TW201809050A - Curable composition, cured film using said composition and overcoat film - Google Patents

Curable composition, cured film using said composition and overcoat film Download PDF

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TW201809050A
TW201809050A TW106112940A TW106112940A TW201809050A TW 201809050 A TW201809050 A TW 201809050A TW 106112940 A TW106112940 A TW 106112940A TW 106112940 A TW106112940 A TW 106112940A TW 201809050 A TW201809050 A TW 201809050A
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鈴木快
大賀一彦
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昭和電工股份有限公司
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/44—Polycarbonates
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
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  • Wood Science & Technology (AREA)
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  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

To provide a thermosetting resin composition which forms a protection film for flexible wiring boards, said protection film having excellent bending resistance and being sufficiently suppressed in warping, while maintaining high electrical insulation reliability under high temperature and high humidity conditions. A curable composition according to the present invention contains: (component A) a compound which has at least one structural unit represented by formula (A) and at least one of an imide bond and an amide bond; (component B) a curing agent; and (component C) an organic solvent. The (component A) contains a compound which is obtained by a reaction that uses, as essential components, (starting material a) a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group, (starting material b) a polyol represented by formula (2), and (starting material c) a polyisocyanate.

Description

硬化性組成物、使用該組成物之硬化膜及被覆膜 Curable composition, cured film and coating film using the same

本發明乃是關於：電氣絕緣性保護膜中所使用之新穎硬化性組成物、使用該組成物之可撓性配線板的保護膜之形成方法及可撓性配線板及電子零件、及該可撓性配線板之製造方法。 The present invention relates to a novel curable composition used in an electrical insulating protective film, a method for forming a protective film for a flexible wiring board using the composition, a flexible wiring board and an electronic part, and the same Manufacturing method of flexible wiring board.

近年來，電子零件的領域中，為了因應小型化、薄型化、高速化，電子零件中所使用之樹脂組成物(例如，封止劑、阻焊劑等)被要求要具有更優異的耐熱性、電氣特性及耐濕性。為此，構成樹脂組成物之樹脂方面，係可使用聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醯胺樹脂來取代環氧樹脂。但是，此等之樹脂乃是樹脂構造剛直且硬化膜欠缺柔軟性。因此，用於薄膜基材時，硬化後的基材會有容易大翹曲、彎曲性差等之問題。 In recent years, in the field of electronic components, in order to respond to miniaturization, thinning, and high speed, resin compositions (for example, sealants, solder resists, etc.) used in electronic components are required to have more excellent heat resistance, Electrical characteristics and humidity resistance. Therefore, in terms of the resin constituting the resin composition, polyimide resin, polyimide resin, and polyimide resin can be used instead of epoxy resin. However, these resins have rigid resin structures and lack flexibility in the cured film. Therefore, when it is used for a film substrate, there are problems that the substrate after curing is easily warped and has poor flexibility.

關於上述的樹脂，為了改善翹曲性及柔軟性，至今檢討了將樹脂改性進行可撓化及低彈性率化，且有各種改性聚醯胺醯亞胺樹脂被提案(例如，參考專利文獻1、2及3)。 Regarding the above-mentioned resins, in order to improve the warpage and softness, the modification of the resin has been reviewed for flexibility and low elasticity, and various modified polyamidoamine imine resins have been proposed (for example, refer to a patent Literatures 1, 2 and 3).

另外，專利文獻4中揭示有企圖改善低翹曲 性、可撓性、焊料耐熱性及耐錫鍍敷性之熱硬化性樹脂組成物。專利文獻4之熱硬化性樹脂組成物，乃是在高溫、高濕下維持高電氣特性之電氣絕緣特性中，具有卓越性能者。 In addition, Patent Document 4 discloses an attempt to improve low warpage Thermosetting resin composition with high flexibility, flexibility, solder heat resistance, and tin plating resistance. The thermosetting resin composition of Patent Document 4 has excellent performance in electrical insulation characteristics that maintain high electrical characteristics under high temperature and high humidity.

但是，近年來，伴隨配線的微細化，在其他場所實施將接續了可撓性配線板之顯示器面板安裝於筐體之際，輸送中會產生配線折斷的問題，所以具有對配線折斷之保護機能(以下稱為「耐彎曲性能」)的保護膜備受期望。 However, in recent years, with the miniaturization of wiring, when a display panel connected to a flexible wiring board is mounted on a casing in other places, the problem of wiring breakage occurs during transportation, so it has a protective function against wiring breakage. A protective film (hereinafter referred to as "bending resistance") is desired.

又，專利文獻5中揭示一種熱硬化性樹脂組成物，乃具有低翹曲性、可撓性、耐彎曲性能之企圖低翹曲性、可撓性及在高溫、高濕下的電氣絕緣特性者，其係包含：含有來自含脂環式二醇之構成單位的聚醯胺醯亞胺改性聚胺基甲酸酯樹脂。 In addition, Patent Document 5 discloses a thermosetting resin composition that has low warpage, flexibility, and bending resistance in an attempt to reduce warpage, flexibility, and electrical insulation characteristics under high temperature and high humidity. It includes a polyamidoamine imine-modified polyurethane resin containing a constituent unit derived from an alicyclic diol.

即使是此熱硬化性樹脂組成物，也並非是完全滿足市場期望的耐彎曲性能，而希望具有更高的耐彎曲性能之電氣絕緣性保護膜。 Even this thermosetting resin composition is not an electrical insulating protective film having higher bending resistance, which does not completely satisfy the bending resistance desired by the market.

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Literature]

〔專利文獻1〕日本特開昭62-106960號公報 [Patent Document 1] Japanese Patent Laid-Open No. 62-106960

〔專利文獻2〕日本特開平8-12763號公報 [Patent Document 2] Japanese Unexamined Patent Publication No. 8-12763

〔專利文獻3〕日本特開平7-196798號公報 [Patent Document 3] Japanese Unexamined Patent Publication No. 7-196798

〔專利文獻4〕日本特開2006-117922號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2006-117922

〔專利文獻5〕日本特開2015-147940號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2015-147940

但是，關於形成可撓性配線板的保護膜之樹脂，已改善了翹曲性及柔軟性之以往的樹脂組成物，在高溫、高濕下，水分子容易浸入，要維持高電氣特性有其難度。為了賦予高電氣特性，於樹脂構造中導入剛直成分且使其具有高玻璃轉移溫度被認為有效，但若依此手法，硬化後的基材容易大翹曲，且會發生彎曲性差等之問題。 However, as for the resin forming the protective film of the flexible wiring board, the conventional resin composition has improved warpage and flexibility. Under high temperature and high humidity, water molecules are easily infiltrated, and it is necessary to maintain high electrical characteristics. Difficulty. In order to impart high electrical characteristics, it is considered effective to introduce a rigid component into the resin structure and make it have a high glass transition temperature. However, if this method is used, the substrate after curing is easily warped, and problems such as poor bendability may occur.

專利文獻4中記載之熱硬化性樹脂組成物，雖然在低翹曲性、可撓性、焊料耐熱性及耐錫鍍敷性之點上被認為有某種程度上的改善，但是難以賦予對配線折斷之保護機能。又，專利文獻5中記載之熱硬化性樹脂組成物雖然具有某個程度的耐彎曲性能，但可說是還不足夠。 Although the thermosetting resin composition described in Patent Document 4 is considered to have improved to some extent in terms of low warpage, flexibility, solder heat resistance, and tin plating resistance, it is difficult to provide Protection function for broken wires. Moreover, although the thermosetting resin composition described in patent document 5 has some degree of bending resistance, it can be said that it is not enough.

因此，本發明係以提供一種於形成可撓性配線板的保護膜時，在高溫、高濕下可邊維持高電氣絕緣信賴性邊充分地控制翹曲，而且在耐彎曲性上表現亦優之熱硬化性樹脂組成物為主要目的。 Therefore, the present invention is to provide a protective film for a flexible wiring board, which can sufficiently control warpage while maintaining high electrical insulation reliability under high temperature and high humidity, and also has excellent performance in bending resistance. A thermosetting resin composition is a main purpose.

本發明者們為了解決上述課題而專致於重複研究的結果發現，因為具有特定的構造，同時，若將以具有醯亞胺鍵及醯胺鍵之至少1種鍵結的化合物作為必須成 分之硬化性組成物印刷於可撓性配線板上，則經印刷之硬化性組成物硬化時，其可撓性配線板的翹曲小，而包含此硬化性組成物的硬化物之保護膜在可撓性及長期電氣絕緣特性上表現優異，再者，被該保護膜所被覆著的可撓性配線板搖動時，會有很大的配線折斷之抑制效果，因而完成本發明。 The present inventors have devoted to repeated research in order to solve the above-mentioned problems, and found that it has a specific structure, and at the same time, if a compound having at least one kind of bond of a sulfonium imine bond and a sulfonium bond is used as a necessary compound When the hardened composition is printed on a flexible wiring board, when the printed hardened composition is hardened, the warpage of the flexible wiring board is small, and a protective film containing the hardened material of the hardened composition is provided. The present invention is excellent in flexibility and long-term electrical insulation characteristics. Furthermore, when the flexible wiring board covered with the protective film is shaken, the effect of suppressing the breakage of the wiring is great, and the present invention has been completed.

〔1〕一種硬化性組成物，其特徵係含有(成分A)下述至少具有1個以式(A)所示之構造單位，且具有醯亞胺鍵及醯胺鍵之至少1種鍵結，且具有與硬化劑反應之官能基的化合物、(成分B)硬化劑、及(成分C)有機溶劑。 [1] A hardenable composition characterized by containing (component A) at least one of the following structural units represented by formula (A), and having at least one kind of bond of a sulfonium imine bond and a sulfonium bond And a compound having a functional group that reacts with a hardener, (component B) a hardener, and (component C) an organic solvent.

波線，表示位於該構造之末端與其他構造之鍵結部位。 The wave line indicates the bonding position between the end of the structure and other structures.

〔2〕如〔1〕中記載之硬化性組成物，其中，前述與硬化劑反應之官能基係羧基、羥基、酸酐基、異氰酸基、醯胺基、胺基之至少1種。 [2] The curable composition according to [1], wherein the functional group that reacts with the curing agent is at least one of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, an amino group, and an amino group.

〔3〕如〔1〕或〔2〕中記載之硬化性組成物，其中，(成分A)係芳香環濃度為1.0~6.0mmol/g。 [3] The curable composition according to [1] or [2], wherein the (component A) -based aromatic ring concentration is 1.0 to 6.0 mmol / g.

〔4〕如〔1〕~〔3〕中任一項記載之硬化性組成物，其中，(成分A)含有：(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物、(原料b)下述一般式(1)、一般式(2)的至少1者所示之多元醇、(原料c)聚異氰酸酯、及(原料d)於原料中用下述式(A2)及/或(A3)使其反應所得之化合物。 [4] The curable composition according to any one of [1] to [3], wherein (component A) contains: (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group Substance, (raw material b) a polyol represented by at least one of the following general formula (1), general formula (2), (raw material c) polyisocyanate, and (raw material d): ) And / or (A3) a compound obtained by reacting it.

(式(1)中，(n+1)個的R1各自獨立地表示由碳數3~36之二醇所衍生的有機殘基，n個的R2各自獨立地表示芳香族系有機殘基、於芳香族系有機殘基上進一步具有取代基之有機殘基、由碳數3~36之二羧酸所衍生的有機殘基選出 的至少1個、n獨立地表示1~60之整數)。 (In formula (1), (n + 1) R 1 each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n R 2 each independently represent an aromatic organic residue. At least one selected from the group consisting of an organic residue further having a substituent on an aromatic organic residue, an organic residue derived from a dicarboxylic acid having 3 to 36 carbon atoms, and n independently represents an integer of 1 to 60 ).

(式(2)中，(m+1)個的R3各自獨立地表示由碳數3~36之二醇所衍生的有機殘基。m獨立地表示1~60之整數)。 (In formula (2), (m + 1) R 3 each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms. M independently represents an integer of 1 to 60).

(式(A2)中，q各自獨立地表示1~10之整數)。 (In formula (A2), q each independently represents an integer of 1 to 10).

(式(A3)中，p各自獨立地表示1~10之整數)。 (In the formula (A3), p each independently represents an integer of 1 to 10).

此外，〔4〕所規定的硬化性組成物中之(成 分A)係預先以(原料a)、(原料b)、(原料c)及(原料d)作為原料，相當於(原料a)、(原料b)、(原料c)及原料(d)之多數的化合物彼此可反應。又，若改變各種單體的摻合比或反應條件，所得的聚合物也會變化。因此，所得的成分A之構造極為多岐，以特定的構造來規定有其困難，這可說是熟知該領域之業者的技術常識。而且，構造如果無法特定，特性也無法規定。意即，〔4〕所規定的聚合組成物不可能以其構造或特性來予以特定，而藉由製程(製法)才可能得以特定，申請時，要以其構造或特性來直接特定該物是不可能的，或可考慮到大概是存在非實際性情事。 In addition, one of the hardening compositions specified in [4] Sub-A) uses (raw material a), (raw material b), (raw material c), and (raw material d) as raw materials, which is equivalent to (raw material a), (raw material b), (raw material c), and raw material (d). Most compounds are reactive with each other. In addition, if the blending ratio or reaction conditions of various monomers are changed, the polymer obtained will also change. Therefore, the structure of the obtained component A is extremely divergent, and it is difficult to specify a specific structure, which can be said to be a technical knowledge of those skilled in the art. Furthermore, if the structure cannot be specified, the characteristics cannot be specified. This means that the polymer composition specified in [4] cannot be specified by its structure or characteristics, but can only be specified by the manufacturing process (manufacturing method). When applying, it is necessary to directly specify the substance by its structure or characteristics. Impossible, or it can be taken into account that there may be impractical sexual affairs.

〔4'〕如〔1〕中記載之硬化性組成物，其中，(成分A)係含有：(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物、(原料b)下述一般式(1)、一般式(2)的至少1者所示之多元醇、(原料c)聚異氰酸酯及(原料d)使下述式(A2)及/或(A3)由原料所成之反應生成物。 [4 ' ] The curable composition according to [1], wherein (component A) contains: (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, and (raw material b) ) Polyols represented by at least one of the following general formula (1) and general formula (2), (raw material c) polyisocyanate, and (raw material d) use the following formulae (A2) and / or (A3) from raw materials The resulting reaction product.

〔5〕如〔1〕~〔4〕中任一項記載之硬化性組成物，其中，(成分A)係具有前述以式(A)所示之構造單位，且具有醯亞胺鍵及醯胺鍵之至少1種鍵結，又進一步具有胺基甲酸酯鍵之化合物。 [5] The curable composition according to any one of [1] to [4], wherein (ingredient A) has a structural unit represented by the formula (A), and has a 醯 imine bond and 醯A compound having at least one kind of amine bond and further having a urethane bond.

〔6〕如〔1〕~〔5〕中任一項記載之硬化性組成物，其中，(成分A)之酸價為10~50mgKOH/g。 [6] The curable composition according to any one of [1] to [5], wherein the acid value of (component A) is 10 to 50 mgKOH / g.

〔7〕如〔1〕~〔6〕中任一項記載之硬化性組成物， 其中，(成分B)包含每1分子具有2個以上環氧基之化合物。 [7] The hardening composition according to any one of [1] to [6], Among them, (component B) includes a compound having two or more epoxy groups per molecule.

〔8〕如〔1〕~〔7〕中任一項記載之硬化性組成物，其中，(成分C)係由醚系溶劑、酯系溶劑、酮系溶劑及芳香族烴系溶劑所成之群選出的至少1種之有機溶劑。 [8] The curable composition according to any one of [1] to [7], wherein (component C) is made of an ether-based solvent, an ester-based solvent, a ketone-based solvent, and an aromatic hydrocarbon-based solvent. Group of at least one organic solvent.

