁內酯溶液(濃度25 mg/mL)1 mL，並於室溫攪拌20小時而使其發生反應，從而獲得含有聚醯胺酸之塗佈液。作為二胺，使用4,4'-二胺基二苯醚，關於二胺之添加量，相對於共聚物中之順丁烯二酸酐單元，設為0.5當量。 繼而，將所獲得之塗佈液500 μm滴注至250 mm見方之玻璃基板，並於130℃使其乾燥1小時而獲得獨立膜。藉由於1 mmHg之真空下，於200℃將所獲得之獨立膜加熱24小時，而使聚醯胺酸醯亞胺化，從而獲得包含醯亞胺交聯型樹脂(A-2-1)之透明膜。 醯亞胺交聯型樹脂(A-2-1)之T10 為385℃，透明膜之T450 nm 為81%。 將所獲得之透明膜剪切為7 mm×25 mm而製作試片，而進行動態黏彈性試驗。其結果為，試片之儲存模數為2.1 GPa，Tg為299℃，確認到具有較高之熱穩定性及機械強度。 [實施例7] (1)醯亞胺交聯型樹脂(A-2-2)之製造 於共聚物(A-2)之DMF溶液(濃度100 mg/mL)1 mL中添加4,4'-亞甲基雙(環己基胺)之DMF溶液(濃度10 mg/mL)1 mL，並於室溫攪拌20小時而使其發生反應，從而獲得含有聚醯胺酸之塗佈液。再者，二胺之添加量係設為約0.4當量。 繼而，將所獲得之塗佈液1 mL滴注至底面為2 cm見方之鐵氟龍(註冊商標)盤中，並於室溫使其乾燥1小時而獲得獨立膜。藉由於1 mmHg之真空下，於200℃將所獲得之獨立膜加熱24小時，而使聚醯胺酸醯亞胺化，從而獲得包含醯亞胺交聯型樹脂(A-2-2)之透明膜。 醯亞胺交聯型樹脂(A-2-2)之T10 為386℃，透明膜之T450 nm 為82%。 [實施例8] (1)醯亞胺交聯型樹脂(A-2-3)之製造 於共聚物(A-2)之γ-丁內酯溶液(濃度100 mg/mL)1 mL中添加4,4'-亞甲基雙(2-甲基環己基胺)之γ-丁內酯溶液(濃度12 mg/mL)1 mL，並於室溫攪拌20小時而使其發生反應，從而獲得含有聚醯胺酸之塗佈液。再者，二胺之添加量係設為約0.4當量。 繼而，將所獲得之塗佈液1 mL滴注至底面為2 cm見方之鐵氟龍(註冊商標)盤中，並於室溫使其乾燥1小時而獲得獨立膜。藉由於1 mmHg之真空下，於200℃將所獲得之獨立膜加熱24小時，而使聚醯胺酸醯亞胺化，從而獲得包含醯亞胺交聯型樹脂(A-2-3)之透明膜。 醯亞胺交聯型樹脂(A-2-3)之Tg為299℃，儲存模數為2.1 GPa，T10 為385℃，透明膜之T450 nm 為81%。 [實施例9] (1)醯亞胺交聯型樹脂(A-2-4)之製造 於共聚物(A-2)之DMF溶液(濃度100 mg/mL)1 mL中添加4,4'-亞甲基雙(環己基胺)之DMF溶液(濃度10 mg/mL)1 mL、Gelest公司製造之DMS-A12之DMF溶液(濃度16 mg/mL)1 mL，並於室溫攪拌20小時而使其發生反應，從而獲得含有聚醯胺酸之塗佈液。再者，二胺之添加量係設為約0.53當量。 繼而，將所獲得之塗佈液1 mL滴注至底面為2 cm見方之鐵氟龍(註冊商標)盤中，並於室溫使其乾燥1小時而獲得獨立膜。藉由於1 mmHg之真空下，於200℃將所獲得之獨立膜加熱24小時，而使聚醯胺酸醯亞胺化，從而獲得包含醯亞胺交聯型樹脂(A-2-4)之透明膜。 醯亞胺交聯型樹脂(A-2-4)之T450 nm 為97%。 [實施例10] (1)醯亞胺交聯型樹脂(A-2-5)之製造 於共聚物(A-2)之γ-丁內酯溶液(濃度100 mg/mL)1 mL中添加4,4'-亞甲基雙(2-甲基環己基胺)之γ-丁內酯溶液(濃度12 mg/mL)1 mL、Gelest公司製造之DMS-A12之γ-丁內酯溶液(濃度16 mg/mL)1 mL，並於室溫攪拌20小時而使其發生反應，從而獲得含有聚醯胺酸之塗佈液。再者，二胺之添加量係設為約0.53當量。 繼而，將所獲得之塗佈液1 mL滴注至底面為2 cm見方之鐵氟龍(註冊商標)盤中，並於室溫使其乾燥1小時而獲得獨立膜。藉由於1 mmHg之真空下，於200℃將所獲得之獨立膜加熱24小時，而使聚醯胺酸醯亞胺化，從而獲得包含醯亞胺交聯型樹脂(A-2-5)之透明膜。 醯亞胺交聯型樹脂(A-2-5)之T10 為375℃，透明膜之T450 nm 為99%。 [參考例1] (1)共聚物(A-3)之合成 藉由二環戊二烯與順丁烯二酸酐之交替共聚，而獲得共聚物(A-3)。二環戊二烯與順丁烯二酸酐之添加比係設為1：1(莫耳比)，聚合反應係於四氫呋喃(THF)中，將偶氮二異丁腈(AIBN)作為自由基聚合起始劑，於室溫、24小時之條件下進行。關於AIBN之使用量，相對於單體成分之總量，設為2.1 mol%。 [化12]更具體而言，將二環戊二烯2000 mg及順丁烯二酸酐1490 mg溶解於3 mL之THF中，並添加60 mg之AIBN作為自由基聚合起始劑，於60℃進行24小時之反應。經過對二乙醚之再沈澱精製，而以白色粉末之形式獲得1100 mg之共聚物(A-3)。 所獲得之共聚物(A-3)之數量平均分子量Mn為3.3×103 ，分子量分佈Mw/Mn為1.8。關於所獲得之共聚物(A-3)，確認到其與實施例1～6同樣地藉由二胺而交聯而成。 [參考例2] (1)共聚物(A-4)之合成 藉由乙烯基降&#158665;烯與順丁烯二酸酐之交替共聚，而獲得共聚物(A-4)。乙烯基降&#158665;烯與順丁烯二酸酐之添加比係設為1：1(莫耳比)，聚合反應係於四氫呋喃(THF)中，將偶氮二異丁腈(AIBN)作為自由基聚合起始劑，於室溫、24小時之條件下進行。關於AIBN之使用量，相對於單體成分之總量，設為2.3 mol%。 [化13]更具體而言，將乙烯基降&#158665;烯2000 mg及順丁烯二酸酐1640 mg溶解於3 mL之THF中，並添加60 mg之AIBN作為自由基聚合起始劑，於60℃進行24小時之反應。經過對二乙醚之再沈澱精製，而以白色粉末之形式獲得3030 mg之共聚物(A-4)。 所獲得之共聚物(A-4)之數量平均分子量Mn為6.6×103 ，分子量分佈Mw/Mn為2.0。關於所獲得之共聚物(A-4)，確認到其與實施例1～6同樣地藉由二胺而交聯而成。 [比較例1] 對於實施例1中所獲得之共聚物(A-1)，不進行利用二胺之交聯而供T10 測定使用，其結果為，T10 為144℃。藉此，確認到藉由利用二胺之交聯，耐熱性顯著地提高。Hereinafter, preferred embodiments of the present invention will be described. (Indoleimine cross-linking type resin) The quinone imine cross-linking type resin of this embodiment is a crosslinked body obtained by crosslinking a copolymer having a cyclic olefin unit and an unsaturated dicarboxylic anhydride unit by a diamine. In the present specification, a cyclic olefin unit means a structural unit derived from a cyclic olefin, and an unsaturated dicarboxylic anhydride unit means a structural unit derived from an unsaturated dicarboxylic anhydride. That is, the copolymer may be a copolymer having a structural unit derived from a cyclic olefin and a structural unit derived from an unsaturated dicarboxylic anhydride, and may be a copolymer containing a monomer component of a cyclic olefin and an unsaturated dicarboxylic anhydride. The quinone imine crosslinked resin of the present embodiment has a quinone bond formed by the reaction of an acid anhydride in a copolymer with an amine group in a diamine. The quinone imine cross-linking resin of the present embodiment exhibits sufficient light transmittance and good heat resistance by providing a ring structure derived from a cyclic olefin and a crosslinked structure via a quinone bond in a molecule. Therefore, the quinone imine crosslinked resin of the present embodiment can be preferably used as a resin material for a surface protective film. <Copolymer> The copolymer in the present embodiment has a cyclic olefin unit and an unsaturated dicarboxylic anhydride unit, and can be crosslinked by a diamine. In the copolymer, the content of the unsaturated dicarboxylic anhydride unit C 2 (mol) and the content of the following maleimide unit 3 Total amount of (mol) C 2 +C 3 (mol) relative to the content of cyclic olefin units C 1 Ratio of (mol) (C 2 +C 3 ) /C 1 For example, it may be from 0.5 to 2.0, preferably from 0.95 to 1.05. Content of unsaturated dicarboxylic anhydride unit C 2 Relative to the above total C 2 +C 3 Ratio C 2 /(C 2 +C 3 For example, it may be 0.01 or more, preferably 0.5 or more, or may be 1 (that is, the content of the maleimide-based unit is 0). The number average molecular weight Mn of the copolymer may be, for example, 190 or more, preferably 1,000 or more, or may be 3,000 or more. The heat resistance of the fluorene imine crosslinked resin is further improved by increasing the number average molecular weight Mn of the copolymer. Further, the number average molecular weight Mn of the copolymer may be, for example, 500,000 or less, preferably 10,000 or less, or 7,000 or less. By reducing the number average molecular weight Mn of the copolymer, there is a tendency that the reaction rate by the crosslinking reaction of the diamine is increased. In the copolymer, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, that is, the molecular weight distribution Mw/Mn, may be, for example, 10 or less, preferably 5 or less. When the Mw/Mn is small, the heat resistance of the quinone imine crosslinked resin is further improved, and the volatile component in the quinone imine crosslinked resin tends to decrease. In the present specification, the number average molecular weight Mn and the weight average molecular weight Mw of the copolymer represent values measured by GPC (Gel Permeation Chromatography) measurement under the following conditions. Machine: "RID-10A/CBM-20A/DGU-20A3, LC-20AD/DPD-M20A/CTO-20A" manufactured by Shimadzu Corporation Pipe column: "TSKgel superHM-N" manufactured by Tosoh Corporation Detector: differential refractive index Rate detector (RI detector / built-in) Solvent: chloroform temperature: 40 ° C Flow rate: 0.3 mL / min Injection amount: 20 μL Concentration: 0.1% by weight Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene (i The cyclic olefin unit cyclic olefin unit is a structural unit derived from a cyclic olefin. The cyclic olefin is a compound having a ring structure and a carbon-carbon double bond including a carbon atom constituting the ring structure and polymerizable with the unsaturated dicarboxylic anhydride. The cyclic olefin may be, for example, a compound containing a ring structure having at least one carbon-carbon double bond in the ring. Such a cyclic olefin is easily subjected to polymerization with an unsaturated dicarboxylic anhydride. Further, according to such a cyclic olefin, since a ring structure is incorporated in the main chain of the copolymer, the shape and mobility of the main chain are restricted, and an imidazole having excellent heat resistance and optical properties can be obtained. The tendency of the joint resin. The ring structure of the cyclic olefin may be a single ring system or a polycyclic ring system. Examples of the ring structure of the monocyclic ring system include a cycloolefin skeleton, a cyclic diene skeleton, and a cyclic triene skeleton. Examples of the ring structure include a ring structure represented by the following formulas (1-1) to (1-5). [Chemical 1] Examples of the ring structure of the polycyclic ring system include a condensed ring and a bridged ring. As a ring structure of a polycyclic ring system, for example, a drop &#158665; an olefin skeleton, a drop &#158665; a diene skeleton, a bicyclo [2.2.2]-2-octene skeleton, a bicyclo [2.2.2]- 2,5-octadiene skeleton, dicyclopentadiene skeleton, dihydrodicyclopentadiene skeleton, terpene skeleton, anthracene skeleton, tetrahydroanthracene skeleton, tetracyclic ring [6.2.1.1 3,6 .0 2,7 ]-4-Dodecene skeleton and the like. Examples of the ring structure include a ring structure represented by the following formulas (2-1) to (2-11). [Chemical 2] The ring structure possessed by the cyclic olefin may have a substituent. Further, the ring structure may be condensed with other rings or may form a spiral ring with other rings. The cyclic olefin is, for example, a compound having a structure represented by the following formulas (3-1) to (3-34). [Chemical 3] The cyclic olefins may have a substituent. The substituent is not particularly limited as long as it does not inhibit the range of the polymerization reaction. The substituent may be, for example, a halogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group, an aryl group, an aralkyl group, a decyl group, a carboxyl group, a hydroxyl group, an amine group, an alkoxycarbonyl group or the like. Further, these substituents may be further substituted by other substituents. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, a fluorine atom, a chlorine atom or a bromine atom is preferred, and a fluorine atom is more preferred. The alkyl group may be linear, branched or cyclic. The carbon number of the alkyl group may be, for example, 1 to 30, preferably 1 to 10. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, and a third butyl group. A moiety in which one or all of the hydrogen atoms of the halogenated alkyl group is substituted with a halogen atom. Examples of the alkyl group and the halogen atom include the same as described above. Examples of the halogenated alkyl group include a trifluoromethyl group, a chloromethyl group, and a bromomethyl group. The alkoxy group is a group represented by -OR (R represents an alkyl group), and examples of the alkyl group of R include the same as described above. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a n-propoxy group, and a third butoxy group. The aryl group has a structure in which one hydrogen atom is removed from an aromatic hydrocarbon. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like. A part or all (preferably one) of one of the hydrogen atoms of the aralkyl group-containing alkyl group is substituted with an aryl group. Examples of the alkyl group and the aryl group are the same as those described above. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group and the like.矽alkyl-Si(R') 3 (R' represents a group represented by an alkyl group, an aryl group or an aralkyl group), and examples of the alkyl group, the aryl group and the aralkyl group as R' include the same as described above. Examples of the decyl group include a trimethyl decyl group, a dimethylphenyl decyl group, a triethyl decyl group, and a diethylphenyl fluorenyl group. The alkoxycarbonyl group is a group represented by COOR (R represents an alkyl group), and examples of the alkyl group as R include the same as described above. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a third butoxycarbonyl group. The cyclic olefin is preferably a compound which does not contain a hetero atom other than oxygen, nitrogen and sulfur, and more preferably a hydrocarbon which does not contain a hetero atom. Specific examples of the cyclic olefin include, for example, terpene, 5-ethylindenyl-2-nor &#158665; enebicyclo[3.2.1]-2-octene, [bicyclo[2.2.1]- 5-hepten-2-yl]triethoxydecane, tert-butyl-5-nor &#158665; ene-2-carboxylate, dicyclopentadiene, 5,6-dihydrodicyclopentane Diene, 5-ethylidene-2-lower &#158665; alkene, hydroxydicyclopentadiene, 2-nor &#158665; alkene, 5-nor &#158665; ene-2,3-dicarboxylic anhydride , 2,5-降&#158665;diene, 5-nor &#158665; ene-2,2-dimethanol, 5-nor &#158665; olefin-2-carboxylic acid methyl ester, 5-nor &# 158665; ene-2-carboxylate, 5-nor &#158665; ene-2,3-dimethanol, cis-5-nor &#158665; ene-exo-2,3-dicarboxylic anhydride, 5-nor &#158665; ene-2-ene, 3-endo-methanol, 5-nor &#158665; ene-2-exo, 3-exo-dimethanol, 5-nor &#158665; alk-2-yl Acid ester, 5-nor &#158665; ene-2-nitrile, 5-nor &#158665; ene-2,3-dicarboxyliminium, 5-nor &#158665; ene-2-methylamine, 5 - 降&#158665; ene-2-methanol, N-(2-ethylhexyl)-5-nor &#158665; ene-2,3-dicarboxylimine, 3a, 4,7,7a-four Hydroquinone, tetracyclo[6.2.1.13,6.02,7]-4-dodecene, 4-vinyl-1-cyclohexene, 5-vinylbicyclo[2.2.1]-2-heptene Tricyclopentadiene, dimethano-benzindenyl, fluorenyl dimethyl Bridge, alpha] -pinene, [beta] -pinene, and limonene. When the cyclic olefin has two or more carbon-carbon double bonds, part or all of the carbon-carbon double bonds may be reacted by a polymerization reaction. That is, the cyclic olefin unit may be a structural unit in which a part or all of the carbon-carbon double bond of the cyclic olefin is reacted by a polymerization reaction, or may have a carbon-carbon double which has a cyclic olefin. A structural unit in which one or all of the bonds are replaced by a single bond. The cyclic olefin unit preferably has at least a part of the ring structure constituting the main chain of the copolymer. Thereby, the shape and mobility of the main chain of the copolymer are controlled by the ring structure of the cyclic olefin unit, whereby a ruthenium imide crosslinked resin having more excellent heat resistance and optical properties can be obtained. (ii) Unsaturated Dicarboxylic Anhydride Unit The unsaturated dicarboxylic anhydride unit is a structural unit derived from an unsaturated dicarboxylic anhydride. The unsaturated dicarboxylic anhydride is a compound in which an unsaturated dicarboxylic acid having a carbon-carbon double bond and two carboxyl groups is dehydrated by intramolecular dehydration to form an acid anhydride. Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, methyl maleic anhydride, methylene succinic anhydride, 2,3-dimethyl maleic anhydride, and 2-(2). -carboxyethyl)-3-methyl maleic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, phenyl maleic anhydride, 2,3-diphenylbutylene Diacid anhydride, allyl succinic anhydride, (2-methyl-2-propenyl) succinic anhydride, 2-butene-1-yl succinic anhydride, cis-4-cyclohexene-1,2-di Carboxylic anhydride, 5-nor &lt;158665; ene-2,3-dicarboxylic anhydride, bicyclo[2.2.2]-5-octene-2,3-dicarboxylic anhydride, and the like. The unsaturated dicarboxylic acid anhydride can be, for example, a compound having a structure represented by the following formula (4-1). [Chemical 4] Where, R 1 Represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or an aryl group, and two R 1 They may be identical to each other or different from each other. If the unsaturated dicarboxylic anhydride is a compound having a structure represented by the formula (4-1), the shape and mobility of the main chain of the copolymer are controlled by a ring structure derived from an unsaturated dicarboxylic anhydride, and thus it is obtained. A quinone imine crosslinked resin which is more excellent in heat resistance and optical properties. As R 1 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom. R 1 The alkyl group may be linear, branched or cyclic. The carbon number of the alkyl group may be, for example, 1 to 30, preferably 1 to 10. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, and a third butyl group. R 1 The halogen atom-based alkyl group has a hydrogen atom which is partially or wholly substituted with a halogen atom. Examples of the alkyl group and the halogen atom include the same as described above. Examples of the halogenated alkyl group include a trifluoromethyl group, a chloromethyl group, and a bromomethyl group. As R 1 Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like. R 1 It is preferably a hydrogen atom, an alkyl group or a halogenated alkyl group, more preferably a hydrogen atom or an alkyl group. Further, from the viewpoint of excellent reactivity with a cyclic olefin and easy production of a copolymer, R is preferred. 1 At least one of them is a hydrogen atom. The unsaturated dicarboxylic anhydride unit may have, for example, a structure other than one or all of the hydrogen atoms of the succinic anhydride. When the unsaturated dicarboxylic anhydride is a compound having a structure represented by the formula (4-1), the unsaturated dicarboxylic anhydride unit may be a structural unit having a structure represented by the following formula (4-2). Furthermore, in the formula, R 1 Synonymous with the above. [Chemical 5] (iii) Maleimide-Based Unit The copolymer in the present embodiment may further have a structural unit derived from a maleimide-based compound (methyleneimine-based unit). The maleimide-based compound is, for example, a compound having a structure represented by the following formula (5-1), and the maleimide-based unit is, for example, represented by the following formula (5-2). Structural unit of structure. [Chemical 6] [Chemistry 7] Where, R 2 Represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or an aryl group, and two R 2 They may be identical to each other or different from each other. R 3 Represents the basis of a price. As R 2 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom. R 2 The alkyl group may be linear, branched or cyclic. The carbon number of the alkyl group may be, for example, 1 to 30, preferably 1 to 10. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, and a third butyl group. R 2 The halogen atom-based alkyl group has a hydrogen atom which is partially or wholly substituted with a halogen atom. Examples of the alkyl group and the halogen atom include the same as described above. Examples of the halogenated alkyl group include a trifluoromethyl group, a chloromethyl group, and a bromomethyl group. As R 2 Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like. R 2 It is preferably a hydrogen atom, an alkyl group or a halogenated alkyl group, more preferably a hydrogen atom or an alkyl group. Further, from the viewpoint of excellent reactivity with a cyclic olefin and an unsaturated dicarboxylic anhydride and production of a copolymer, it is preferably R. 2 At least one of them is a hydrogen atom. R 3 The basis of one of the valences is not particularly limited as long as it does not inhibit the polymerization reaction with the cyclic olefin. As R 3 The one-valent group may, for example, be an alkyl group, a halogenated alkyl group, an aryl group, an alkoxycarbonyl group, an aralkyl group or a nonyl group. The monovalent group may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an amine group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a decane. Base. Examples of the alkyl group, the halogenated alkyl group, the aryl group, the aralkyl group, the alkoxy group, the alkoxycarbonyl group and the decyl group include the same examples as described above. The alkylthio group-SR (R represents an alkyl group), and the alkyl group as R may be the same as the above. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group and the like. The aryloxy group and the arylthio group are each a group represented by -OR" and -SR"(R" represents an aryl group), and examples of the aryl group of R" include the same as described above. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the arylthio group include a phenylthio group and a naphthylthio group. (iv) Other structural unit The copolymer in the present embodiment may further have a structural unit other than the above. For example, the copolymer may further have a structural unit derived from a bis-butylene diimide-based compound having two maleimide groups. Examples of the bis-n-butylene imino-based compound include 4,4′-bis-s-butylenediamine diphenylmethane and 1,6-bis(m-butylene imino)hexane. , bis(3-ethyl-5-methyl-4-maleimidophenylene)methane, 1,4-bis(methyleneimine)butane, 2,2-double [ 4-(4-maleoximeimide phenoxy)phenyl]propane, 1,2-bis(m-butyleneimine)ethane, N,N'-1,4-phenylene Dim-butyleneimine, N,N'-1,3-phenylenebissuccinimide, and the like. Further, the copolymer may further have a structural unit derived from an olefin compound which can be alternately copolymerized with an unsaturated dicarboxylic anhydride or a maleimide compound. Examples of the olefin compound include styrene derivatives such as styrene, hydrazine, α-methylstyrene, and p-methylstyrene; ethyl vinyl ether, n-propyl vinyl ether, and isopropyl vinyl ether; An alkyl monovinyl ether derivative such as butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether or cyclohexyl vinyl ether. The copolymer in the present embodiment can be obtained, for example, by a polymerization reaction of a monomer component containing a cyclic olefin and an unsaturated dicarboxylic anhydride. The monomer component may further contain a maleimide-based compound, and may further contain other monomers. The form of the polymerization reaction is not particularly limited, and for example, it may be a radical polymerization. When the polymerization reaction is a radical polymerization, a known radical polymerization initiator can be used as the polymerization initiator. Examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN, azobisisobutyronitrile), di-tert-butyl peroxide, t-butyl hydroperoxide, and benzamidine peroxide (BPO). Benzoyl peroxide), methyl ethyl ketone peroxide, redox initiator (hydrogen peroxide and iron (II) salt, persulfate and sodium hydrogen sulfite, etc.), triethylborane (Et 3 B), diethyl zinc (Et 2 Zn) and so on. Further, atom transfer radical polymerization (ATRP, Atom Transfer Radical Polymerization), Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT), polymerization via nitrogen oxides (NMP, Nitroxide Mediated) may also be used. Polymerization) and