〔9〕如〔1〕~〔8〕中任一項記載之硬化性組成物，其中，進一步包含(成分D)由無機微粒子及有機微粒子所成之群選出的至少1種之微粒子。 [9] The curable composition according to any one of [1] to [8], further comprising (component D) at least one kind of fine particles selected from the group consisting of inorganic fine particles and organic fine particles.

〔10〕如〔1〕~〔9〕中任一項記載之硬化性組成物，其中，令成分(A)與成分(B)之合計量為100質量份時，包含1~55質量份之成分(B)。 [10] The curable composition according to any one of [1] to [9], wherein when the total amount of the component (A) and the component (B) is 100 parts by mass, 1 to 55 parts by mass is included. Ingredient (B).

〔11〕如〔1〕~〔10〕中任一項記載之硬化性組成物，其中，令成分(A)、成分(B)、成分(C)及成分(D)之合計量(不含成分(D)時，成分(A)、成分(B)及成分(C)之合計量)為100質量份時，包含25~75質量份之成分(C)。 [11] The curable composition according to any one of [1] to [10], wherein a total amount of the component (A), the component (B), the component (C), and the component (D) (excluding In the case of the component (D), when the total amount of the component (A), the component (B), and the component (C) is 100 parts by mass, 25 to 75 parts by mass of the component (C) is included.

〔12〕一種硬化膜，其特徵係包含前述〔1〕~〔11〕中任一項記載之硬化性組成物的硬化物。 [12] A cured film comprising a cured product of the curable composition according to any one of the above [1] to [11].

〔13〕一種可撓性配線板用被覆膜，其特徵係藉由將前述〔1〕~〔11〕中任一項記載之硬化性組成物塗佈於在可撓性基板上形成有配線而成的可撓性配線板之形成有配線的表面之一部分或全部，並予以硬化所得。 [13] A coating film for a flexible wiring board, characterized in that wiring is formed on a flexible substrate by applying the curable composition described in any one of [1] to [11] above. A part or all of the surface of the formed flexible wiring board on which wiring is formed is hardened.

〔14〕一種可撓性配線板，其特徵係在可撓性基板上形成有配線而成的可撓性配線板之形成有配線的表面之一 部分或全部，藉由前述〔13〕中記載之被覆膜所被覆而成。 [14] A flexible wiring board characterized in that it is one of the surfaces on which a wiring is formed on a flexible wiring board in which wiring is formed on a flexible substrate Part or all of them are covered with the coating film described in the above [13].

〔15〕如〔14〕中記載之可撓性配線板，其中，配線係錫鍍敷銅配線。 [15] The flexible wiring board according to [14], wherein the wiring is tin-plated copper wiring.

〔16〕一種藉由被覆膜所被覆之可撓性配線板之製造方法，其特徵係包含下述(步驟1)及(步驟3)與因應必要之(步驟2)：(步驟1)將前述〔1〕~〔11〕中任一項記載之硬化性組成物印刷於可撓性配線板之配線圖型部的至少一部分，而於該圖型上形成印刷膜之步驟、(步驟2)藉由將步驟1所得之印刷膜置於40~100℃之氛圍下，而使印刷膜中之溶劑的一部分或全量蒸發之步驟、(步驟3)藉由將步驟1所得之印刷膜或步驟2所得之印刷膜於100~170℃加熱，使其硬化並形成被覆膜之步驟。 [16] A method for manufacturing a flexible wiring board covered with a coating film, which includes the following (step 1) and (step 3) and (step 2) as necessary: (step 1) The step of printing the curable composition according to any one of the above [1] to [11] on at least a part of a wiring pattern portion of a flexible wiring board, and forming a printed film on the pattern, (step 2) The step of evaporating a part or the entire amount of the solvent in the printed film by placing the printed film obtained in step 1 under an atmosphere of 40 to 100 ° C. (step 3) The printed film obtained in step 1 or step 2 The step of heating the obtained printed film at 100 to 170 ° C. to harden it and form a coating film.

〔17〕一種電子零件，其特徵係具有前述〔12〕中記載之硬化膜。 [17] An electronic component characterized by having the hardened film described in [12] above.

此外，本說明書中記載之「(n+1)個的R1各自獨立地表示」之表現，意指(n+1)個的R1，即使是全部為相同的構造，一部分是相同構造且其他的一部分為不同的構造，全部為不同構造，等等的也沒關係。又，本說明書中記載之「n個的R2各自獨立地表示」及「(m+1)個的R3 各自獨立地表示」等表現，也同樣地意指n個的R2及(m+1)個的R3，即使是全部為相同的構造，一部分是相同構造且其他的一部分為不同的構造，全部為不同構造，等等的也沒關係。 Furthermore, described in the present specification, "(n + 1) th, R 1 each independently represent a" performance, the means (n + 1) th R 1, even if all the same structure, and a portion of the same configuration The other parts are different structures, all are different structures, etc. It doesn't matter. In addition, expressions such as "n R 2 are each independently represented" and "(m + 1) R 3 are each independently represented" described in the present specification also mean n R 2 and (m It does not matter that +1) of R 3 are all the same structure, some are the same structure and others are different structures, all are different structures, and so on.

藉由將本發明之硬化性組成物予以硬化，可獲得低翹曲性、可撓性、長期絕緣信賴性優異的硬化膜，將該硬化膜作為保護膜進行被覆，在可撓性配線板動搖時可增大配線折斷之抑制效果。 By curing the curable composition of the present invention, a cured film having low warpage, flexibility, and long-term insulation reliability can be obtained. The cured film is covered as a protective film, and the flexible wiring board is shaken. It can increase the effect of suppressing the break of the wiring.

又，本發明可提供一種由前述硬化性組成物的硬化物所成之保護膜，以及藉由該保護膜所被覆之可撓性配線板，其係可邊維持高絕緣信賴性邊充分地抑制翹曲且同時彎曲性亦優的可撓性配線板。 Further, the present invention can provide a protective film made of a cured product of the hardenable composition, and a flexible wiring board covered with the protective film, which is capable of being sufficiently suppressed while maintaining high insulation reliability. A flexible wiring board that is warped and has excellent bendability.

〔實施發明之形態〕 [Form of Implementing Invention]

以下，謹就本發明之較佳的實施形態來詳細說明。惟，本發明並不受限於以下的實施形態。 Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

硬化性組成物 Hardening composition

本發明之硬化性組成物，係以含有下述成分為其特徵：(成分A)下述至少具有1個以式(A)所示之構造單位，且具有醯亞胺鍵及醯胺鍵之至少1種鍵結，且具有與 硬化劑反應之官能基的化合物、(成分B)硬化劑、及(成分C)有機溶劑。 The curable composition of the present invention is characterized by containing the following components: (component A) The following has at least one structural unit represented by the formula (A), and has a sulfonium imine bond and a sulfonium bond At least 1 bond and has A functional group-reactive compound, (component B) a curing agent, and (component C) an organic solvent.

波線(在以後的式中亦相同)，表示位於該構造之末端與其他構造之鍵結部位。 The wave line (also the same in the following formulas) indicates the position where the end of the structure is bonded to other structures.

(成分A) (Ingredient A)

作為本發明之硬化性組成物的必須成分之(成分A)，乃具有以式(A)所示之構造單位，且具有醯亞胺鍵及醯胺鍵(-C(=O)-NH-)之至少1方的鍵結之化合物。 (Component A), which is an essential component of the curable composition of the present invention, has a structural unit represented by the formula (A), and has a fluorene imine bond and a fluorene bond (-C (= O) -NH- ) At least one side of the bonded compound.

(成分A)亦可進一步具有胺基甲酸酯鍵(-O-C(=O)-NH-)。再者，(成分A)具有與硬化劑反應之官能基。可與硬化劑反應的較佳官能基方面，可舉出羧基、羥基、酸酐基、異氰酸基、醯胺基、胺基之至少1種的官能基。具有異氰酸基時，異氰酸基係以封端化劑所保護者為佳。又在其他的基中，既可以封端化劑所保護，且封端體脫離而反應者乃被視為官能基。 (Component A) may further have a urethane bond (-O-C (= O) -NH-). Moreover, (component A) has a functional group which reacts with a hardener. As a preferable functional group which can react with a hardening | curing agent, the functional group of at least 1 sort (s) of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, an amino group, and an amino group is mentioned. When having an isocyanate group, the isocyanate group is preferably protected by a blocking agent. And in other groups, it can be protected by a blocking agent, and the blocking body is detached and the reactant is regarded as a functional group.

若具有醯亞胺鍵及醯胺鍵之至少1種鍵結，而且以式(A)所示之構造單位作為必須成分的話，硬化性組成物硬化時的硬化物之收縮會變少，且硬化膜本身具有可撓性高、耐彎曲性優異的效果。 If there is at least one kind of bond between a sulfonium imine bond and a sulfonium bond, and if the structural unit represented by the formula (A) is used as an essential component, the shrinkage of the hardened material when the hardening composition is hardened will be reduced, and the hardening will be hardened. The film itself has the effects of high flexibility and excellent bending resistance.

作為本發明之硬化性組成物的必須成分之(成分A)之芳香環濃度，係以1.0~6.0mmol/g者為佳，最佳為1.5~5.0mmol/g。若為6.0mmol/g以下，則可兼具翹曲與耐彎曲性。又，若為1.0mmol/g以上時，可得充分的耐彎曲性。所謂的芳香環濃度意指每1g該化合物之芳香環的數目(mmol)。此外，芳香環濃度是由置入比算出來的，藉由1H-NMR、13C-NMR及IR決定構造之後，可藉由比較1H-NMR之來自芳香環的質子數與來自單元的質子 數(以1H-NMR之積分曲線來比較)進行解析。 The aromatic ring concentration (component A), which is an essential component of the curable composition of the present invention, is preferably 1.0 to 6.0 mmol / g, and most preferably 1.5 to 5.0 mmol / g. When it is 6.0 mmol / g or less, both warpage and bending resistance can be achieved. When it is 1.0 mmol / g or more, sufficient bending resistance can be obtained. The so-called aromatic ring concentration means the number (mmol) of aromatic rings per 1 g of the compound. In addition, the aromatic ring concentration is calculated from the insertion ratio. After the structure is determined by 1 H-NMR, 13 C-NMR, and IR, the number of protons from the aromatic ring and the units from the unit can be compared by 1 H-NMR. The number of protons (compared by the integral curve of 1 H-NMR) was analyzed.

此外，本說明書之芳香環的數，係如下述般，如式(51)之苯環乃計數1個芳香環的數目。如式(52)之聯苯基構造及式(53)之9H-茀構造，因有2個苯環2，乃計數2個芳香環的數目。如式(54)之萘構造可計數2個芳香環的數目。同樣地蒽構造(式(55))或菲構造(式(56))乃計數3個芳香環的數目。聯伸三苯構造(式(77))或聯萘構造(式(58))則計數4個芳香環的數目。 In addition, the number of aromatic rings in this specification is as follows, and the number of one aromatic ring is counted as a benzene ring of Formula (51). For example, the biphenyl structure of formula (52) and the 9H-fluorene structure of formula (53), because there are two benzene rings 2, the number of two aromatic rings is counted. The naphthalene structure of formula (54) can count the number of 2 aromatic rings. Similarly, the anthracene structure (formula (55)) or the phenanthrene structure (formula (56)) counts the number of three aromatic rings. The number of four aromatic rings is counted in the triphenylene structure (Formula (77)) or the binaphthyl structure (Formula (58)).

此外，式(51')~式(58')之○的數目各自表示式(51)~式(58)之芳香環的數目。 In addition, the number of ○ in Formula (51 ' ) to Formula (58 ' ) each represents the number of aromatic rings in Formula (51) to Formula (58).

(成分A)可舉出包含下述者：(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物、(原料b)一般式(1)、一般式(2)的至少1者所示之多元醇、(原料c)聚異氰酸酯、(原料d)使式(A2)及/或(A3)作為原料之反應生成物。 (Component A) Examples include (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (raw material b) a general formula (1), a general formula (2) A reaction product of at least one of the polyol, (raw material c) polyisocyanate, and (raw material d) using formula (A2) and / or (A3) as raw materials.

接著，就該(成分A)的合成方法進行說明。(成分A)例如可以下述方法1~3來合成。 Next, a method for synthesizing (component A) will be described. (Component A) can be synthesized, for example, by the following methods 1 to 3.

(方法1) (method 1)

使(原料b)下述一般式(1)、一般式(2)的至少1 者所示之多元醇 Make (raw material b) at least 1 of the following general formula (1) and general formula (2) Polyol

(式(1)中，(n+1)個的R1各自獨立地表示由碳數3~36之二醇所衍生的有機殘基，n個的R2各自獨立地表示芳香族系有機殘基、於芳香族系有機殘基上進一步具有取代基之有機殘基、由碳數3~36之二羧酸所衍生的有機殘基選出的至少1個、n獨立地表示1~60之整數) (In formula (1), (n + 1) R 1 each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n R 2 each independently represent an aromatic organic residue. At least one selected from the group consisting of an organic residue further having a substituent on an aromatic organic residue, an organic residue derived from a dicarboxylic acid having 3 to 36 carbon atoms, and n independently represents an integer of 1 to 60 )

(式(2)中，m+1個的R3各自獨立地表示由碳數3~36之二醇所衍生的有機殘基。m獨立地表示1~60之整數)及(原料d)式(A2)及/或式(A3)之二醇化合物， (式(A2)中，q各自獨立地表示1~10之整數。較佳的q方面，為1~4之整數，特別佳為1~2之整數，q的平均值係以1~4為佳，更佳為1或2) (In formula (2), m + 1 R 3 each independently represents an organic residue derived from a diol having 3 to 36 carbon atoms. M independently represents an integer of 1 to 60) and (raw material d) formula (A2) and / or a diol compound of formula (A3), (In the formula (A2), q each independently represents an integer of 1 to 10. The preferred aspect of q is an integer of 1 to 4, particularly preferably an integer of 1 to 2. The average value of q is 1 to 4 as Good, more preferably 1 or 2)

(式(A3)中，p各自獨立地表示1~10之整數。較佳的p方面，為1~4之整數，特別佳為1~2之整數，p的平均值係以1~4為佳，更佳為1或2) (In the formula (A3), p each independently represents an integer of 1 to 10. The preferred aspect of p is an integer of 1 to 4, particularly preferably an integer of 1 to 2. The average value of p is 1 to 4 as Good, more preferably 1 or 2)

與(原料c)聚異氰酸酯反應，得到具有胺基甲酸酯鍵且末端具有異氰酸基之聚異氰酸酯化合物，並使所得之含有具有胺基甲酸酯鍵且末端具有異氰酸基之化合物之聚異氰酸酯化合物與(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物反應。 Reacting with (raw material c) polyisocyanate to obtain a polyisocyanate compound having a urethane bond and having an isocyanate group at the terminal, and allowing the obtained compound to have a urethane bond and having an isocyanate group at the terminal The polyisocyanate compound is reacted with (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group.

(方法2) (Method 2)

使(原料c)聚異氰酸酯與(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物反應，得到具有醯亞胺鍵及醯胺鍵之至少1種鍵結且於末端具有異氰酸基之聚異氰酸酯，並對此，使(原料b)前述一般式(1)、一般式(2)的至少1者所示之多元醇及(原料d)前述式(A2)及/或(A3)所示之二醇化合物反應。 The (raw material c) polyisocyanate is reacted with the (raw material a) trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group to obtain at least one kind of bond having a sulfonium imine bond and a sulfonium bond at the end For the polyisocyanate having an isocyanate group, (Polymer b) the polyol represented by at least one of the general formula (1) and the general formula (2) and (raw material d) the formula (A2) and And / or the diol compound represented by (A3) is reacted.