other methods such as living radical polymerization and precision radical polymerization. The amount of use of the radical polymerization initiator may be, for example, 0.1 to 10 mol%, preferably 1 to 5 mol%, based on the total amount of the monomer components. The polymerization reaction is preferably carried out in a solvent. As the solvent, for example, tetrahydrofuran (THF, tetrahydrofuran), dioxane, dioxolane, acetone, chloroform, toluene, dimethylformamide, dimethylformyl bromide can be preferably used. DMAc, dimethyl acetamide, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, cyclopentanone, cyclohexanone, Ethylene glycol dimethyl ether solvent such as tetramethyl urea, 1,3-dimethyl-2-imidazolidinone or diethylene glycol dimethyl ether, cellosolve solvent such as ethyl cellosolve, propylene glycol monomethyl A glycol ester solvent such as ether acetate or a glycol ether solvent such as propylene glycol monomethyl ether. The conditions of the polymerization reaction are not particularly limited. For example, the reaction temperature may be -20 to 200 ° C, and the reaction time may be 0.1 to 100 hours. <Crosslinked body> The fluorene imine crosslinked resin of the present embodiment is a crosslinked product obtained by crosslinking the above copolymer with a diamine, which is formed by the reaction of an acid anhydride and a diamine in the copolymer. Yttrium imine bond. In the present embodiment, some or all of the unsaturated dicarboxylic anhydride units in the copolymer may react with the diamine to form a quinone bond. The amount of the unsaturated dicarboxylic anhydride unit remaining in the quinone imide crosslinked resin is preferably 90 mol% or less, more preferably 70 mol%, based on the total amount of the unsaturated dicarboxylic anhydride unit in the copolymer. Hereinafter, it is more preferably 50 mol% or less. The diamine may be a compound having two amine groups which can react with an acid anhydride in the copolymer to form an oximine bond. Examples of the diamine include an aromatic diamine and an aliphatic diamine. In the present specification, an aromatic diamine means a compound having two amine groups bonded to an aromatic ring, and an aliphatic diamine means having two bonds to sp 3 A compound of carbon amine. Further, the diamine may also have an amine group bonded to the aromatic ring and bonded to the sp 3 A compound of carbon amine. The aromatic diamine is, for example, a compound having a structure represented by the following formulas (6-1) to (6-4). [化8] Where Q 1 Indicates the basis of the divalent. These aromatic diamines may also have a substituent. The substituent is not particularly limited as long as it does not inhibit the range of the crosslinking reaction. The substituent may, for example, be a halogen atom, an alkyl group, a halogenated alkyl group, an aryl group, a sulfo group, an alkoxy group, an aryloxy group, a decyl group, a hydroxyl group, a thiol group, an alkylthio group, an arylthio group, a nitrile group or a ketone group. , carboxyl group, etc. Further, these substituents may be further substituted by other substituents. Examples of the halogen atom, the alkyl group, the halogenated alkyl group, the aryl group, the alkoxy group, the aryloxy group, the decyl group, the alkylthio group and the arylthio group include the same examples as described above. The ketone group -COR'(R' represents an alkyl group, an aryl group or an aralkyl group), and examples of the alkyl group, the aryl group and the aralkyl group as R' include the same examples as described above. Examples of the ketone group include a methylcarbonyl group, a phenylcarbonyl group, a benzylcarbonyl group and the like. Q 1 The base of the divalent amount is not particularly limited as long as it does not hinder the range of the crosslinking reaction. Specific examples of the basis of the divalent group include: -O-, -S-, -CH 2 -, -SO 2 -, -CO-, -OC 6 H 4 -O-, -NHCO-, -OC 6 H 4 -C(Me) 2 -C 6 H 4 -O-, -OC 6 H 4 -C(CF 3 ) 2 -C 6 H 4 -O-, -C(Me) 2 -C 6 H 4 -C(Me) 2 -, -OC 6 H 4 -C 6 H 4 -O-, -OC 6 H 4 -SO 2 -C 6 H 4 -O-, -C 6 H 4 -, -NHCO-C 6 H 4 -CONH-, -CONH-C 6 H 4 -NHCO-, -(Si(OMe) 2 -O) n -,-(Si(OEt) 2 -O) n -, - (Si(OPh) 2 -O) x -Wait. Further, x represents an integer of 1 or more, preferably an integer of 1 to 100. The aliphatic diamine is, for example, a compound having a structure represented by the following formulas (7-1) to (7-7). [Chemistry 9] Where Q 2 Indicates the basis of the divalent. The aliphatic diamines may also have a substituent. The substituent is not particularly limited as long as it does not inhibit the range of the crosslinking reaction. The substituent may, for example, be a halogen atom, an alkyl group, a halogenated alkyl group, an aryl group, a sulfo group, an alkoxy group, an aryloxy group, a decyl group, a hydroxyl group, a thiol group, an alkylthio group, an arylthio group, a nitrile group or a ketone group. , carboxyl group, etc. Further, these substituents may be further substituted by other substituents. Examples of the bases include the same examples as described above. Q 2 The base of the divalent amount is not particularly limited as long as it does not hinder the range of the crosslinking reaction. Specific examples of the basis of the divalent group include: -O-, -S-, -CH 2 -, -SO 2 -, -CO-, -OC 6 H 4 -O-, -NHCO-, -OC 6 H 4 -C(Me) 2 -C 6 H 4 -O-, -OC 6 H 4 -C(CF 3 ) 2 -C 6 H 4 -O-, -C(Me) 2 -C 6 H 4 -C(Me) 2 -, -OC 6 H 4 -C 6 H 4 -O-, -OC 6 H 4 -SO 2 -C 6 H 4 -O-, -C 6 H 4 -, -NHCO-C 6 H 4 -CONH-, -CONH-C 6 H 4 -NHCO-, -(Si(OMe) 2 -O) n -,-(Si(OEt) 2 -O) n -, - (Si(OPh) 2 -O) x -, 9, 9-arylene and the like. Further, x represents an integer of 1 or more, preferably an integer of 1 to 100. Further, the diamine may be, for example, a polyoxyalkylene-based diamine obtained by introducing an amine group to a terminal or a side chain of a polyoxyalkylene oxide. The polyoxyalkylene-based diamine may have a molecular weight of, for example, 100 to 100,000 or 200 to 50,000. Specific examples of the diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,2-phenylenediamine, 4,4'-extended ethyldiphenylamine, and 2,2'- Ethyldiphenylamine, 3,3'-diaminodiphenylethane, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diamine linkage Benzene, 3,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethyl Biphenyl, 4,4'-diamino octafluorobiphenyl, 2,5-dimethyl-1,4-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine , 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 1,3,5-tris(4- Aminophenyl)benzene, 2,5-dichloro-1,4-phenylenediamine, 2,6-dibromo-1,4-phenylenediamine, 2,7-diaminoguanidine, 1,5- Diaminonaphthalene, 1,4-diaminonaphthalene, 2,6-diaminonaphthalene, 1,3-diaminoguanidine, 1,6-diaminoguanidine, 1,8-diaminoguanidine, 3,3'-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'- Dimethyldiphenylmethane, 4,4'-methylenebis(2-chloroaniline), 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'- Methylene bis(2,6-diethylaniline), 4,4"-diamino-para-triphenyl, α,α'-double ( 4-aminophenyl)-1,4-diisopropylbenzene, 1,1-bis(4-aminophenyl)cyclohexane, 1,3-bis[2-(4-aminophenyl) -2-propyl]benzene, 4,4'-diamino-2,2'-dimethylbibenzyl, o-toluidine, m-toluidine, 