(方法3) (Method 3)

使(原料c)聚異氰酸酯與(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物反應，得到具有醯亞胺鍵及醯胺鍵之至少1種鍵結且末端具有酸酐基及/或羧基的化合物，並對此，使(原料b)前述一般式(1)、一般式(2)的至少1者所示之多元醇及(原料d)前述式(A2)及/或(A3)所示之二醇反應。 The (raw material c) polyisocyanate is reacted with the (raw material a) trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group to obtain at least one kind of bond having a fluorene imine bond and a fluorene bond, and having A compound of an acid anhydride group and / or a carboxyl group, and in this regard, (raw material b) a polyol represented by at least one of the general formula (1) and general formula (2) and (raw material d) the formula (A2) and And / or the diol shown in (A3).

(方法1) (method 1)

方法1的合成法，首先，係使(原料b)前述一般式(1)、一般式(2)的至少1者所示之多元醇及(原料d)前述式(A2)及/或式(A3)之二醇化合物與(原料c)聚異氰酸酯反應，合成具有胺基甲酸酯鍵且末端具有異氰酸基之聚異氰酸酯化合物(以下記為「(A1-1)化合物」)。 The synthesis method of method 1 first comprises using a polyol represented by at least one of the aforementioned general formula (1) and (2) and (raw material d) the aforementioned formula (A2) and / or formula ((b) The diol compound of A3) reacts with (raw material c) polyisocyanate to synthesize a polyisocyanate compound (hereinafter referred to as "(A 1 -1) compound") having a urethane bond and an isocyanate group at the terminal.

構成原料(b)之多元醇係如式(1)或一般式(2)所示。 The polyol constituting the raw material (b) is represented by formula (1) or general formula (2).

式(1)中，(n+1)個的R1各自獨立地表示由具有3~36個的碳原子之二醇所衍生的有機殘基。換言之，上述所謂由二醇所衍生的有機殘基，係由二醇去掉2個羥基所得之2價的基。 In formula (1), (n + 1) R 1 each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms. In other words, the above-mentioned organic residue derived from a diol is a divalent group obtained by removing two hydroxyl groups from a diol.

具有3~36個的碳之二醇方面，可舉例如1,3-丙烷二醇、1,2-丙烷二醇、1,4-丁烷二醇、2-甲基-1,3-丙烷二醇、1,5-戊烷二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇、1,8-辛烷二醇、1,9-壬烷二醇、2-甲基-1,8-辛烷二醇、1,9-壬烷二醇、1,10-癸烷二醇、1,12-十二烷二醇、氫化二聚物(C36)二醇、二乙二醇、三乙二醇等之鏈狀的二醇、 1,2-環戊烷二甲醇、1,3-環戊烷二甲醇及雙(羥基甲基)三環〔5.2.1.0〕癸烷等之5員環二醇、以及1,2-環己烷二醇、1,3-環己烷二醇、1,4-環己烷二醇、1,2-環己烷二甲醇、1,3-環己烷二甲醇、1,4-環己烷二甲醇、及2,2-雙(4-羥基環己基)-丙烷等之6員環二醇等之具有脂環構造之二醇等。R1係由此等之二醇去掉末端羥基之構造。 Examples of diols having 3 to 36 carbons include 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and 2-methyl-1,3-propane Diol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonane Diol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydrogenated dimer ( C36) Chain diols such as diols, diethylene glycol, and triethylene glycol, 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, and bis (hydroxymethyl) tricyclic [5.2.1.0] 5-membered cyclodiols such as decane, and 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2- 6-membered cyclodiols such as cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 2,2-bis (4-hydroxycyclohexyl) -propane A diol having an alicyclic structure. R 1 is a structure in which a terminal hydroxy group is removed from such a diol.

R1的較佳例方面，係碳數為3~18且鏈狀構造之2價的烴基，更佳例方面，係碳數4~9且鏈狀構造之2價的烴基，特別佳的例子方面，係碳數4~6且鏈狀構造之2價的烴基。意即，可衍生R1之有機殘基的較佳二醇方面，可舉例如1,3-丙烷二醇、1,2-丙烷二醇、1,4-丁烷二醇、2-甲基-1,3-丙烷二醇、1,5-戊烷二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇、1,8-辛烷二醇、1,9-壬烷二醇、2-甲基-1,8- 辛烷二醇、1,9-壬烷二醇、1,10-癸烷二醇，更佳的二醇方面，可舉例如1,4-丁烷二醇、2-甲基-1,3-丙烷二醇、1,5-戊烷二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇、1,8-辛烷二醇、1,9-壬烷二醇、2-甲基-1,8-辛烷二醇、1,9-壬烷二醇，特別佳的二醇方面，可舉例如1,4-丁烷二醇、2-甲基-1,3-丙烷二醇、1,5-戊烷二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇，最佳的二醇方面，為1,6-己烷二醇、3-甲基-1,5-戊烷二醇。 A preferred example of R 1 is a divalent hydrocarbon group having 3 to 18 carbon atoms and a chain structure, and a more preferable example is a divalent hydrocarbon group having 4 to 9 carbon atoms and a chain structure. Particularly preferred examples On the one hand, it is a bivalent hydrocarbon group having 4 to 6 carbon atoms and a chain structure. In other words, preferred diols from which organic residues of R 1 can be derived include, for example, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-methyl -1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and more preferable diols, for example Such as 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5- Pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, particularly preferred Examples of the alcohol include 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl -1,5-pentanediol. The best diols are 1,6-hexanediol and 3-methyl-1,5-pentanediol.

又，式(1)中，n個的R2各自獨立地表示由2價的芳香族基或具有取代基之2價的芳香族基、由碳數3~36之二羧酸所衍生的有機殘基選出的至少1種。 In formula (1), n R 2 each independently represent an organic group derived from a divalent aromatic group or a divalent aromatic group having a substituent, and a dicarboxylic acid having 3 to 36 carbon atoms. At least one residue is selected.

構成R2之2價的芳香族基方面，可舉出伸苯基或具有取代基之伸苯基為佳。伸苯基方面，可舉例如1,2-伸苯基、1,3-伸苯基、1,4-伸苯基。具有取代基之伸苯基的取代基方面，可舉出碳數1~10之烷基，具體而言，可舉出3-甲基-1,2-伸苯基、4-甲基-1,2-伸苯基、4-甲基-1,3-伸苯基、2-甲基-1,4-伸苯基、3-乙基-1,2-伸苯基、4-乙基-1,2-伸苯基、4-乙基-1,3-伸苯基、2-乙基-1,4-伸苯基等作為取代基之具有烷基的伸苯基、3-溴-1,2-伸苯基、4-溴-1,2-伸苯基、4-溴-1,3-伸苯基、2-溴-1,4-伸苯基、3-氯-1,2-伸苯基、4-氯-1,2-伸苯基、4-氯-1,3-伸苯基、2-氯-1,4-伸苯基等之具有鹵素的伸苯基。構成R2之碳數3~36之二羧酸的殘基方面，具體而言，可舉出丙二酸、琥珀酸、己二酸、癸二酸、十二烷二酸、工廿烷二酸、二聚酸、馬 來酸、苯二甲酸、異苯二甲酸、蘋果酸、酒石酸等之殘基。二羧酸殘基之R2係由此等之二羧酸去掉末端羧基之構造之實質上可例示出與R1相同的2價烴基。 As the divalent aromatic group constituting R 2 , a phenylene group or a phenylene group having a substituent is preferred. Examples of the phenylene include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene. Examples of the substituent of the phenyl group having a substituent include an alkyl group having 1 to 10 carbon atoms, and specifically, 3-methyl-1,2-phenylene and 4-methyl-1 2,2-phenylene, 4-methyl-1,3-phenylene, 2-methyl-1,4-phenylene, 3-ethyl-1,2-phenylene, 4-ethyl 1,2-phenylene, 4-ethyl-1,3-phenylene, 2-ethyl-1,4-phenylene, etc. as the substituents, alkylene with alkyl groups , 3-bromo-1,2-phenylene, 4-bromo-1,2-phenylene, 4-bromo-1,3-phenylene, 2-bromo-1,4-phenylene, 3 -Chloro-1,2-phenylene, 4-chloro-1,2-phenylene, 4-chloro-1,3-phenylene, 2-chloro-1,4-phenylene with halogen Phenylene. As the residue of a dicarboxylic acid having 3 to 36 carbon atoms constituting R 2 , specifically, malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and cokerane di Residues of acids, dimer acids, maleic acid, phthalic acid, isophthalic acid, malic acid, tartaric acid, etc. R 2 of the dicarboxylic acid residue is a structure in which a terminal carboxyl group is removed from such a dicarboxylic acid, and a divalent hydrocarbon group substantially the same as R 1 can be exemplified.

此等之中，R2方面，較佳為1,2-伸苯基、1,3-伸苯基、1,4-伸苯基及作為取代基之具有烷基的伸苯基，更佳為1,2-伸苯基、1,3-伸苯基、1,4-伸苯基，特別佳為1,2-伸苯基、1,3-伸苯基。 Among these, in terms of R 2 , 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and a phenylene group having an alkyl group as a substituent are more preferable. It is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and particularly preferably 1,2-phenylene and 1,3-phenylene.

又，最佳的R1與R2的組合，係當R1為1,2-伸苯基時，R2為1,6-己烷二醇、3-甲基-1,5-戊烷由二醇所衍生的有機殘基，R1為1,3-伸苯基時，R2為3-甲基-1,5-戊烷由二醇所衍生的有機殘基。 The best combination of R 1 and R 2 is when R 1 is 1,2-phenylene, and R 2 is 1,6-hexanediol, 3-methyl-1,5-pentane. For a diol-derived organic residue, when R 1 is 1,3-phenylene, R 2 is a 3-methyl-1,5-pentane-derived organic residue.

n表示1~60之整數。較佳的n方面，為1~45之整數，特別佳為1~30之整數。n的平均值係以3~11為佳，更佳為5~10。 n represents an integer from 1 to 60. The preferred n aspect is an integer of 1 to 45, particularly preferably an integer of 1 to 30. The average value of n is preferably from 3 to 11, more preferably from 5 to 10.

具有3~36個的碳之二醇方面，可舉例如1,3-丙烷二醇、1,2-丙烷二醇、1,4-丁烷二醇、2-甲基-1,3-丙烷二醇、1,5-戊烷二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇、1,8-辛烷二醇、1,9-壬烷二醇、2-甲基-1,8-辛烷二醇、1,9-壬烷二醇、1,10-癸烷二醇、1,12-十二烷二醇、氫化二聚物(C36)二醇、二乙二醇、三乙二醇等之鏈狀的二醇、 1,2-環戊烷二甲醇、1,3-環戊烷二甲醇及雙(羥基甲基)三環〔5.2.1.0〕癸烷等之5員環二醇、以及1,2-環己烷二醇、1,3-環己烷二醇、1,4-環己烷二醇、1,2-環己烷二甲 醇、1,3-環己烷二甲醇、1,4-環己烷二甲醇、及2,2-雙(4-羥基環己基)-丙烷等之6員環二醇等之具有脂環構造之二醇等。 Examples of diols having 3 to 36 carbons include 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and 2-methyl-1,3-propane Diol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonane Diol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydrogenated dimer ( C36) chain diols such as diols, diethylene glycol, and triethylene glycol, 5-membered cyclodiols such as 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, bis (hydroxymethyl) tricyclo [5.2.1.0] decane, and 1,2-cyclohexane Alkanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethylamine 6-membered cyclic diols such as alcohols, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 2,2-bis (4-hydroxycyclohexyl) -propane, etc. have alicyclic structures Diols, etc.

R3的較佳例方面，係碳數為3~18且鏈狀構造之2價的烴基，更佳例方面，係碳數4~9且鏈狀構造之2價的烴基，特別佳的例子方面，係碳數4~6且鏈狀構造之2價的烴基。意即，可衍生R3之有機殘基的較佳二醇方面，可舉例如1,3-丙烷二醇、1,2-丙烷二醇、1,4-丁烷二醇、2-甲基-1,3-丙烷二醇、1,5-戊烷二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇、1,8-辛烷二醇、1,9-壬烷二醇、2-甲基-1,8-辛烷二醇、1,9-壬烷二醇、1,10-癸烷二醇，更佳的二醇方面，可舉例如1,4-丁烷二醇、2-甲基-1,3-丙烷二醇、1,5-戊烷二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇、1,8-辛烷二醇、1,9-壬烷二醇、2-甲基-1,8-辛烷二醇、1,9-壬烷二醇，特別佳的二醇方面，可舉例如1,4-丁烷二醇、2-甲基-1,3-丙烷二醇、1,5-戊烷二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇，最佳的二醇方面，為1,6-己烷二醇、3-甲基-1,5-戊烷二醇。 A preferred example of R 3 is a divalent hydrocarbon group having a carbon number of 3 to 18 and a chain structure, and a more preferable example is a bivalent hydrocarbon group having a carbon number of 4 to 9 and a chain structure. A particularly preferable example On the one hand, it is a bivalent hydrocarbon group having 4 to 6 carbon atoms and a chain structure. In other words, preferred diols from which organic residues of R 3 can be derived include, for example, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-methyl -1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and more preferable diols, for example Such as 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5- Pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, particularly preferred Examples of the alcohol include 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl -1,5-pentanediol. The best diols are 1,6-hexanediol and 3-methyl-1,5-pentanediol.

m表示1~60之整數。較佳的m方面，為1~45之整數，特別佳為1~30之整數，m的平均值係以3~11為佳，更佳為5~10。 m represents an integer from 1 to 60. The preferred m is an integer from 1 to 45, particularly preferably an integer from 1 to 30. The average value of m is preferably from 3 to 11, and more preferably from 5 to 10.

一般式(1)、一般式(2)之二醇的數平均分子量係以500~5000者為佳，750~4000者更佳，1000~3000者特別佳。 The number average molecular weight of the diols of general formula (1) and general formula (2) is preferably 500 to 5000, more preferably 750 to 4000, and particularly preferably 1,000 to 3000.

(原料d)方面所使用的式(A2)及/或(A3)所示之化合物係如前述。 The compound represented by formula (A2) and / or (A3) used in (raw material d) is as described above.