3,3'-diethylbenzidine, 3,3',5,5'-tetramethylbenzidine, 2,2',5,5'-tetrachlorobenzidine, 2,2'-bis(trifluoromethyl)-4,4'-di Aminobiphenyl, 3,3'-dihydroxybenzidine, 1,5-bis(4-aminophenoxy)pentane, 3,3'-diaminobenzidine, o-dimethoxyaniline, 9 ,9-bis(4-aminophenyl)anthracene, 9,9-bis(4-amino-3-chlorophenyl)anthracene, 9,9-bis(4-amino-3-fluorophenyl) Indole, 9,9-bis(4-amino-3-methylphenyl)anthracene, 9,9-bis(3-amino-4-hydroxyphenyl)anthracene, 2,7-diamino-9 , 9-di-n-octyl hydrazine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 4,6-diaminoresorcinol, 2,5-diamino-1, 4-phenyldithiol, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenyl ether, 3,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]diphenylamine, 4,4'-[1,4-phenylene bis(1) -Methyl-ethylidene)]diphenylamine, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-amino-2-trifluoromethylphenoxy) Benzene, 4,4'-diaminodiphenylamine, 4,4'-diaminobenzimidamide, 3,4'-diaminobenzamide, bis(2-aminophenyl)sulfide Ether, bis(4-aminophenyl) sulfide, 4,4'-dithiodiphenylamine, 2,2'-dithiodiphenylamine, 3,3'-diaminodiphenylanthracene, 4 , 4'-diaminodiphenylanthracene, 2,2'-benzidine disulfonic acid, bis[4-(3-aminophenoxy)phenyl]indole, bis[4-(4-amino) Phenoxy)phenyl]anthracene, bis(3-amino-4-hydroxyphenyl)anthracene, 3,7-diamino-2,8-dimethyldibenzothiophene, 2,2-double (3-Amino-4-methylphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-amine Phenyl phenyl) hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2' - bis(trifluoromethyl)benzidine, 4,4'-diaminostilbene, 3,6-diaminocarbazole, 2,6-diaminopurine, 3,9-bis[2 -(3,5-diamine -2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, benzoguanamine, 2,4-diamino-6 -Methyl-1,3,5-tri- &lt;134116;, 2,4-diamino-6-dimethylamino-1,3,5-tri &#134116;, 2,4-diamine -6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-tri &#134116;, 2,4-diamino-6-[2-(2-10 Monoalkyl-1-imidazolium)ethyl]-1,3,5-tri &#134116;, 2,2'-diamino-4,4'-bithiazole, ethylenediamine, 1,2-di Aminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Heptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl- 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,2-diamino-2-methylpropane, 2,3-dimethyl-2,3- Butanediamine, 2-methyl-1,5-diaminopentane, 2,2'-oxybis(ethylamine), 1,2-bis(2-aminoethoxy)ethane, 1,4-butanediol bis(3-aminopropyl)ether, diethylene glycol bis(3-aminopropyl)ether, 1,14-diamino-3,6,9,12-tetra Oxatetradecane, di-ethyltriamine, tri-ethyltetramine, 3,3'-diaminodipropylamine, 2,2'- Diamino-N-methyldiethylamine, 3,3'-diamino-N-methyldipropylamine, N,N'-bis(2-aminoethyl)-1,3- Propylenediamine, N,N'-bis(3-aminopropyl)ethylenediamine, N,N'-bis(3-aminopropyl)-1,4-butanediamine, 2,2'- Thiobis(ethylamine), m-xylylenediamine, p-xylylenediamine, cis-1,3-bis(aminomethyl)cyclohexane, 1,3-bis(3-aminopropyl) Tetramethyldioxane, an amine-modified polyoxyxide oil manufactured by Shin-Etsu Chemical Co., Ltd. (for example, X-22-1660B-3 (Mw: 4400), X-22-161B (Mw: 3000), X- 22-161A (Mw: 1600), X-22-9409 (Mw: 1340), etc., dimethyl oxoxane type diamine manufactured by Gelest Corporation (for example, DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A31, DMS-A32, DMS-A35, etc.), 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, cis-1,3-cyclohexanediamine, trans-1 , 3-cyclohexanediamine, cis-1,4-cyclohexanediamine, trans-1,4-cyclohexanediamine, 4,4'-methylenebis(2-methylcyclohexylamine), 1 , 3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), bis(aminomethyl) ) 降 &#158665; alkane, isophorone diamine, 3 (4), 8 (9)-bis (aminomethyl) tricyclic [5.2.1.0 2,6 ] decane, 3-aminobenzylamine, 4-aminobenzylamine, and the like. The cross-linking reaction of the copolymer with the diamine, for example, the first step of forming a poly-proline by reacting the copolymer with a diamine, and the second step of forming a quinone bond by dehydration of poly-proline And implementation. The first step may be, for example, a step of obtaining a poly-proline by reacting the copolymer with a diamine in a solvent. The reaction temperature may be, for example, -20 to 200 ° C, and the reaction time may be, for example, 0.1 to 100 hours. The solvent used in the first step may be any solvent which can dissolve the copolymer and the diamine. Further, the solvent is preferably a solvent which can dissolve the produced polylysine. As the solvent, for example, dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), γ-butyrolactone, N,N-dimethylformamide (DMF) can be preferably used. , dimethyl hydrazine (DMSO), tetrahydrofuran (THF), tetramethyl urea, 1,3-dimethyl-2-imidazolidinone, phenol, p-chlorophenol, pyridine, cyclopentanone, cyclohexanone, and the like. The amount of the diamine which reacts with the copolymer is, for example, 0.05 equivalent or more, more preferably 0.5 equivalent or more, based on the content of the unsaturated dicarboxylic anhydride unit in the copolymer. Further, the amount of the diamine can be, for example, 1.5 equivalents or less, more preferably 1.0 equivalents or less, based on the content of the unsaturated dicarboxylic anhydride unit in the copolymer. In the first step, a reaction liquid containing polylysine can be obtained. In one aspect, polylysine can be recovered from the reaction solution and the recovered polyamic acid can be used in the second step. Further, in another aspect, the reaction solution may be applied onto a substrate to form a coating film of polylysine, and then the second step may be carried out. In the second step, a quinone imine bond is formed by a dehydration reaction of polyproline to obtain a quinone imine crosslinked resin. The dehydration reaction can be carried out, for example, by heating polylysine. The reaction temperature of the dehydration reaction may be, for example, 100 to 400 ° C, and the reaction time may be, for example, 0.1 to 100 hours. Further, the aspect of the crosslinking reaction is not limited to those described above. For example, the crosslinking reaction may be a reaction in which a copolymer is reacted with a diamine using a dehydrating catalyst to form a quinone bond at a stage. Examples of the dehydration catalyst include pyridine, 2-hydroxypyridine, triethylamine, imidazole, and N-methylpiperidine. Further, the crosslinking reaction can be carried out in the presence of a dehydrating agent that traps the produced water. Examples of the dehydrating agent include acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The quinone imine crosslinked resin of the present embodiment has a quinone bond formed by the reaction of an acid anhydride in a copolymer with an amine group in a diamine. The quinone imine cross-linking resin of the present embodiment has sufficient light transmittance and good heat resistance by providing a ring structure derived from a cyclic olefin and a crosslinked structure via a quinone bond in a molecule. Therefore, the quinone imine crosslinked resin of the present embodiment can be preferably used as a resin material for a surface protective film. (Transparent film) The transparent film of this embodiment contains the above-mentioned quinone imine crosslinked type resin. The transparent film of this embodiment can be preferably