(原料c)方面，可使用使(原料b)及(原料d)反應之聚異氰酸酯。(原料c)聚異氰酸酯方面，若為具有2個以上異氰酸基之化合物，並無特別限制。聚異氰酸酯的具體例方面，可舉出1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、異佛爾酮二異氰酸酯、4,4'-二環己基甲烷二異氰酸酯、1,3-雙(異氰酸基甲基)環己烷、1,4-雙(異氰酸基甲基)環己烷、降冰片烯二異氰酸酯及異佛爾酮二異氰酸酯的雙脲體等之環狀脂肪族聚異氰酸酯； 二苯基甲烷-2,4'-二異氰酸酯、3,2'-二甲基二苯基甲烷-2,4'-二異氰酸酯、3,3'-二甲基二苯基甲烷-2,4'-二異氰酸酯、4,2'-二甲基二苯基甲烷-2,4'-二異氰酸酯、4,3'-二甲基二苯基甲烷-2,4'-二異氰酸酯、5,2'-二甲基二苯基甲烷-2,4'-二異氰酸酯、5,3'-二甲基二苯基甲烷-2,4'-二異氰酸酯、6,2'-二甲基二苯基甲烷-2,4'-二異氰酸酯、6,3'-二甲基二苯基甲烷-2,4'-二異氰酸酯、3,2'-二乙基二苯基甲烷-2,4'-二異氰酸酯、3,3'-二乙基二苯基甲烷-2,4'-二異氰酸酯、4,2'-二乙基二苯基甲烷-2,4'-二異氰酸酯、4,3'-二乙基二苯基甲烷-2,4'-二異氰酸酯、5,2'-二乙基二苯基甲烷-2,4'-二異氰酸酯、5,3'-二乙基二苯基甲烷-2,4'-二異氰酸酯、6,2'-二乙基二苯基甲烷-2,4'-二異氰酸酯、6,3'-二乙基二苯基甲烷-2,4'-二異氰酸酯、3,2'-二甲氧基二苯基甲烷-2,4'-二異氰酸酯、3,3'-二甲氧基二苯基甲烷-2,4'-二 異氰酸酯、4,2'-二甲氧基二苯基甲烷-2,4'-二異氰酸酯、4,3'-二甲氧基二苯基甲烷-2,4'-二異氰酸酯、5,2'-二甲氧基二苯基甲烷-2,4'-二異氰酸酯、5,3'-二甲氧基二苯基甲烷-2,4'-二異氰酸酯、6,2'-二甲氧基二苯基甲烷-2,4'-二異氰酸酯、6,3'-二甲氧基二苯基甲烷-2,4'-二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、二苯基甲烷-3,3'-二異氰酸酯、二苯基甲烷-3,4'-二異氰酸酯、二苯基醚-4,4'-二異氰酸酯、二苯甲酮-4,4'-二異氰酸酯、二苯基碸-4,4'-二異氰酸酯、2,4-三氯乙烯二異氰酸酯、2,6-三氯乙烯二異氰酸酯、m-二甲伸苯基二異氰酸酯、p-二甲伸苯基二異氰酸酯、1,5-萘二異氰酸酯、4,4'-〔2,2雙(4-苯氧基苯基)丙烷〕二異氰酸酯等具有芳香環之聚異氰酸酯；六亞甲基二異氰酸酯的雙脲體、離胺酸三異氰酸酯、離胺酸二異氰酸酯、六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯及2,2,4-三甲基己烷亞甲基二異氰酸酯鏈狀脂肪族聚異氰酸酯；異佛爾酮二異氰酸酯的異三聚氰酸酯體、六亞甲基二異氰酸酯的異三聚氰酸酯體等具有雜環之聚異氰酸酯等，可將此等單獨使用，亦可組合2種以上使用。 As for (raw material c), a polyisocyanate which reacts (raw material b) and (raw material d) can be used. (Raw material c) In the case of a polyisocyanate, it is not particularly limited as long as it is a compound having two or more isocyanate groups. Polyisocyanate Specific examples of the aspects may include 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4 '- dicyclohexylmethane diisocyanate, 1 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, norurene diisocyanate and diurea of isophorone diisocyanate, etc. the cyclic aliphatic polyisocyanate; diphenylmethane-2,4 '- diisocyanate, 3,2' - dimethyl-diphenylmethane-2,4 '- diisocyanate, 3,3' - dimethyl diphenylmethane 2,4 '- diisocyanate, 4,2' - dimethyl-diphenylmethane-2,4 '- diisocyanate, 4,3' - dimethyl-diphenylmethane-2,4 '- diisocyanate, 5,2' - dimethyl-diphenylmethane-2,4 '- diisocyanate, 5,3' - dimethyl-diphenylmethane-2,4 '- diisocyanate, 6,2 '- dimethyl-diphenylmethane-2,4' - diisocyanate, 6,3 '- dimethyl-diphenylmethane-2,4' - diisocyanate, 3,2 '- diethyl diphenyl methane-2,4 '- diisocyanate, 3,3' - diphenylmethane-diethyl-2,4 '- diisocyanate, 4,2' - diethyl diphenyl Methane-2,4 '- diisocyanate, 4,3' - diphenylmethane-diethyl-2,4 '- diisocyanate, 5,2' - diphenylmethane-diethyl-2,4 '- diisocyanate, 5,3 '- diphenylmethane-diethyl-2,4' - diisocyanate, 6,2 '- diphenylmethane-diethyl-2,4' - diisocyanate, 6,3 '- diethyl diphenylmethane-2,4 '- diisocyanate, 3,2' - diphenylmethane-dimethoxy-2,4 '- diisocyanate, 3,3' - dimethoxy diphenyl methane-2,4 '- diisocyanate, 4,2' - diphenylmethane-dimethoxy-2,4 '- diisocyanate, 4,3' - diphenylmethane-2,4-dimethoxy ' - diisocyanate, 5,2 '- diphenylmethane-dimethoxy-2,4' - diisocyanate, 5,3 '- diphenylmethane-dimethoxy-2,4' - diisocyanate, 6, 2 '- diphenylmethane-dimethoxy-2,4' - diisocyanate, 6,3 '- diphenylmethane-dimethoxy-2,4' - diisocyanate, 4,4 '- diphenyl methane diisocyanate, diphenylmethane 3,3 '- diisocyanate, diphenylmethane 3,4' - diisocyanate, diphenylether-4,4 '- diisocyanate, benzophenone-4, 4 '- diisocyanate, Phenyl sulfone 4,4 '- diisocyanate, 2,4-diisocyanate trichlorethylene, TCE 2,6-diisocyanate, m- phenylene diisocyanate, dimethyl diisocyanate, p-phenylene-dimethoxyphenyl two Polyisocyanates with aromatic rings such as isocyanate, 1,5-naphthalene diisocyanate, 4,4 ' -[2,2bis (4-phenoxyphenyl) propane] diisocyanate; bisurea of hexamethylene diisocyanate Polymer, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and 2,2,4-trimethylhexane methylene Diisocyanate chain aliphatic polyisocyanate; isoisocyanate of isophorone diisocyanate, isotricyanate of hexamethylene diisocyanate, and other polyisocyanates with heterocyclic rings. These can be used alone or in combination of two or more.

若考慮所合成之具有胺基甲酸酯鍵且末端具有異氰酸基之化合物，與此後使其反應之(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物的反應性，此等之中，較佳者為具有芳香環之聚異氰酸酯，更佳為二苯基甲烷-4,4'-二異氰酸酯、二苯基甲烷-3,3'-二異氰酸酯、二苯 基甲烷-3,4'-二異氰酸酯、二苯基醚-4,4'-二異氰酸酯等具有芳香環之聚異氰酸酯，最佳為二苯基甲烷-4,4'-二異氰酸酯。 If a compound having a urethane bond and an isocyanate group at its terminal is considered, the reaction of (the raw material a) a trivalent and / or a tetravalent polycarboxylic acid derivative having an anhydride group reactivity, among these, preferred are the polyisocyanate having an aromatic rings, more preferably diphenylmethane 4,4 '- diisocyanate, diphenylmethane 3,3' - diisocyanate, diphenyl methane-3,4 '- diisocyanate, diphenylether-4,4' - diisocyanate, and the like having an aromatic ring of poly isocyanate, most preferably diphenylmethane 4,4 '- diisocyanate.

又，聚異氰酸酯為了避免經日變化，異氰酸基係可以封端劑來予以安定化。封端劑方面，可舉出以羥基丙烯酸酯、甲醇、丁酮肟為代表之醇、苯酚、肟，並無特別限制。 In addition, in order to prevent the polyisocyanate from changing over time, an isocyanate group can be stabilized by a blocking agent. As the capping agent, alcohols, phenols, and oximes typified by hydroxyacrylate, methanol, and butanone oxime are not particularly limited.

(原料d)之二醇化合物與(原料b)之多元醇的混合比率，雖可適當地選擇最終所導入之式A的構造單位之量，但最終的成分A中，芳香環濃度係如前述，可混合成為如1.0~6.0mmol/g之量。 Although the mixing ratio of the diol compound of (raw material d) and the polyol of (raw material b) can be appropriately selected as the amount of the structural unit of formula A that is finally introduced, the final aromatic component concentration in the final component A is as described above. , Can be mixed into an amount such as 1.0 ~ 6.0mmol / g.

對(原料b)及原料(d)之合計而言，與(原料c)之聚異氰酸酯的摻合比例，係可因應生成之(A1-1)化合物的數平均分子量為多少來適當地調整。惟，生成之(A1-1)化合物的末端因是異氰酸基，有必要為(原料b)及原料(d)之羥基數<(原料c)之異氰酸基數。 For the total of (raw material b) and raw material (d), the blending ratio with the polyisocyanate of (raw material c) can be appropriately adjusted according to the number average molecular weight of the compound (A 1 -1) produced. . However, since the terminal of the produced (A 1 -1) compound is an isocyanate group, it is necessary that the number of the isocyanate groups in the (raw material b) and the raw material (d) is less than the (raw material c).

合成末端具有異氰酸基之(A1-1)化合物時，係以將異氰酸基數與羥基數之比率(異氰酸基數/羥基數)調整為1.01以上為佳，調整至2.0以下更佳。 When synthesizing an (A 1 -1) compound having an isocyanate group at the end, it is better to adjust the ratio of the number of isocyanate groups to the number of hydroxyl groups (isocyanate number / number of hydroxyl groups) to 1.01 or more, and to 2.0 or less. good.

末端具有異氰酸基之(A1-1)化合物的數平均分子量，係以500~30000者為佳，1000~25000者更佳，1500~20000者特別佳。 The number average molecular weight of the (A 1 -1) compound having an isocyanate group at its terminal is preferably 500 to 30,000, more preferably 1,000 to 25,000, and particularly preferably 1500 to 20,000.

接著，(方法1)中，係使末端具有異氰酸基 之(A1-1)化合物與(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物反應，而生成具有胺基甲酸酯鍵，與醯胺鍵及/或醯亞胺鍵之化合物。此外，(原料a)為具有酸酐基之3價的聚羧酸衍生物時，會成為具有1組酸酐與1個羧基的情況。又(原料a)為具有酸酐基之4價的聚羧酸衍生物時，會成為具有2組酸酐，或者具有1組酸酐基與2個羧基的情況。上述羧基亦可與醇形成酯鍵而成為衍生物。在此所謂的聚羧酸衍生物，意指具有酸酐基之聚羧酸，或其羧酸酯等之衍生物。 Next, in (Method 1), a (A 1 -1) compound having an isocyanate group at its terminal is reacted with a (or raw material a) a trivalent and / or a tetravalent polycarboxylic acid derivative having an acid anhydride group to produce Compounds having a urethane bond, a hydrazine bond, and / or a fluorenimine bond. In addition, when (raw material a) is a trivalent polycarboxylic acid derivative having an acid anhydride group, it may have a group of acid anhydrides and one carboxyl group. When (raw material a) is a tetravalent polycarboxylic acid derivative having an acid anhydride group, it may have two groups of acid anhydrides or one group of acid anhydride groups and two carboxyl groups. The carboxyl group may form an ester bond with an alcohol to form a derivative. The polycarboxylic acid derivative herein means a polycarboxylic acid having an acid anhydride group, or a derivative thereof such as a carboxylic acid ester.

構成(原料a)之具有酸酐基之3價的聚羧酸衍生物方面，並無特別限定，但可舉例如下述一般式(3)或(4)所示之化合物。 The trivalent polycarboxylic acid derivative having an acid anhydride group constituting (raw material a) is not particularly limited, and examples thereof include compounds represented by the following general formula (3) or (4).

(式(3)中，R4表示氫原子、碳數1~10之烷基或苯基)。 (In the formula (3), R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group).

(式(4)中，R5表示氫原子、碳數1~10之烷基或苯基、Y1表示-CH2-、-CO-、-SO2-、或-O-)。 (In formula (4), R 5 represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 10 carbon atoms, and Y 1 represents -CH 2- , -CO-, -SO 2- , or -O-).

上述之R4、R5方面，係以氫原子為佳，Y1方面，為-CO-、或-O-為佳。 In terms of R 4 and R 5 described above, a hydrogen atom is preferred, and in terms of Y 1 , -CO- or -O- is preferred.

具有酸酐基之3價的聚羧酸衍生物方面，由成本面等來看，無水偏苯三甲酸特別佳。 In terms of a trivalent polycarboxylic acid derivative having an acid anhydride group, anhydrous trimellitic acid is particularly preferable in terms of cost and the like.

具有酸酐基之4價的聚羧酸衍生物亦無特別限定，可舉例如下述一般式(5)所示之四羧酸二酐。此等，係可單獨使用1種或組合2種以上使用。 The tetravalent polycarboxylic acid derivative having an acid anhydride group is not particularly limited, and examples thereof include a tetracarboxylic dianhydride represented by the following general formula (5). These can be used alone or in combination of two or more.

(式(5)中，Y2表示4價的有機基)。 (In the formula (5), Y 2 represents a tetravalent organic group).

式(5)所示之四羧酸二酐方面，並無特別限定，但可舉例如均苯四甲酸二酐、3,3',4,4'-二苯甲酮四羧 酸二酐、2,3,2',3'-二苯甲酮四羧酸二酐、2,3,3',4'-二苯甲酮四羧酸二酐、3,3',4,4'-二苯基四羧酸二酐、2,2',3,3'-二苯基四羧酸二酐、4,4'-氧基二苯二甲酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)碸二酐、3,4,9,10-苝四羧酸二酐、雙(3,4-二羧基苯基)醚二酐、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、1,2,4,5-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、菲-1,8,9,10-四羧酸二酐、吡嗪-2,3,5,6-四羧酸二酐、噻吩-2,3,4,5-四羧酸二酐、雙(3,4-二羧基苯基)二甲基矽烷二酐、雙(3,4-二羧基苯基)二苯基矽烷二酐、1,4-雙(3,4-二羧基苯基二甲基矽烷基)苯二酐、1,3-雙(3,4-二羧基苯基)-1,1,3,3-四甲基二環己烷二酐、p-苯基雙(偏苯三甲酸單酯酸酐)、乙烯四羧酸二酐、1,2,3,4-丁烷四羧酸二酐、十氫化萘-1,4,5,8-四羧酸二酐、4,8-二甲基-1,2,3,5,6,7-六氫萘-1,2,5,6-四羧酸二酐、環戊烷-1,2,3,4-四羧酸二酐、吡咯啶-2,3,4,5-四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、雙(外切-雙環〔2,2,1〕庚烷-2,3-二羧酸酐)碸、雙環-(2,2,2)-辛(7)-烯-2,3,5,6-四羧酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、2,2-雙〔4-(3,4-二羧基苯氧基)苯基〕六氟丙烷二酐、4,4'-雙(3,4-二羧基苯氧基)二苯基硫醚二酐、1,4-雙(2-羥基 六氟異丙基)苯雙(偏苯三甲酸酐)、1,3-雙(2-羥基六氟異丙基)苯雙(偏苯三甲酸水物)、5-(2,5-二側氧基四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、四氫呋喃-2,3,4,5-四羧酸二酐、1,3,3a,4,5,9b-六氫-5(四氫-2,5-二側氧基-3-喃基)萘并〔1,2-c〕呋喃-1,3-二酮、乙二醇雙(偏苯三甲酸酐)(亦稱「乙二醇雙去氫偏苯三甲酸酯」或「TMEG」)等。 Formula (5) shown quater aspect dianhydride is not particularly limited, but for example, such as pyromellitic dianhydride, 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride, 2,3,2 ', 3' - benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4' - benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4' - diphenyl tetracarboxylic dianhydride, 2,2 ', 3,3' - diphenyl tetracarboxylic dianhydride, 4,4 '- oxybis acid dianhydride, 2,2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5 1,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Carboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic acid Acid dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane Dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) phthalic anhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3 -Tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester anhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, ten Naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetrahydronaphthalene Carboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride) hydrazone, bicyclo- (2,2,2) -oct (7) -ene- 2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyl phenoxy) phenyl] hexafluoropropane dianhydride, 4,4 '- bis (3,4-dicarboxy phenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxy-hexafluoroisopropylidene Propyl) benzenebis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid), 5- (2,5-dioxotetrahydrofuran) ) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 1,3,3a, 4,5,9b- Hexa-5 (tetrahydro-2,5- Dioxan-3-anyl) naphtho [1,2-c] furan-1,3-dione, ethylene glycol bis (trimellitic anhydride) "Triformate" or "TMEG").