used as a film substrate for a surface protective film, for example. Furthermore, in the present specification, the transparent film means visible light transmittance (T 450 nm ) is a film of 60% or more. Visible light transmittance of transparent film (T 450 nm It is preferably 80% or more, more preferably 85% or more. The thickness of the transparent film is not particularly limited, and may be, for example, 1 μm or more, or 10 μm or more, 500 μm or less, or 1000 μm or less. The transparent film may further contain a component other than the quinone imine crosslinked resin. For example, the transparent film may further contain an antioxidant, a light stabilizer, an antistatic agent, a lubricant, a flame retardant, a plasticizer, a clearing agent, a nucleating agent, a filler, and the like. Hereinafter, a preferred aspect of the method for producing a transparent film will be described. The method for producing a transparent film according to the aspect of the invention may further comprise: a preparation step of preparing a coating liquid containing a polyamic acid as a reactant of a copolymer and a diamine; and a coating step of coating the coating liquid On the substrate, a coating film containing polyamic acid is formed; and a heating step of heating the coating film to obtain a transparent film containing a ruthenium imide crosslinked resin. In the preparation step, for example, a copolymer and a diamine may be reacted in a solvent to obtain a reaction liquid containing poly-proline, and the reaction liquid is used as a coating liquid. Further, polylysine may be recovered from the reaction liquid, and the recovered polyamic acid may be dissolved in a solvent to obtain a coating liquid. In the coating step, a coating liquid is applied onto a substrate to form a coating film. The coating method is not particularly limited, and a known coating method (for example, a spin coating method, a bar coating method, a slit method, a die coating method, or the like) can be used. In the coating step, the solvent can be removed after coating of the coating liquid. The method for removing the solvent is not particularly limited, and a known removal method (for example, heating under reduced pressure, heating under normal pressure, heating by a hot plate, heating under a hot air stream, drying under a gas stream, far-infrared heating, etc.) can be used. ). The substrate is not particularly limited as long as it has a surface on which a coating film having a desired shape can be formed. As the substrate, for example, a glass substrate; a metal foil substrate such as copper or aluminum; a metal ribbon substrate such as steel or stainless steel; polytetrafluoroethylene, PPS (Polyphenylene Sulfite), and PET (Polyethylene Terephthalate) can be preferably used. A resin sheet substrate such as polyethylene terephthalate), acrylic resin, polyethylene, polypropylene, or polystyrene. In the heating step, the coating film is heated to carry out a dehydration reaction of polyamic acid to obtain a transparent film containing a ruthenium imide crosslinked resin. The heating temperature may be a temperature at which the dehydration reaction of polyproline is carried out, and may be, for example, 100 to 400 ° C, preferably 200 to 300 ° C. The heating time may be, for example, 0.1 to 100 hours, preferably 1 to 10 hours. (Surface Protective Film) The surface protective film of the present embodiment includes the transparent film and a metal deposited layer provided on at least one surface of the transparent film. The transparent film contains a ruthenium imide crosslinked resin and is excellent in heat resistance. Therefore, in the present embodiment, it is possible to obtain a surface protective film which is excellent in light transmittance, such as expansion or deformation due to heat of the transparent film, even when the metal is vapor-deposited on the transparent film. . The metal deposition layer is a thin metal layer formed by vapor deposition on a transparent film. The metal may be, for example, aluminum, ruthenium or the like, or a metal oxide thereof. The vapor deposition method is not particularly limited, and a known vapor deposition method can be used. The thickness of the metal deposition layer may be, for example, 1 to 1000 nm or 100 to 500 nm. The surface protective film of the present embodiment can be preferably used, for example, for surface protection of a display of a portable information terminal, a touch panel, a computer display, a television display, a digital signage, or the like. The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. [Example 1] (1) Synthesis of Copolymer (A-1) The copolymer (A-1) was obtained by alternate copolymerization of a olefin and maleic anhydride. The ratio of the addition of ene to maleic anhydride is 1:1 (mole ratio), the polymerization is carried out in tetrahydrofuran (THF), and azobisisobutyronitrile (AIBN) is used as a free radical. The polymerization initiator was carried out at room temperature for 24 hours. The amount of AIBN used was set to 1.9 mol% based on the total amount of the monomer components. [化10] More specifically, 200 mg of olefin and 2080 mg of maleic anhydride were dissolved in 3 mL of THF, and 60 mg of AIBN was added as a radical polymerization initiator for 24 hours at 60 ° C. The reaction. After reprecipitation purification of diethyl ether, 2650 mg of the copolymer (A-1) was obtained as a white powder. The obtained copolymer (A-1) has a number average molecular weight Mn of 4.8 × 10 3 The molecular weight distribution Mw/Mn was 1.7. Further, the number average molecular weight Mn and the molecular weight distribution Mw/Mn were measured by the following methods. <Measurement of Number Average Molecular Weight Mn and Weight Average Molecular Weight Mw> The number average molecular weight Mn and the weight average molecular weight Mw were measured by GPC measurement under the following conditions. Machine: "RID-10A/CBM-20A/DGU-20A3, LC-20AD/DPD-M20A/CTO-20A" manufactured by Shimadzu Corporation Pipe column: "TSKgel superHM-N" manufactured by Tosoh Corporation Detector: differential refractive index Rate detector (RI detector / built-in) Solvent: chloroform temperature: 40 ° C Flow rate: 0.3 mL / min Injection amount: 20 μL Concentration: 0.1% by weight Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene (2 Manufacture of quinone imine cross-linking resin (A-1-1) dimethyl group of diamine added to 1 mL of dimethyl acetamide solution (concentration 100 mg/mL) of copolymer (A-1) 1 mL of an acetamide solution (concentration: 25 mg/mL) was stirred at room temperature for 20 hours to obtain a coating liquid containing polylysine. As the diamine, 4,4'-diaminodiphenyl ether is used, and the amount of the diamine added is set to 1 equivalent with respect to the maleic anhydride unit in the copolymer (that is, relative to the maleic acid). The anhydride unit is 1 mole and the diamine is 0.5 mole. Then, 500 μL of the obtained coating liquid was dropped into a 250 mm square glass substrate, and dried at 100 ° C for 1 hour to obtain a separate film. The obtained bismuth amide was imidized by heating the obtained independent film at 200 ° C for 24 hours