較佳為四羧酸二酐，係有乙二醇雙(偏苯三甲酸酐)(TMEG)、3,3',4,4'-二苯基四羧酸二酐(BPDA)、均苯四甲酸二酐(PMDA)、3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)、4,4'-氧基二苯二甲酸二酐(ODPA)。 It is preferably a tetracarboxylic dianhydride, based ethylene glycol bis (trimellitic anhydride) (TMEG), 3,3 ', 4,4' - diphenyl tetracarboxylic dianhydride (BPDA), pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 ' - benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '- oxybis acid dianhydride (ODPA).

此等之四羧酸二酐可單獨使用或混合2種以上使用。 These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

末端具有異氰酸基之(A'-1)化合物與(原料a)之混合比率，若是最終生成的化合物為具有胺基甲酸酯鍵與醯胺鍵及/或醯亞胺鍵之範圍，並無特別限制。 Having a terminal isocyanate group of the compound (A '-1) the mixing ratio (starting material a), the compound having the finally generated if and / range of a urethane bond or an amide bond with the acyl bond of the imine XI, There are no particular restrictions.

方法1中，亦可使(A1-1)化合物與(A1-1)化合物以外的聚異氰酸酯(以下記為(A1-2)化合物)同時地與前述(原料a)反應，而得具有胺基甲酸酯鍵，與醯胺鍵及/或醯亞胺鍵之化合物。(A1-2)化合物方面，若為(A1-1)化合物以外的聚異氰酸酯，則無特別限定，可舉例如前述(原料c)等。此等可單獨使用1種或組合2種以上使用。原料a的酸酐基與羧基加總的總數與A1-1中 之異氰酸基及A1-2中之異氰酸基數加總的異氰酸基的總數的比，並無特別限制，以0.9：1.0~1.1：1.0的範圍者為佳，更佳為0.95：1.0~1.05：1.0的範圍。 Method 1, also make (A 1 -1) compound (A 1 -1) other than the polyisocyanate compound (hereinafter referred to as (A 1 -2) compound) simultaneously in the reaction of (raw material A), to give Compounds having a urethane bond, a hydrazine bond, and / or a fluorenimine bond. The (A 1 -2) compound is not particularly limited as long as it is a polyisocyanate other than the (A 1 -1) compound, and examples thereof include the aforementioned (raw material c). These can be used individually by 1 type or in combination of 2 or more types. The ratio of the total number of the acid anhydride groups and the carboxyl groups of the raw material a to the total number of the isocyanate groups in A 1 -1 and the total number of isocyanate groups in A 1 -2 is not particularly limited. The range of 0.9: 1.0 to 1.1: 1.0 is preferable, and the range of 0.95: 1.0 to 1.05: 1.0 is more preferable.

本實施形態中，係可與上述聚異氰酸酯一起併用胺化合物。胺化合物方面，可舉出將上述聚異氰酸酯化中的異氰酸基轉換成胺基之化合物。異氰酸基轉換成胺基，可藉由公知的方法來進行。 In this embodiment, an amine compound can be used together with the polyisocyanate. Examples of the amine compound include compounds in which an isocyanate group in the above-mentioned polyisocyanate is converted into an amine group. The conversion of an isocyanate group into an amine group can be performed by a known method.

(A1-2)化合物的總量之50~100質量%係以芳香族聚異氰酸酯者為佳。此芳香族聚異氰酸酯若考量溶解性、機械特性及成本面等之平衡，4,4'-二苯基甲烷二異氰酸酯者特別佳。 50 to 100% by mass of the total amount of the (A 1 -2) compound is preferably an aromatic polyisocyanate. This aromatic polyisocyanates if considerations of solubility, mechanical properties and balance of the costs and other surfaces, 4,4 '- diphenylmethane diisocyanate are particularly preferred.

(方法2) (Method 2)

(方法2)的合成法，首先，使(原料c)聚異氰酸酯與(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物反應，合成具有醯亞胺鍵及醯胺鍵之至少1種鍵結的聚異氰酸酯(以下記為「(A2-1)化合物」)。於其中，係使(原料b)前述一般式(1)、一般式(2)的至少1者所示之多元醇及(原料d)前述式(A2)及/或(A3)所示之二醇化合物反應。 (Method 2) The synthesis method firstly reacts (raw material c) a polyisocyanate with (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group to synthesize a fluorene imine bond and fluorene amine At least one type of bonded polyisocyanate (hereinafter referred to as "(A 2 -1) compound"). Among them, (raw material b) the polyol represented by at least one of the aforementioned general formula (1) and general formula (2) and (raw material d) the second represented by the aforementioned formula (A2) and / or (A3) Alcohol compounds react.

使(原料c)之聚異氰酸酯與(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物反應時的摻合比例，可因應所欲生成的(A2-1)化合物之數平均分子量為多少來適當地調整。惟，因使生成的(A2-1)化合物之末 端為異氰酸基，(原料a)之酸酐基的數與羧基的數加總的總數<(原料c)之異氰酸基數有必要。在此，羧基的數中，係如式(3)所示之化合物中的-COOR3及式(4)所示之化合物中的-COOR4，亦包含R3及R4為氫原子之羧基的數。。 The blending ratio when reacting the polyisocyanate of (raw material c) with the trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group can be generated according to the desired (A 2 -1) compound The number average molecular weight is appropriately adjusted. However, since the terminal of the produced (A 2 -1) compound is an isocyanate group, the sum of the number of acid anhydride groups and the number of carboxyl groups in (raw material a) must be less than the number of isocyanate groups in (raw material c). . Here, the number of carboxyl groups, and a compound represented by the formula -COOR 3 (4) as the compound of formula (3) in the formula of the -COOR 4, R 3 and also R 4 comprises a carboxyl group of a hydrogen atom The number. .

合成末端具有異氰酸基之(A2-1)化合物時，異氰酸基數與酸酐基的數與羧基的數加總的總數之比率(異氰酸基數/酸酐基的數與羧基的數加總的總數)係以調整至1.01以上者為佳，且調整至2.0以下者佳。 When synthesizing an (A 2 -1) compound having an isocyanate group at the end, the ratio of the number of isocyanate groups to the number of acid anhydride groups to the total number of carboxyl groups (the number of isocyanate groups / the number of acid anhydride groups and the number of carboxyl groups) The total number is preferably adjusted to 1.01 or more, and adjusted to 2.0 or less.

末端具有異氰酸基之(A2-1)化合物的數平均分子量，係以500~15000者為佳，800~10000者更佳，1000~5000者特別佳。 The number average molecular weight of the (A 2 -1) compound having an isocyanate group at the terminal is preferably 500 to 15,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 5,000.

接著，使末端具有異氰酸基之(A2-1)化合物，與(原料b)及(原料d)反應，而生成具有胺基甲酸酯鍵，與醯胺鍵及/或醯亞胺鍵之化合物。(A2-1)化合物，與(原料b)及(原料d)之摻合比率係可因應最終之化合物的酸價或目的分子量來選擇。 Next, the (A 2 -1) compound having an isocyanate group at the terminal is reacted with (raw material b) and (raw material d) to form a urethane bond, a sulfonium bond, and / or sulfonimine Bonded compounds. The compounding ratio of (A 2 -1) compound to (raw material b) and (raw material d) can be selected according to the acid value or the target molecular weight of the final compound.

又，使末端具有異氰酸基之(A2-1)化合物，與(原料b)及(原料d)反應時，可一起使用如2,2-二羥甲基丙酸或2,2-二羥甲基丁烷酸般的具有羧基之多元醇。A2-1中之異氰酸基的總數，與原料b中之羥基數，及如2,2-二羥甲基丙酸或2,2-二羥甲基丁烷酸的具有羧基之多元醇中之羥基數加總的羥基之總數的比，並無特別限制，A2-1中具有醯胺基時，以0.9：1.0~1.1：1.0的範圍者 為佳，更佳為0.95：1.0~1.05：1.0的範圍。又，A2-1中不具有醯胺基且亦不使用如2,2-二羥甲基丙酸或2,2-二羥甲基丁烷酸之具有羧基之多元醇時，0.9：1.0~0.95：1.0的範圍、或1.0：0.95~1.0：0.9的範圍者為佳。 When the (A 2 -1) compound having an isocyanate group at its terminal is reacted with (raw material b) and (raw material d), for example, 2,2-dimethylolpropionic acid or 2,2- Dimethylolbutanoic acid-containing polyol having a carboxyl group. The total number of isocyanate groups in A 2 -1, the number of hydroxyl groups in raw material b, and the polyvalent carboxyl group such as 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid There is no particular limitation on the ratio of the total number of hydroxyl groups in the alcohol to the total number of hydroxyl groups. When A 2 -1 has an amidino group, it is preferably in the range of 0.9: 1.0 to 1.1: 1.0, more preferably 0.95: 1.0 ~ 1.05: The range of 1.0. In addition, when A 2 -1 does not have a sulfonylamino group and a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid is not used, 0.9: 1.0 A range of ~ 0.95: 1.0 or a range of 1.0: 0.95 ~ 1.0: 0.9 is preferred.

此外，(方法2)之合成法中所使用的(原料b)及(d)係可使用與前述(方法1)中說明的(原料b)及(d)相同者。再者，亦可進一步追加多元醇，藉由末端異氰酸基與追加的多元醇反應而使胺基甲酸酯鍵生成。 The (raw materials b) and (d) used in the synthesis method of (method 2) can be the same as the (raw materials b) and (d) described in (method 1). Further, a polyol may be further added, and a urethane bond may be formed by reacting a terminal isocyanate group with the additional polyol.

(方法3) (Method 3)

(方法3)的合成法，首先，使(原料c)聚異氰酸酯與(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物反應，合成具有醯亞胺鍵及醯胺鍵之至少1種鍵結且末端具有酸酐基及/或羧基的化合物(以下記為「(A3-1)化合物」)。 (Method 3) The synthesis method firstly reacts (raw material c) a polyisocyanate with (raw material a) a trivalent and / or a tetravalent polycarboxylic acid derivative having an acid anhydride group to synthesize a fluorenimine bond and fluorenamine A compound having at least one type of bond and having an acid anhydride group and / or a carboxyl group at the terminal (hereinafter referred to as "(A 3 -1) compound").

(原料c)與(原料a)之摻合比例可因應所欲生成之(A3-1)化合物之數平均分子量為多少來適當地調整。惟，因為要使生成之(A3-1)化合物的末端為酸酐基及/或羧基，(原料a)之酸酐基的數與羧基的數加總的總數>(原料c)之異氰酸基數有其必要。 The blending ratio of (raw material c) and (raw material a) can be appropriately adjusted according to the number average molecular weight of the (A 3 -1) compound to be produced. However, since the end of the compound to be produced (A 3 -1) is an acid anhydride group and / or a carboxyl group, the total number of the number of acid anhydride groups and the number of carboxyl groups in (raw material a) is> isocyanate of (raw material c). Cardinalities are necessary.

合成末端具有酸酐基及/或羧基之(A3-1)化合物時，酸酐基的數與羧基的數加總的總數和異氰酸基數之比率(酸酐基的數與羧基的數加總的總數/異氰酸基數)係以調整至1.01以上者為佳，調整至2.0以下者佳。 When synthesizing (A 3 -1) compounds having acid anhydride groups and / or carboxyl groups at the end, the ratio of the total number of acid anhydride groups to the number of carboxyl groups and the number of isocyanate groups (the sum of the number of acid anhydride groups and the number of carboxyl groups The total number / isocyanate number) is preferably adjusted to 1.01 or more, and adjusted to 2.0 or less.

末端具有酸酐基及/或羧基之(A3-1)化合物的數平均分子量，係以500~15000者為佳，800~10000者更佳，1000~5000者特別佳。 The number-average molecular weight of the (A 3 -1) compound having an acid anhydride group and / or a carboxyl group at the terminal is preferably 500 to 15,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 5,000.

接著，使末端具有酸酐基及/或羧基之(A3-1)化合物與(原料b)及(原料d)反應，而生成具有胺基甲酸酯鍵，與醯胺鍵及/或醯亞胺鍵之化合物。A3-1中之酸酐基的總數與原料b中之羥基數的比，並無特別限制，以0.9：1.0~1.1：1.0的範圍者為佳，更佳為0.95：1.0~1.05：1.0的範圍。此外，(方法3)之合成法中所使用的(原料a)~(原料d)係可使用與(方法1)之合成法中所使用的(原料a)~(原料d)相同者。 Next, the (A 3 -1) compound having an acid anhydride group and / or a carboxyl group at the terminal is reacted with (raw material b) and (raw material d) to form a urethane bond with a sulfonamide bond and / or fluorene. Amine bond compounds. The ratio of the total number of acid anhydride groups in A 3 -1 to the number of hydroxyl groups in raw material b is not particularly limited, and it is preferably in the range of 0.9: 1.0 to 1.1: 1.0, more preferably 0.95: 1.0 to 1.05: 1.0 range. The (raw material a) to (raw material d) used in the synthesis method of (method 3) can be the same as the (raw material a) to (raw material d) used in the synthesis method of (method 1).

從提昇耐藥品性及電氣特性、酸價等之官能基之控制的觀點來看，係以於最初的反應獲得末端具有異氰酸基之化合物的方法(意即，(方法1)與(方法2))為佳。 From the viewpoint of improving the chemical resistance, functional characteristics, and the control of functional groups such as acid value, the method (meaning, (Method 1) and (Method 1) and (Method 1) and (Method 1) 2)) is better.

此等(方法1)~(方法3)之各原料的反應可藉由於有機溶劑，較佳為非含氮系極性溶劑的存在下，使此等加熱來進行。 The reaction of each of these (Method 1) to (Method 3) can be carried out by heating them in the presence of an organic solvent, preferably a non-nitrogen-based polar solvent.

上述非含氮系極性溶劑，例如可由二乙二醇二甲基醚、二乙二醇二乙基醚、三乙二醇二甲基醚及三乙二醇二乙基醚等之醚系溶劑；二甲基亞碸、二乙基亞碸、二甲基碸及環丁碸等之含硫系溶劑；γ-丁內酯及乙酸賽路蘇等之酯系溶劑；環己酮及甲基乙基酮等之酮系溶劑；以及甲苯及二甲苯等之芳香族烴系溶劑來選出。此等可單獨使用1 種或組合2種以上使用。 The non-nitrogen-containing polar solvent may be, for example, an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. ; Sulfur-based solvents such as dimethyl fluorene, diethyl fluorene, dimethyl fluorene, and cyclobutyl fluorene; γ-butyrolactone and acetic acid acetate solvents; cyclohexanone and methyl Ketone solvents such as ethyl ketone; and aromatic hydrocarbon solvents such as toluene and xylene are selected. These can be used alone1 One type or a combination of two or more types.