under a vacuum of 1 mmHg to obtain a ruthenium-containing crosslinked resin (A-1-1). Transparent film. For the obtained quinone imine crosslinked resin (A-1-1), the following method was used to determine the 10% weight loss temperature (T 10 ). The result is that T 10 At 386 ° C, higher heat resistance was confirmed. Moreover, the visible light transmittance of the transparent film by the following method (T 450 nm The result of the measurement is, T 450 nm It is 82%. Further, as a result of measuring the pencil hardness by the following method, the obtained transparent film had a pencil hardness of 2H. <Measurement Method of 10% Weight Loss Temperature> A 10% weight loss temperature was measured by a thermogravimetric analyzer ("Thermo plus Evo TG8120" manufactured by RIGAKU Co., Ltd.). This was obtained by heating nitrogen gas under a nitrogen atmosphere, and setting the scanning temperature to 30 ° C to 500 ° C, heating at a temperature rising rate of 10 ° C / min, and measuring the test. The weight loss is 10% of the temperature. <Method for Measuring Light Transmittance> Using a spectrophotometer Jasco V-670 spectrophotometer as a measuring device, the transmittance of a sample having a wavelength of 280 to 800 nm was measured, and the transmittance for light having a wavelength of 450 nm was determined. <Pencil Hardness Test> Automatic measurement was performed using a continuous load type surface measuring machine TRIBOGEAR TYPE-22 manufactured by HEIDON Shinto Scientific Co., Ltd. as a measuring device. [Example 2] (1) Production of quinone imine crosslinked resin (A-1-2) In addition to 2,2'-bis(trifluoromethyl)benzidine DMAc solution (concentration 25 mg/mL) A transparent film containing a ruthenium imide crosslinked resin (A-1-2) was produced in the same manner as in Example 1 except that 1.6 mL was used as the diamine. T of yttrium imide crosslinked resin (A-1-2) 10 379 ° C, transparent film T 450 nm It is 74%. [Example 3] (1) Production of ruthenium imine crosslinked resin (A-1-3) except for the use of 3(4), 8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6 A transparent film containing a ruthenium imide crosslinked resin (A-1-3) was produced in the same manner as in Example 1 except that 1 mL of a DMAc solution (concentration: 25 mg/mL) of decane was used as the diamine. About T of yttrium imide crosslinked resin (A-1-3) 10 And transparent film T 450 nm Both represent values substantially equivalent to those of the second embodiment. [Example 4] (1) Preparation of ruthenium imine crosslinked resin (A-1-4) Manufactured from Gelest Co., Ltd. in 1 mL of a THF solution (concentration: 100 mg/mL) of the copolymer (A-1) 1 mL of DMS-A12 (aminopropyl-terminated dimethyloxane, molecular weight 900-1000) in THF (concentration: 37 mg/mL), and stirred at room temperature for 20 hours to cause reaction to obtain A coating solution of polylysine. Further, the amount of the diamine added was set to be about 0.45 equivalent. Then, 1 mL of the obtained coating liquid was dropped into a Teflon (registered trademark) disk having a bottom surface of 2 cm square, and dried at room temperature for 1 hour to obtain a separate film. The obtained lysine was imidized by heating the obtained independent film at 200 ° C for 24 hours under a vacuum of 1 mmHg to obtain a ruthenium-containing crosslinked resin (A-1-4). Transparent film. T of yttrium imide crosslinked resin (A-1-4) 10 352 ° C, transparent film T 450 nm It is 97%. Further, the pencil hardness was measured as F to H. [Example 5] (1) Preparation of quinone imine cross-linking type resin (A-1-5) Addition of Shin-Etsu Chemical Industry Co., Ltd. in 1 mL of THF solution (concentration: 100 mg/mL) of copolymer (A-1) Amine-modified polyoxyxanic acid X-22-9409 (aminophenyl-terminated dimethyloxane, molecular weight 1340) in THF (concentration 57 mg / mL) 1 mL, and stirred at room temperature for 20 hours This was allowed to react to obtain a coating liquid containing polylysine. Further, the amount of the diamine added was set to be about 0.3 equivalent. Then, 1 mL of the obtained coating liquid was dropped into a Teflon (registered trademark) disk having a bottom surface of 2 cm square, and dried at room temperature for 1 hour to obtain a separate film. The obtained lysine was imidized by heating the obtained independent film at 200 ° C for 24 hours under vacuum of 1 mmHg to obtain a ruthenium-containing crosslinked resin (A-1-5). Transparent film. T of yttrium imide crosslinked resin (A-1-5) 10 359 ° C, transparent film T 450 nm It is 84%. [Example 6] (1) Synthesis of copolymer (A-2) was obtained by copolymerization of olefin, maleic anhydride, and N-ethyl maleimide. Copolymer (A-2). The addition ratio of ene, maleic anhydride, and N-ethyl maleimide was set to 3:1:2. The polymerization was carried out in THF, and AIBN was used as a radical polymerization initiator at room temperature for 24 hours. The amount of AIBN used was set to 1.6 mol% based on the total amount of the monomer components. [11] More specifically, a solution of 2000 mg of olefin, 710 mg of maleic anhydride, and 1780 mg of N-ethyl maleimide was dissolved in 3 mL of THF, and 60 mg was added thereto. AIBN was used as a radical polymerization initiator at 24 ° C for 24 hours. After reprecipitation of diethyl ether, 3340 mg of the copolymer (A-2) was obtained as a white powder. The obtained copolymer (A-2) has a number average molecular weight Mn of 4.7 × 10 3 The molecular weight distribution Mw/Mn was 1.7. (2) Preparation of quinone imine cross-linking resin (A-2-1) γ-addition of diamine to 1 mL of γ-butyrolactone solution (concentration 100 mg/mL) of copolymer (A-2) 1 mL of a butyrolactone solution (concentration: 25 mg/mL) was stirred at room temperature for 20 hours to obtain a coating liquid containing polylysine. As the diamine, 4,4'-diaminodiphenyl ether was used, and the amount of the diamine added was 0.5 equivalent based on the maleic anhydride unit in the copolymer. Then, the obtained coating liquid 500 μm was dropped into a 250 mm square glass substrate, and dried at 130 ° C for 1 hour to obtain a separate film. The obtained lysine was imidized by heating the obtained independent film at 200 ° C for 24 hours under a vacuum of 1 mmHg to obtain a ruthenium-containing crosslinked resin (A-2-1). Transparent film. T of yttrium imide crosslinked resin (A-2-1) 10 385 ° C, transparent film T 450 nm It is 81%. The obtained transparent film was cut into 7 mm × 25 mm to prepare a test piece, and a dynamic viscoelasticity test was performed. As a result, the test piece had a storage modulus of 2.1 GPa and a Tg of 299 ° C, which was confirmed to have high thermal stability and mechanical strength. [Example 7] (1) Preparation of quinone imine crosslinked resin (A-2-2) 4,4' was added to 1 mL of a DMF solution (concentration: 100 mg/mL) of the copolymer (A-2) 1 mL of a methylene bis(cyclohexylamine) DMF solution (concentration: 10 mg/mL) was stirred at room temperature for 20 hours to obtain a coating liquid containing polylysine. Further, the amount of the diamine added was set to be about 0.4 equivalent. Then, 1 mL of the obtained coating liquid was dropped into a Teflon (registered trademark) disk having a bottom surface of 2 cm square, and dried at room temperature for 1 hour to obtain a separate film. The obtained bismuth amide was imidized by heating the obtained independent film at 200 ° C for 24 hours under a vacuum of 1 mmHg to obtain a ruthenium-containing crosslinked resin (A-2-2). Transparent film. T of quinone imine cross-linking resin (A-2-2) 10 386 ° C, transparent film T 450 nm It is 82%. [Example 8] (1) Production of ruthenium imine crosslinked resin (A-2-3) was added to 1 mL of γ-butyrolactone solution (concentration: 100 mg/mL) of copolymer (A-2) 1 mL of 4,4'-methylenebis(2-methylcyclohexylamine) γ-butyrolactone solution (concentration 12 mg/mL), and stirred at room temperature for 20 hours to cause reaction A coating solution containing polyamic acid. Further, the amount of the diamine added was set to be about 0.4 equivalent. Then, 1 mL of the obtained coating liquid was dropped into a Teflon (registered trademark) disk having a bottom surface of 2 cm square, and dried at room temperature for 1 hour to obtain a separate film. The obtained bismuth amide was imidized by heating the obtained independent film at 200 ° C for 24 hours under a vacuum of 1 mmHg to obtain a ruthenium-containing crosslinked resin (A-2-3). Transparent film. The bismuth imide crosslinked resin (A-2-3) has a Tg of 299 ° C and a storage modulus of 2.1 GPa, T 10 385 ° C, transparent film T 450 nm It is 81%. [Example 9] (1) Preparation of ruthenium imine crosslinked resin (A-2-4) 4,4' was added to 1 mL of a DMF solution (concentration: 100 mg/mL) of the copolymer (A-2) - 1 mL of methylene bis(cyclohexylamine) in DMF solution (concentration 10 mg/mL), 1 mL of DMS-A12 DMF solution (concentration 16 mg/mL) manufactured by Gelest, and stirred at room temperature for 20 hours. Instead, it is allowed to react to obtain a coating liquid containing polyamic acid. Further, the amount of the diamine added was set to be about 0.53 equivalent. Then, 1 mL of the obtained coating liquid was dropped into a Teflon (registered trademark) disk having a bottom surface of 2 cm square, and dried at room temperature for 1 hour to obtain a separate film. The obtained bismuth amide was imidized by heating the obtained independent film at 200 ° C for 24 hours under vacuum of 1 mmHg to obtain a ruthenium-containing crosslinked resin (A-2-4). Transparent film. T of yttrium imide crosslinked resin (A-2-4) 450 nm It is 97%. [Example 10] (1) Preparation of quinone imine crosslinked resin (A-2-5) was added to 1 mL of γ-butyrolactone solution (concentration 100 mg/mL) of copolymer (A-2) 4,4'-methylenebis(2-methylcyclohexylamine) γ-butyrolactone solution (concentration 12 mg/mL) 1 mL, DMS-A12 γ-butyrolactone solution manufactured by Gelest The concentration was 16 mg/mL) 1 mL, and the mixture was stirred at room temperature for 20 hours to cause a reaction to obtain a coating liquid containing polylysine. Further, the amount of the diamine added was set to be about 0.53 equivalent. Then, 1 mL of the obtained coating liquid was dropped into a Teflon (registered trademark) disk having a bottom surface of 2 cm square, and dried at room temperature for 1 hour to obtain a separate film. The obtained bismuth amide was imidized by heating the obtained independent film at 200 ° C for 24 hours under a vacuum of 1 mmHg to obtain a ruthenium-containing crosslinked resin (A-2-5). Transparent film. T of quinone imine cross-linking resin (A-2-5) 10 375 ° C, transparent film T 450 nm It is 99%. [Reference Example 1] (1) Synthesis of Copolymer (A-3) The copolymer (A-3) was obtained by alternately copolymerizing dicyclopentadiene and maleic anhydride. The addition ratio of dicyclopentadiene to maleic anhydride is set to 1:1 (mole ratio), the polymerization reaction is carried out in tetrahydrofuran (THF), and azobisisobutyronitrile (AIBN) is used as a radical polymerization. The initiator was carried out at room temperature under 24 hours. The amount of AIBN used was 2.1 mol% based on the total amount of the monomer components. [化12] More specifically, dicyclopentadiene 2000 mg and maleic anhydride 1490 mg were dissolved in 3 mL of THF, and 60 mg of AIBN was added as a radical polymerization initiator at 60 ° C for 24 hours. reaction. After reprecipitation purification of diethyl ether, 1100 mg of a copolymer (A-3) was obtained as a white powder. The obtained copolymer (A-3) has a number average molecular weight Mn of 3.3 × 10 3 The molecular weight distribution Mw/Mn was 1.8. The obtained copolymer (A-3) was confirmed to be crosslinked by a diamine in the same manner as in Examples 1 to 6. [Reference Example 2] (1) Synthesis of Copolymer (A-4) The copolymer (A-4) was obtained by alternate copolymerization of a vinyl group and a maleic anhydride with a vinyl group. Vinyl drop &#158665; the addition ratio of the alkene to the maleic anhydride is set to 1:1 (mole ratio), the polymerization reaction is carried out in tetrahydrofuran (THF), and azobisisobutyronitrile (AIBN) is used as The radical polymerization initiator was carried out at room temperature for 24 hours. The amount of AIBN used was set to 2.3 mol% based on the total amount of the monomer components. [Chemistry 13] More specifically, vinyl acetate &lt;158665; olefin 2000 mg and maleic anhydride 1640 mg were dissolved in 3 mL of THF, and 60 mg of AIBN was added as a radical polymerization initiator at 60 ° C. 24 hours reaction. After reprecipitation purification of diethyl ether, 3030 mg of a copolymer (A-4) was obtained as a white powder. The obtained copolymer (A-4) has a number average molecular weight Mn of 6.6 × 10 3 The molecular weight distribution Mw/Mn was 2.0. The obtained copolymer (A-4) was confirmed to be crosslinked by a diamine in the same manner as in Examples 1 to 6. [Comparative Example 1] The copolymer (A-1) obtained in Example 1 was not subjected to crosslinking by using a diamine for T. 10 The measurement is used, and the result is T 10 It is 144 °C. Thereby, it was confirmed that the heat resistance was remarkably improved by crosslinking with a diamine.

無no

Claims (5)

一種醯亞胺交聯型樹脂，其係利用二胺將具有環狀烯烴單元及不飽和二羧酸酐單元之共聚物交聯而成。A quinone imine crosslinked resin obtained by crosslinking a copolymer having a cyclic olefin unit and an unsaturated dicarboxylic anhydride unit by a diamine. 如請求項1之醯亞胺交聯型樹脂，其中上述環狀烯烴單元具有降&#158665;烷骨架。The imine cross-linking type resin according to claim 1, wherein the cyclic olefin unit has a reduced &#158665; alkane skeleton. 如請求項1或2之醯亞胺交聯型樹脂，其中上述不飽和二羧酸酐單元包含順丁烯二酸酐單元。The imine crosslinked type resin according to claim 1 or 2, wherein the unsaturated dicarboxylic anhydride unit comprises a maleic anhydride unit. 一種透明膜，其包含如請求項1至3中任一項之醯亞胺交聯型樹脂。A transparent film comprising the quinone imine crosslinked resin according to any one of claims 1 to 3. 一種表面保護膜，其具備： 如請求項4之透明膜；及 金屬蒸鍍層，其設置於上述透明膜之至少一個面上。A surface protective film comprising: the transparent film of claim 4; and a metal deposition layer provided on at least one surface of the transparent film.
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JP2020070340A (en) * 2018-10-31 2020-05-07 住友ベークライト株式会社 Polymer, resin composition and resin film
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