上述溶劑之中，又以選擇生成之樹脂可溶解的溶劑來使用為佳。又，係以使用適合於合成後直接作為熱硬化性組成物之溶劑者為佳。上述溶劑之中，為了效率更佳且均一系來進行反應，係以γ-丁內酯或包含γ-丁內酯之混合溶劑者為佳。 Among the above solvents, it is preferable to select and use a solvent in which the resulting resin is soluble. In addition, it is preferable to use a solvent suitable for use as a thermosetting composition directly after synthesis. Among the above solvents, in order to perform the reaction more efficiently and uniformly, γ-butyrolactone or a mixed solvent containing γ-butyrolactone is preferred.

為了合成(成分A)，溶劑之使用量相對於合成各自的(A'-1)、(B'-1)、(C'-1)化合物之原材料的總量100質量份，係以80~500質量份者為佳。此使用量，若相對於原材料的總量100質量份為80~500質量份的話，合成時的黏度也不會過高，也不會有因為不能攪拌而難以合成的情事，且反應速度也不會極端地降低，以此為佳。 For the synthesis of (Component A), and the amount of the solvent with respect to 100 parts by mass of the total synthesis of the respective (A '-1), (B ' -1), (C '-1) of the raw material compound, 80 to line 500 parts by mass is preferred. If this amount is 80 to 500 parts by mass based on 100 parts by mass of the total amount of raw materials, the viscosity during synthesis will not be too high, and it will not be difficult to synthesize because it cannot be stirred, and the reaction speed will not be high. It will be extremely low, which is better.

反應溫度係以70~210℃者為佳，75~190℃者更佳，80~180℃者特別佳。此溫度若未達70℃則有反應時間過長的傾向，若超過210℃則有反應中容易引起膠體化之傾向。反應時間可依反應容器之容量、所採用之反應條件來適當地選擇。 The reaction temperature is preferably 70 to 210 ° C, more preferably 75 to 190 ° C, and particularly preferably 80 to 180 ° C. If the temperature is less than 70 ° C, the reaction time tends to be too long, and if it exceeds 210 ° C, the reaction tends to cause colloid formation during the reaction. The reaction time can be appropriately selected depending on the capacity of the reaction container and the reaction conditions used.

因應需要，亦可於三級胺類、鹼金屬、鹼土類金屬、錫、鋅、鈦、鈷等之金屬或半金屬化合物等之觸媒存在下來進行反應。 Depending on the needs, the catalyst can also be reacted in the presence of catalysts such as tertiary amines, alkali metals, alkaline earth metals, metals such as tin, zinc, titanium, and cobalt, or semi-metal compounds.

觸媒方面，可使用1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)、4-二甲基胺基吡啶、等，但觸媒並非是必須使用的。 As for the catalyst, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 4-dimethylaminopyridine, etc. may be used, but the catalyst is not necessarily used.

此外，原料(c)聚異氰酸酯在使生成物(A)及(B)與(原料a)、生成物(C)及(D)，與(原料b)多元醇及(原料d)反應時，亦可因應分子量調整或酸價調整等目的而再度添加。 In addition, when the raw material (c) polyisocyanate reacts the products (A) and (B) with (raw material a), the products (C) and (D), and (raw material b) the polyol and (raw material d), It can also be added again for purposes such as molecular weight adjustment or acid value adjustment.

此外，本說明書中，數平均分子量意指以膠體滲透層析(GPC)所測定，並使用標準聚苯乙烯之檢量線來換算之值。數平均分子量、質量平均分子量及分散度係如以下所定義。 In this specification, the number average molecular weight means a value measured by colloidal permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene. The number average molecular weight, the mass average molecular weight, and the degree of dispersion are defined as follows.

(a)數平均分子量(Mn) (a) Number average molecular weight (Mn)

Mn=Σ(NiMi)/ΣNi=ΣXiMi Mn = Σ (N i M i ) / ΣN i = ΣX i M i

(Xi=分子量Mi之分子的莫耳分率=Ni/ΣNi) (X i = Mohr fraction of the molecule of molecular weight M i = N i / ΣN i )

(b)質量平均分子量(Mw) (b) Mass average molecular weight (Mw)

Mw=Σ(NiMi 2)/ΣNiMi=ΣWiMi Mw = Σ (N i M i 2 ) / ΣN i M i = ΣW i M i

(Wi=分子量Mi之分子的質量分率=NiMi/ΣNiMi) (W i = mass fraction of molecule of molecular weight M i = N i M i / ΣN i M i )

(c)分子量分布(分散度) (c) Molecular weight distribution (degree of dispersion)

分散度=Mw/Mn Dispersion = Mw / Mn

又，本說明書中，在沒有特別的限制之下，GPC的測定條件係如以下所述。 In addition, in this specification, the measurement conditions of GPC are as follows without limitation.

裝置名：日本分光股份公司製HPLC單元HSS-2000 Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation

管柱：Shodex(註冊商標)管柱LF-804×3本(直列) Column: Shodex (registered trademark) column LF-804 × 3 (in-line)

移動相：四氫呋喃 Mobile phase: tetrahydrofuran

流速：1.0mL/min Flow rate: 1.0mL / min

檢出器：日本分光股份公司製RI-2031Plus Detector: RI-2031Plus, manufactured by JASCO Corporation

溫度：40.0℃ Temperature: 40.0 ℃

試料量：樣品環100μL Sample volume: 100 μL of sample loop

試料濃度：調整至0.1質量%前後。 Sample concentration: before and after adjustment to 0.1% by mass.

(成分A)之酸價較佳為10~50mgKOH/g。更佳為10~35mgKOH/g，特別佳為15~30mgKOH/g。(成分A)之酸價若為10~50mgKOH/g，則翹曲不會過大，硬化也充足，因此可抑制耐候性或彎曲性等之降低，而較佳。酸價的調整可以依反應所生成的羧基之量來進行調整。 The acid value of (component A) is preferably 10 to 50 mgKOH / g. It is more preferably 10 to 35 mgKOH / g, and particularly preferably 15 to 30 mgKOH / g. If the acid value of (component A) is 10 to 50 mgKOH / g, the warpage will not be too large, and the hardening will be sufficient. Therefore, it is possible to suppress the deterioration of weather resistance and bendability, etc., and it is preferable. The adjustment of the acid value can be adjusted according to the amount of the carboxyl group generated by the reaction.

此外，(成分A)之酸價可藉由以下的方法來測定。首先，精秤包含(成分A)之溶液約1g。之後，相對於此，添加異丙基醇/甲苯=1/2(質量比)之混合溶劑30g，均一地溶解。於所得的溶液中適量地添加作為指示劑之酚酞，並使用0.1N之KOH溶液(醇性)進行滴定。然後，由滴定結果以下述式(α)：A=10×Vf×56.1/(Wp×I)‧‧‧‧‧式(α)來算出酸價。式(α)中，A表示酸價(mgKOH/g)，Vf表示0.1N之KOH溶液的滴定量(mL)，Wp表示包含(成分A)之溶液的質量(g)，I表示包含(成分A)之溶液的不揮發分之比例(質量%)。 The acid value of (component A) can be measured by the following method. First, the fine scale contains about 1 g of the solution of (component A). Thereafter, 30 g of a mixed solvent of isopropyl alcohol / toluene = 1/2 (mass ratio) was added thereto, and the mixture was uniformly dissolved. To the obtained solution, an appropriate amount of phenolphthalein was added as an indicator, and titration was performed using a 0.1N KOH solution (alcoholic). Then, the acid value was calculated from the result of the titration using the following formula (α): A = 10 × Vf × 56.1 / (Wp × I) ‧ ‧ ‧ ‧ ‧ formula (α). In the formula (α), A represents an acid value (mgKOH / g), Vf represents a titer (mL) of a 0.1N KOH solution, Wp represents a mass (g) of a solution containing (component A), and I represents a component containing (component A) The non-volatile matter ratio (% by mass) of the solution.

如此進行所得之成分A的數平均分子量，係以5000~65000者為佳，6000~40000者更佳，7000~25000者特別佳。數平均分子量若為5000~65000，則可抑制耐候性或耐藥品性的降低，亦因可維持對非含氮系極性溶劑之溶解性，而較佳。 The number average molecular weight of the component A obtained in this way is preferably 5,000 to 65,000, more preferably 6,000 to 40,000, and particularly preferably 7,000 to 25,000. If the number average molecular weight is 5,000 to 65,000, it is possible to suppress a decrease in weather resistance or chemical resistance, and it is also preferable because the solubility in a non-nitrogen-based polar solvent can be maintained.

接著，就作為本發明之硬化性組成物的必須成分之(成分B)進行說明。 Next, (component B) which is an essential component of the curable composition of this invention is demonstrated.

本實施形態之硬化性組成物，進一步含有可使前述(成分A)硬化之硬化劑。硬化劑方面，係1分子中具有2個以上可與成分(A)之官能基反應之官能基的化合物。成分(A)當具有羧基、羥基、酸酐基、異氰酸基、醯胺基、胺基之任一者時，成分(B)之硬化劑係以具有複數個可與該等官能基反應之環氧基、異氰酸基、羥基、羧基者為佳。 The curable composition according to this embodiment further contains a curing agent that can harden the aforementioned (component A). The hardener is a compound having two or more functional groups capable of reacting with the functional group of the component (A) in one molecule. When the component (A) has any of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, a amine group, and an amine group, the hardener of the component (B) has a plurality of compounds that can react with these functional groups. An epoxy group, an isocyanate group, a hydroxyl group, or a carboxyl group is preferred.

作為硬化劑所使用的含環氧基之化合物方面，可舉出1分子中具有1個以上的環氧基之1種以上的化合物，再以包含1分子中具有2個以上之環氧基的化合物者為佳。此外，包含1分子中具有2個以上之環氧基的化合物時，其係可單獨使用，亦可與分子中具有2個以上的環氧基之化合物一起，亦可含分子中具有1個的環氧基之化合物。 As the epoxy group-containing compound used as the hardener, one or more compounds having one or more epoxy groups in one molecule, and one containing two or more epoxy groups in one molecule may be mentioned. Compounds are preferred. In addition, when a compound containing two or more epoxy groups is contained in one molecule, it may be used alone or together with a compound having two or more epoxy groups in the molecule, or may contain one having one or more molecules in the molecule. Epoxy compounds.

作為硬化劑所使用的含環氧基之化合物的具體例方面，可舉出使以苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂為首的苯酚、甲酚、二甲苯酚、間苯二酚、苯二酚、苯酚類及/或α-萘酚、β-萘酚、二羥基萘等之萘酚類，與具有甲醛、乙醛、丙醛、苯甲醛、水楊醛等之醛基的化合物，在酸性觸媒下縮合或共縮合所得之酚醛清漆樹脂予以環氧化之酚醛清漆型環氧樹脂、雙酚A、雙酚F、雙酚S、烷基取代或非取代的聯苯酚、二苯乙烯系 苯酚類等之二環氧丙基醚(雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、聯苯基型環氧化合物、二苯乙烯型環氧化合物)、丁烷二醇、聚乙二醇、聚丙烯二醇等之醇類的環氧丙基醚、苯二甲酸、異苯二甲酸、四氫苯二甲酸等之羧酸類的環氧丙基酯型環氧樹脂、苯胺、雙(4-胺基苯基)甲烷、異三聚氰酸等之使鍵結於氮原子之活性氫以環氧丙基取代者等之環氧丙基型或甲基環氧丙基型的環氧樹脂、p-胺基苯酚等之胺基苯酚類的使鍵結於氮原子之活性氫及苯酚性羥基之活性氫以環氧丙基取代者等之環氧丙基型或甲基環氧丙基型的環氧樹脂、將分子內的烯烴鍵予以環氧化所得之乙烯基環己烯二環氧化物、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、2-(3,4-環氧基)環己基-5,5-螺環(3,4-環氧基)環己烷-m-二氧陸圜等之脂環型環氧樹脂、對位二甲伸苯基及/或間位二甲伸苯基改性苯酚樹脂的環氧丙基醚、萜烯改性苯酚樹脂的環氧丙基醚、二環戊二烯改性苯酚樹脂的環氧丙基醚、環戊二烯改性苯酚樹脂的環氧丙基醚、多環芳香環改性苯酚樹脂的環氧丙基醚、含萘環之苯酚樹脂的環氧丙基醚、鹵素化苯酚酚醛清漆型環氧樹脂、氫醌型環氧樹脂、三羥甲基丙烷型環氧樹脂、將烯烴鍵以過乙酸等之過酸予以氧化所得之線狀脂肪族環氧樹脂、二苯基甲烷型環氧樹脂、苯酚芳烷基樹脂、萘酚芳烷基樹脂等之芳烷基型苯酚樹脂的環氧化物、含硫原子之環氧樹脂、三環〔5,2,1,02,6〕癸烷二甲醇的二環氧丙基醚、1,3-雙(1-金剛 烷基)-4,6-雙(縮水甘油醚基)苯、1-[2',4'-雙(縮水甘油醚基)苯基]金剛烷、1,3-雙(4'-縮水甘油醚基苯基)金剛烷及1,3-雙[2',4'-雙(縮水甘油醚基)苯基]金剛烷等之具有金剛烷構造之環氧樹脂。 Specific examples of the epoxy group-containing compound used as the hardener include phenol, cresol, xylenol, and the like, including phenol novolac epoxy resin and o-cresol novolac epoxy resin. Resorcinol, resorcinol, phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde Novolak-type epoxy resin, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or non-substituted Diglycidyl ethers such as biphenol and stilbene phenols (bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, biphenyl type epoxy compound, Stilbene type epoxy compound), butylene glycol, polyethylene glycol, polypropylene glycol and other alcohols such as glycidyl ether, phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc. Use of carboxylic acid type epoxypropyl ester epoxy resin, aniline, bis (4-aminophenyl) methane, isotricyanic acid, etc. Glycidyl-type or methylglycidyl-type epoxy resins in which active hydrogen bonded to a nitrogen atom is substituted with a glycidyl group, and aminophenols such as p-aminophenol are bonded Epoxy-based or methyl-epoxy-based epoxy resins in which the active hydrogen of the nitrogen atom and the active hydrogen of the phenolic hydroxyl group are substituted with an epoxy group, etc., are obtained by epoxidizing an olefin bond in the molecule. Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl -5,5-spiro (3,4-epoxy) cyclohexane-m-dioxolane and other alicyclic epoxy resins, para-m-phenylene and / or meta-methylene Glycidyl ether of phenyl modified phenol resin, Glycidyl ether of terpene modified phenol resin, Glycidyl ether of dicyclopentadiene modified phenol resin, Cyclopentadiene modified phenol resin Glycidyl ether, Glycidyl ether of polycyclic aromatic ring modified phenol resin, Glycidyl ether of naphthalene ring-containing phenol resin, Halogenated phenol novolac epoxy resin, Hydroquinone epoxy Resin, trimethylolpropane epoxy resin, Aryl-type phenols such as linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracid such as peracetic acid, diphenylmethane type epoxy resins, phenol aralkyl resins, naphthol aralkyl resins, etc. an epoxide resin, an epoxy resin containing sulfur atoms, tricyclo [5,2,1,0 2,6] decane-diglycidyl ether dimethanol, 1,3-bis (1-adamantyl yl) -4,6-bis (glycidyl ether) benzene, 1- [2 ', 4' - bis (ether-yl) phenyl] adamantane, 1,3-bis (4 '- glycidyl ether yl) adamantane and 1,3-bis [2 ', 4' - bis (ether-yl) phenyl] adamantane, etc. of an epoxy resin having an adamantane structure.

前述1分子中具有2個以上之環氧基的化合物方面，係以1分子中具有2個以上的環氧基且具有芳香環構造及/或脂環構造之化合物為佳。 The compound having two or more epoxy groups in one molecule is preferably a compound having two or more epoxy groups in one molecule and having an aromatic ring structure and / or an alicyclic structure.

在重視後述的本發明之硬化膜其長期電氣絕緣性能時，1分子中具有2個以上的環氧基且具有芳香環構造及/或脂環構造的化合物之中，二環戊二烯改性苯酚樹脂的環氧丙基醚(意即，三環〔5,2,1,02,6〕具有癸烷構造及芳香環構造且具有2個以上的環氧基之化合物)、1,3-雙(1-金剛烷基)-4,6-雙(縮水甘油醚基)苯、1-[2',4'-雙(縮水甘油醚基)苯基]金剛烷、1,3-雙(4'-縮水甘油醚基苯基)金剛烷及1,3-雙[2',4'-雙(縮水甘油醚基)苯基]金剛烷等之具有金剛烷構造之環氧樹脂(意即，三環〔3,3,1,13,7〕具有癸烷構造及芳香環構造且具有2個以上的環氧基之化合物)等之具有三環癸烷構造及芳香環構造且具有2個以上的環氧基之化合物因可提供吸水率低的硬化物而較佳，特別佳為下述式(6)中記載之化合物。 When attaching importance to the long-term electrical insulation performance of the cured film of the present invention described later, dicyclopentadiene is modified among compounds having two or more epoxy groups and having an aromatic ring structure and / or an alicyclic structure in one molecule. Glycidyl ether of a phenol resin (meaning a compound having a tricyclic [5,2,1,0 2,6 ] having a decane structure and an aromatic ring structure and having two or more epoxy groups), 1, 3 - bis (1-adamantyl) -4,6-bis (glycidyl ether) benzene, 1- [2 ', 4' - bis (ether-yl) phenyl] adamantane, 1,3-bis (4 '- yl phenyl glycidyl ether) adamantane and 1,3-bis [2', 4 '- bis (ether-yl) phenyl] adamantane, etc. of an epoxy resin having an adamantane structure (meaning That is, a tricyclic [3,3,1,1 3,7 ] compound having a decane structure and an aromatic ring structure and having two or more epoxy groups) and the like having a tricyclodecane structure and an aromatic ring structure and having A compound having two or more epoxy groups is preferred because it can provide a cured product having a low water absorption rate, and particularly preferably a compound described in the following formula (6).

(式(6)中之l表示正的整數)。 (L in Formula (6) represents a positive integer).

另外，當重視本發明之前述與(成分A)之反應性時，在1分子中具有2個以上的環氧基且具有芳香環構造及/或脂環構造的化合物之中，使苯胺、雙(4-胺基苯基)甲烷的鍵結於氮原子之活性氫以環氧丙基取代者等之環氧丙基型或甲基環氧丙基型的環氧樹脂、p-胺基苯酚等之胺基苯酚類的使鍵結於氮原子之活性氫及苯酚性羥基之活性氫以環氧丙基取代者等之環氧丙基型或甲基環氧丙基型的環氧樹脂等之具有胺基及芳香環構造且具有2個以上的環氧基之化合物為佳，特別佳為下述式(7)中記載之化合物。 In addition, when the reactivity with (component A) of the present invention is emphasized, among compounds having two or more epoxy groups in one molecule and having an aromatic ring structure and / or an alicyclic structure, aniline and bis (4-Aminophenyl) methane, epoxy-type or methyl-epoxy-type epoxy resin, active hydrogen bonded to a nitrogen atom, substituted with a glycidyl group, p-aminophenol Glycidyl-type or methyl-glycidyl-type epoxy resins, etc., in which active hydrogens bonded to nitrogen atoms and active hydrogens of phenolic hydroxyl groups are substituted with glycidyl groups such as aminophenols A compound having an amine group and an aromatic ring structure and having two or more epoxy groups is preferred, and a compound described in the following formula (7) is particularly preferred.

又，作為硬化劑所使用之具有複數個異氰酸酯之化合物，即聚異氰酸酯化合物方面，可舉例如二異氰酸酯化合物、三異氰酸酯、其他4官能以上的異氰酸酯。 若考慮(成分A)與硬化劑混合時的經日變化，係以使用以封端劑使異氰酸基安定化之聚異氰酸酯化合物者為佳。此等可單獨使用1種或組合2種以上使用。 In addition, as the polyisocyanate compound, that is, a compound having a plurality of isocyanates used as a curing agent, for example, a diisocyanate compound, a triisocyanate, and other tetrafunctional or higher isocyanates can be mentioned. In consideration of the change over time when (component A) is mixed with the hardener, it is preferable to use a polyisocyanate compound that stabilizes an isocyanate group with a blocking agent. These can be used individually by 1 type or in combination of 2 or more types.

封端劑方面，可舉出醇、苯酚、肟等，並無特別限制。此封端異氰酸酯方面，可舉例如旭化成化學公司製的商品名「DURANATE17B-60PX、TPA-B80E、MF-B60X、MF-K60X、E402-B80T」、昭和電工公司製的商品名「KARENZ MOI-BM、MOI-BP」、住化BAYER胺基甲酸酯公司製的商品名「BL-3175、BL-4165、Desmo Cup 11、Desmo Cup-12」等。封端異氰酸酯係以配合(成分A)之熱硬化溫度來選擇為佳，低溫硬化時，係以BL-3175特別佳。 Examples of the end-capping agent include alcohol, phenol, and oxime, and are not particularly limited. Examples of the blocked isocyanate include, for example, the brand names "DURANATE17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T" manufactured by Asahi Kasei Chemicals, and the brand name "KARENZ MOI-BM" manufactured by Showa Denko Corporation. "MOI-BP", "BL-3175, BL-4165, Desmo Cup 11, Desmo Cup-12", etc., manufactured by Sumika BAYER Urethane Co., Ltd. The blocked isocyanate is preferably selected in accordance with the heat curing temperature of (component A). For low temperature curing, BL-3175 is particularly preferred.

作為硬化劑所使用之含羥基之化合物方面，若包含1分子中具有羥基之1種以上的化合物且其中之至少1種為1分子中具有2個以上的羥基之化合物，並無特別限制。 The hydroxyl-containing compound used as the hardener is not particularly limited as long as it contains one or more compounds having a hydroxyl group in one molecule and at least one of them is a compound having two or more hydroxyl groups in one molecule.

作為硬化劑所使用之含羥基之化合物中，可舉出多元醇等，具體例方面，可舉出乙二醇、丙三醇、丁烷二醇、季戊四醇等。 Examples of the hydroxyl-containing compound used as the curing agent include polyhydric alcohols. Specific examples include ethylene glycol, glycerol, butanediol, and pentaerythritol.

作為硬化劑所使用之含羧基之化合物方面，若包含1分子中具有羧基之1種以上的化合物且其中之至少1種為1分子中具有2個以上的羧基之化合物，並無特別限制。 The carboxyl group-containing compound used as the hardener is not particularly limited as long as it contains one or more compounds having a carboxyl group in one molecule and at least one of them is a compound having two or more carboxyl groups in one molecule.

作為硬化劑所使用之含羧基之化合物中，可 舉出多價羧酸等，具體例方面，可舉出苯二甲酸、琥珀酸、偏苯三甲酸、己二酸、均苯四甲酸等。 Among the carboxyl-containing compounds used as hardeners, Examples of the polyvalent carboxylic acid include phthalic acid, succinic acid, trimellitic acid, adipic acid, and pyromellitic acid.

硬化劑方面，可單獨或併用含環氧基之化合物、聚異氰酸酯化合物、含羥基之化合物及含羧基之化合物，並可配合(成分A)之反應性基來選擇。例如，(成分A)具有羥基時，係以使用封端異氰酸酯為佳，(成分A)具有羧基或胺基時，係以使用含環氧基之化合物者為佳。硬化劑若是可與(成分A)之反應性基反應者，並不受限於含環氧基之化合物、聚異氰酸酯化合物、含羥基之化合物及含羧基之化合物。 As for the hardener, an epoxy group-containing compound, a polyisocyanate compound, a hydroxyl group-containing compound, and a carboxyl group-containing compound can be used alone or in combination, and can be selected by blending with the reactive group of (component A). For example, when (component A) has a hydroxyl group, it is preferable to use a blocked isocyanate, and when (component A) has a carboxyl group or an amine group, it is preferable to use an epoxy group-containing compound. The hardening agent is not limited to an epoxy group-containing compound, a polyisocyanate compound, a hydroxyl group-containing compound, and a carboxyl group-containing compound as long as it can react with the reactive group of (component A).

本發明之硬化性組成物中的(成分B)之量，相對於硬化性組成物中之(成分A)與(成分B)之總量，1~55質量%，較佳為2~45質量%，更佳為2.5~30質量%。本發明之硬化性組成物中的(成分B)之量，相對於硬化性組成物中之(成分A)與(成分B)之總質量，若為1~55質量%，從後述的本發明之硬化膜的耐溶劑性之觀點來看較佳，且可取得以藉由硬化膜所被覆為特徵之可撓性配線板的低翹曲性與較佳的電氣絕緣信賴性與配線折斷之抑制效果的平衡。 The amount of (ingredient B) in the curable composition of the present invention is 1 to 55% by mass, and preferably 2 to 45% by mass relative to the total amount of (ingredient A) and (ingredient B) in the curable composition. %, More preferably 2.5 to 30% by mass. The amount of (ingredient B) in the curable composition of the present invention is 1 to 55% by mass based on the total mass of (ingredient A) and (ingredient B) in the curable composition. From the viewpoint of solvent resistance of the cured film, it is preferable, and low warpage of a flexible wiring board characterized by being covered with the cured film, better reliability of electrical insulation, and suppression of wiring breakage can be obtained. Balance of effects.

又，本發明之硬化性組成物中的(成分A)之量，相對於硬化性組成物中之(成分A)與(成分B)之總量，45~99質量%，較佳為55~98質量%，更佳為70~97.5質量%。本發明之硬化性組成物中的(成分A)之量，相對於硬化性組成物中之(成分A)與(成分B)之總量， 若為45~99質量%，從後述的本發明之硬化膜的耐溶劑性之觀點來看較佳，又，可取得以藉由硬化膜所被覆為特徵之可撓性配線板的低翹曲性與配線折斷之抑制效果的平衡。 The amount of (ingredient A) in the curable composition of the present invention is 45 to 99% by mass, preferably 55 to 99% by mass based on the total amount of (ingredient A) and (ingredient B) in the curable composition. 98% by mass, more preferably 70 to 97.5% by mass. The amount of (ingredient A) in the curable composition of the present invention is relative to the total amount of (ingredient A) and (ingredient B) in the curable composition, If it is 45 to 99% by mass, it is preferable from the viewpoint of the solvent resistance of the cured film of the present invention to be described later, and low warpage of a flexible wiring board characterized by being covered with the cured film can be obtained. The balance between the performance and the suppression effect of wiring breakage.

接著，就作為本發明之硬化性組成物的必須成分之(成分C)來進行說明。 Next, (component C) which is an essential component of the curable composition of this invention is demonstrated.

成分C方面所用的有機溶劑方面，若為可溶解(成分A)及(成分B)之溶劑，並無特別限制，可舉例如二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇乙基甲基醚、二乙二醇二丁基醚、二乙二醇丁基甲基醚、二乙二醇異丙基甲基醚、三乙二醇二甲基醚、三乙二醇丁基甲基醚、四乙二醇二甲基醚、二丙二醇二甲基醚、三丙二醇二甲基醚等之醚系溶劑、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、二丙二醇單甲基醚乙酸酯、二丙二醇單乙基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯、甲氧基丙酸甲基、甲氧基丙酸乙基、乙氧基丙酸甲基、乙氧基丙酸乙基、γ-丁內酯等之酯系溶劑、十氫萘等之烴系溶劑、環己酮等之酮系溶劑、甲苯、二甲苯等之芳香族烴系溶劑，此等之溶劑可單獨使用，亦可併用2種以上。 The organic solvent used for the component C is not particularly limited as long as it is a solvent capable of dissolving the (component A) and (component B). Examples thereof include diethylene glycol dimethyl ether and diethylene glycol diethyl ether. , Diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, triethyl Ether solvents such as glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether Ether ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Ether ether acetate, diethylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, Ester solvents such as γ-butyrolactone, hydrocarbon solvents such as decalin, ketone solvents such as cyclohexanone, and aromatic hydrocarbon solvents such as toluene and xylene. These solvents can be used alone. Two or more types may be used in combination.

此等之中，若考慮網版印刷性及有機溶劑之揮發性的平衡，γ-丁內酯、二乙二醇二乙基醚、二乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯為佳，更佳為 γ-丁內酯、二乙二醇單乙基醚乙酸酯、二乙二醇二乙基醚，最佳為γ-丁內酯的單獨溶劑、γ-丁內酯與二乙二醇單乙基醚乙酸酯的2種混合溶劑、γ-丁內酯與二乙二醇二乙基醚之2種混合溶劑、及γ-丁內酯、二乙二醇單乙基醚乙酸酯及二乙二醇二乙基醚之3種混合溶劑。 Among these, when considering the balance between screen printing and the volatility of organic solvents, γ-butyrolactone, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol Alcohol monomethyl ether acetate is more preferred, more preferably γ-butyrolactone, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, preferably a separate solvent for γ-butyrolactone, γ-butyrolactone and diethylene glycol monoethyl ether Two mixed solvents of ethyl ether acetate, two mixed solvents of γ-butyrolactone and diethylene glycol diethyl ether, and γ-butyrolactone and diethylene glycol monoethyl ether acetate And three mixed solvents of diethylene glycol diethyl ether.

此等之較佳的溶劑組合，因作為網版印刷油墨之溶劑表現優異而較佳。 These preferred solvent combinations are preferred because they perform well as solvents for screen printing inks.

又，作為此等之較佳的有機溶劑之一部份，可將製造前述(成分A)時的合成用溶劑直接使用作為本發明之硬化性組成物的有機溶劑之一部份，且製程上較佳。 In addition, as part of these preferable organic solvents, the solvent for synthesis used in the production of the aforementioned (component A) can be directly used as a part of the organic solvent of the curable composition of the present invention. Better.

本發明之硬化性組成物中的(成分C)之含量，相對於作為本發明之硬化性組成物的成分之(成分A)、(成分B)、(成分C)及後述的(成分D)之總量(惟，本發明之硬化性組成物中不含(成分D)時，係(成分A)、(成分B)及(成分C)之總量)，較佳為25~75質量份，更佳為35~65質量份。(成分C)之含量，相對於作為本發明之硬化性組成物的成分之(成分A)、(成分B)、(成分C)及後述的填充材的總量(惟，本發明之硬化性組成物中不含填充材時，係(成分A)、(成分B)及(成分C)之總量)若為25~75質量份的範圍，則硬化性組成物之黏度在網版印刷法下的印刷表現良好，且因網版印刷後的硬化性組成物之滲透所致的擴散不會變得如此地大，其結果從所欲塗佈硬化性組成物之部位 (意即，印刷版的形狀)可知，實際的硬化性組成物之印刷面積不會變得過大。 The content of (component C) in the curable composition of the present invention is relative to (component A), (component B), (component C), and (component D) described later as the components of the curable composition of the present invention. The total amount (however, when (component D) is not included in the curable composition of the present invention, it is the total amount of (component A), (component B), and (component C)), preferably 25 to 75 parts by mass , More preferably 35 to 65 parts by mass. The content of (ingredient C) is the total amount of (ingredient A), (ingredient B), (ingredient C) and the filler described later (except for the hardening property of the present invention) with respect to the hardening composition of the present invention. When the filler is not included in the composition, if the total amount of (component A), (component B), and (component C) is in the range of 25 to 75 parts by mass, the viscosity of the hardening composition is determined by the screen printing method. The printing performance in the lower layer is good, and the diffusion due to the penetration of the hardening composition after screen printing does not become so large. As a result, the portion where the hardening composition is to be applied is as a result. (Meaning the shape of the printing plate) It can be seen that the printing area of the actual curable composition does not become too large.

又，上述硬化性組成物中，(成分C)相對於(成分A)100質量份，係以含有0.5~20質量份的量者為佳。 Moreover, in the said curable composition, it is preferable that (component C) is 0.5-20 mass parts with respect to 100 mass parts of (component A).

又，本發明之硬化性組成物中，(成分D)方面係以包含由無機微粒子及有機微粒子所成之群選出的至少1種之微粒子者為佳。 In the curable composition of the present invention, the (component D) is preferably one containing at least one kind of fine particles selected from the group consisting of inorganic fine particles and organic fine particles.

無機微粒子方面，可舉例如氧化矽(SiO2)、氧化鋁(Al2O3)、二氧化鈦(TiO2)、氧化鉭(Ta2O5)、二氧化鋯(ZrO2)、氮化矽(Si3N4)、鈦酸鋇(BaO‧TiO2)、碳酸鋇(BaCO3)、鈦酸鉛(PbO‧TiO2)、鈦酸鋯酸鉛(PZT)、鈦酸鋯酸鑭鉛(PLZT)、氧化鎵(Ga2O3)、尖晶石(MgO‧Al2O3)、多鋁紅柱石(3Al2O3‧2SiO2)、菫青石(2MgO‧2Al2O3‧5SiO2)、滑石(3MgO‧4SiO2‧H2O)、鈦酸鋁(TiO2-Al2O3)、含氧化釔之二氧化鋯(Y2O3-ZrO2)、矽酸鋇(BaO‧8SiO2)、氮化硼(BN)、碳酸鈣(CaCO3)、硫酸鈣(CaSO4)、氧化鋅(ZnO)、鈦酸鎂(MgO‧TiO2)、硫酸鋇(BaSO4)、有機皂土、碳(C)、水滑石等，此等可單獨使用1種或組合2種以上使用。 The inorganic fine particles include, for example, silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), titanium dioxide (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconium dioxide (ZrO 2 ), and silicon nitride ( Si 3 N 4 ), barium titanate (BaO‧TiO 2 ), barium carbonate (BaCO 3 ), lead titanate (PbO‧TiO 2 ), lead zirconate titanate (PZT), lead zirconate titanate (PLZT) ), Gallium oxide (Ga 2 O 3 ), spinel (MgO‧Al 2 O 3 ), mullite (3Al 2 O 3 ‧ 2SiO 2 ), vermiculite (2MgO‧2Al 2 O 3 ‧ 5SiO 2 ) , Talc (3MgO‧4SiO 2 ‧H 2 O), aluminum titanate (TiO 2 -Al 2 O 3 ), yttrium oxide-containing zirconia (Y 2 O 3 -ZrO 2 ), barium silicate (BaO‧8SiO 2 ), boron nitride (BN), calcium carbonate (CaCO 3 ), calcium sulfate (CaSO 4 ), zinc oxide (ZnO), magnesium titanate (MgO‧TiO 2 ), barium sulfate (BaSO 4 ), organic bentonite , Carbon (C), hydrotalcite, etc. These can be used alone or in combination of two or more.

有機微粒子方面，係以具有醯胺鍵、醯亞胺鍵、酯鍵或醚鍵之耐熱性樹脂的微粒子為佳。此等之樹脂方面，從耐熱性及機械特性之觀點來看，較佳可舉出聚醯 亞胺樹脂或其前驅物、聚醯胺醯亞胺樹脂或其前驅物、或聚醯胺樹脂。此等可單獨使用1種或組合2種以上使用。 The organic fine particles are preferably fine particles of a heat-resistant resin having a fluorene bond, a fluorene imine bond, an ester bond, or an ether bond. In terms of these resins, from the viewpoints of heat resistance and mechanical properties, polyfluorene is preferred. An imine resin or a precursor thereof, a polyimide resin or a precursor thereof, or a polyimide resin. These can be used individually by 1 type or in combination of 2 or more types.

此等之中，較佳者為(成分D)可包含由氧化矽微粒子及水滑石微粒子選出的至少一者。 Among these, it is preferable that (component D) may include at least one selected from silica fine particles and hydrotalcite fine particles.

本發明之硬化性組成物中所使用之氧化矽微粒子，乃定義成也包含如以粉末物理性地被覆或以有機化合物化學性地表面處理過之微粒子。 The silicon oxide fine particles used in the curable composition of the present invention are defined as including fine particles that are physically coated with a powder or chemically surface-treated with an organic compound.

本發明之硬化性組成物中所使用之氧化矽粒子，若是分散於本發明之硬化性組成物中而形成糊劑者，並無特別限制，可舉例如日本AEROSIL公司所提供之AEROSIL®等。 Curable composition of the present invention as used in the silicon oxide particles, if dispersed in the curable composition of the present invention are formed by paste, not particularly limited, and the like can be exemplified as AEROSIL ® provided by Japan AEROSIL companies.

此等之AEROSIL®所代表之氧化矽微粒子，因也被用於賦予網版印刷時的印刷性，此時也被使用作為賦予搖變性為目的。 Since these silica particles represented by AEROSIL ® are also used to impart printability during screen printing, they are also used at this time for imparting shake properties.

又，水滑石係以Mg6Al2(OH)16CO3‧4H2O等為代表之天然產出的黏土礦物之一種，是層狀的無機化合物。又，水滑石可為合成物，如此的水滑石係Mg/Al系層狀化合物，可藉由與位於層間之碳酸基進行離子交換而使氯化物離子(Cl-)及/或硫酸離子(SO4-)之陰離子得以固定化。使用此機能，在可捕捉成為銅或錫之遷移原因的氯化物離子(Cl-)或硫酸離子(SO4-)並提昇絕緣信賴性的目的下，可有效地使用。 In addition, hydrotalcite is a layered inorganic compound that is a naturally occurring clay mineral represented by Mg 6 Al 2 (OH) 16 CO 3 ‧ 4H 2 O and the like. Further, the hydrotalcite may be synthetic, such hydrotalcite Mg / Al-based lamellar compound, by ion-exchange with the carbonate group located between the layer of the chloride ion (Cl -) and / or a sulfate ion (SO 4- ) Anions are immobilized. With this function, the capture of copper or tin be reasons for the chloride ions (Cl -) or sulfate ions (SO 4-) and improve the insulation reliability of the object can be effectively used.

水滑石之市售品方面，可舉例如堺化學股份公司的STABIACE HT-1、STABIACE HT-7、STABIACE HT-P或、協和化學工業股份公司的DHT-4A、DHT-4A2、DHT-4C等。 For commercially available hydrotalcites, for example, STABIACE HT-1, STABIACE HT-7, STABIACE HT-P or DHT-4A, DHT-4A2, DHT-4C, etc. of Kyowa Chemical Industry Co., Ltd.

此等之無機微粒子及/或有機微粒子之平均粒子徑較佳為0.01~10μm、更佳為0.1~5μm。 The average particle diameter of these inorganic fine particles and / or organic fine particles is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm.

又，(成分D)之摻合量，相對於(成分A)、(成分B)、(成分C)及(成分D)之總量，為0.1~60質量%，較佳為0.3~55質量%，更佳為0.5~40質量%。(成分D)之摻合量，相對於(成分A)、(成分B)、(成分C)及(成分D)之總量，若落在0.1~60質量%的範圍，硬化性組成物之黏度在網版印刷法下的印刷表現良好，且因網版印刷後的硬化性組成物之滲透所致的擴散不會變得如此地大，其結果從所欲塗佈硬化性組成物之部位(意即，印刷版的形狀)可知，實際的硬化性組成物之印刷面積不會變得過大。 The blending amount of (component D) is 0.1 to 60% by mass, and preferably 0.3 to 55% by mass with respect to the total amount of (component A), (component B), (component C), and (component D). %, More preferably 0.5 to 40% by mass. If the blending amount of (component D) is in the range of 0.1 to 60% by mass with respect to the total amount of (component A), (component B), (component C), and (component D), the amount of the hardening composition The viscosity exhibits good printing performance by the screen printing method, and the diffusion caused by the penetration of the hardening composition after the screen printing does not become so large. As a result, the position where the hardening composition is to be applied is obtained as a result. (Meaning the shape of the printing plate) It can be seen that the printing area of the actual curable composition does not become too large.

又，上述硬化性組成物中，(成分D)相對於(成分A)100質量份，係以包含1~30質量份之量者為佳。 Moreover, in the said curable composition, it is preferable that (component D) contains 1-30 mass parts with respect to 100 mass parts of (component A).

本發明之硬化性組成物中，使(成分D)分散的方法方面，通常，適用在塗料領域所實施的輥軋、混合器混合等，若為可充分地進行分散之方法即可。 In the method for dispersing (component D) in the curable composition of the present invention, it is generally applicable to rolling, mixer mixing, and the like performed in the field of coatings, and it is sufficient if it is a method capable of sufficiently dispersing.

再者，本發明之硬化性組成物在以印刷時消除或抑制泡的產生之目的下，係可包含消泡劑且以包含者為佳。 In addition, the curable composition of the present invention may preferably include an antifoaming agent for the purpose of eliminating or suppressing the generation of bubbles during printing.

本發明之硬化性組成物中所使用之消泡劑的具體例方面，可舉例如BYK-077(BYK JAPAN股份公司 製)、SN-DEFOAMER 470(SAN NOPCO股份公司製)、TSA750S(Momentive Performance Materials公司製)、聚矽氧油SH-203(東麗‧Dow Corning股份公司製)等之聚矽氧系消泡劑、DAPPO SN-348(SAN NOPCO股份公司製)、DAPPO SN-354(SAN NOPCO股份公司製)、DAPPO SN-368(SAN NOPCO股份公司製)、Disparlon 230HF(楠本化成股份公司製)等之丙烯酸系聚合物系消泡劑、SURFYNOL DF-110D(日信化學工業股份公司製)、SURFYNOL DF-37(日信化學工業股份公司製)等之乙炔二醇系消泡劑、FA-630等之含氟之聚矽氧系消泡劑等。此等可單獨使用1種或組合2種以上使用。 Specific examples of the antifoaming agent used in the curable composition of the present invention include BYK-077 (BYK JAPAN Co., Ltd.) ), SN-DEFOAMER 470 (manufactured by SAN NOPCO), TSA750S (manufactured by Momentive Performance Materials), silicone oil SH-203 (manufactured by Toray Dow Corning), etc. , DAPPO SN-348 (made by SAN NOPCO Corporation), DAPPO SN-354 (made by SAN NOPCO Corporation), DAPPO SN-368 (made by SAN NOPCO Corporation), Disparlon 230HF (made by Nanben Chemical Co., Ltd.), etc. Acetylene glycol-based defoamers such as polymer-based defoamers, SURFYNOL DF-110D (manufactured by Nissin Chemical Industry Co., Ltd.), SURFYNOL DF-37 (manufactured by Nissin Chemical Industry Co., Ltd.), FA-630, etc. Silicone-based antifoaming agent such as fluorine. These can be used individually by 1 type or in combination of 2 or more types.

消泡劑的含量，相對於(成分A)、(成分B)、(成分C)及(成分D)之總量(惟，本發明之硬化性組成物中不含(成分D)時，係(成分A)、(成分B)及(成分C)之總量)100質量份，係以0.01~5質量份者為佳，更佳為0.05~4質量份，特別佳為0.1~3質量份。 The content of the antifoaming agent is relative to the total amount of (ingredient A), (ingredient B), (ingredient C), and (ingredient D) (however, when (ingredient D) is not included in the curable composition of the present invention, The total amount of (ingredient A), (ingredient B) and (ingredient C)) 100 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and particularly preferably 0.1 to 3 parts by mass .

又，上述硬化性組成物中，消泡劑相對於(成分A)100質量份，係以含有0.2~10質量份之量者為佳。 Moreover, in the said curable composition, it is preferable that it is 0.2-10 mass parts with respect to 100 mass parts of (component A) defoamer.

再者，本發明之硬化性組成物，係可包含硬化促進劑且以包含者為佳。硬化促進劑方面，若為促進環氧基與羧基之反應的化合物，並無特別限定，可舉例如三聚氰胺、乙醯三聚氰二胺、苯并三聚氰二胺、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪、2,4-甲基丙烯醯氧基乙基-s-三嗪、 2,4-二胺基-6-乙烯基-s-三嗪、2,4-二胺基一6-乙烯基-s-三嗪‧異三聚氰酸加成物等之三嗪系化合物、咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-十一基咪唑、2-十七基咪唑、1-芐基一2-甲基咪唑、2-苯基一4-甲基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-胺基乙基一2-乙基一4-甲基咪唑、1-胺基乙基-2-甲基咪唑、1-(氰基乙基胺基乙基)-2-甲基咪唑、N-〔2-(2-甲基一1-咪唑基)乙基〕尿素、1-氰基乙基-2-十一基咪唑、1-氰基乙基-2-甲基咪唑嗡偏苯三甲酸酯、1-氰基乙基-2-苯基咪唑嗡偏苯三甲酸酯、1-氰基乙基-2-乙基-4-甲基咪唑嗡偏苯三甲酸酯、1-氰基乙基-2-十一基咪唑嗡偏苯三甲酸酯、2,4-二胺基-6-〔2'-甲基咪唑基-(1')〕-乙基-s-三嗪、2,4-二胺基-6-〔2'-十一基咪唑基-(1')〕-乙基-s-三嗪、2,4-二胺基-6-〔2'-乙基-4'-甲基咪唑基-(1')〕-乙基-s-三嗪、1-十二烷基-2-甲基-3-芐基咪唑嗡氯化物、N,N'-雙(2-甲基-1-咪唑基乙基)尿素、N,N'-雙(2-甲基-1-咪唑基乙基)己二醯胺、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4.5-二羥基甲基咪唑、2-甲基咪唑‧異三聚氰酸加成物、2-苯基咪唑‧異三聚氰酸加成物、2,4-二胺基-6-〔2'-甲基咪唑基-(1')〕-乙基-s-三嗪‧異三聚氰酸加成物、2-甲基一4-甲醯基咪唑、2-乙基一4-甲基一5-甲醯基咪唑、2-苯基-4-甲基甲醯基咪唑、1-芐基-2-苯基咪唑、1,2-二甲基咪唑、1-(2-羥基乙基)咪唑、乙烯基咪唑、1-甲基咪唑、1-烯丙基咪唑、2-乙基咪唑、2-丁基咪 唑、2-丁基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯并〔1,2-a〕苯并咪唑、1-芐基-2-苯基咪唑溴化氫鹽、1-十二烷基-2-甲基-3-芐基咪唑嗡氯化物等之咪唑化合物、1,5-二氮雜雙環(4.3.0)壬烯-5及其鹽、1,8-二氮雜雙環(5.4.0)十一烯-7及其鹽等之二氮雜雙環烯烴等之環脒化合物及環脒化合物之衍生物、三乙烯二胺、芐基二甲基胺、三乙醇胺、二甲基胺基乙醇、參(二甲基胺基甲基)苯酚等之胺系化合物、三苯基膦、二苯基(p-甲苯基)膦、參(烷基苯基)膦、參(烷氧基苯基)膦、參(烷基‧烷氧基苯基)膦、參(二烷基苯基)膦、參(三烷基苯基)膦、參(四烷基苯基)膦、參(二烷氧基苯基)膦、參(三烷氧基苯基)膦、參(四烷氧基苯基)膦、三烷基膦、二烷基芳基膦、烷基二芳基膦等之膦系化合物、氰二疊氮等。 The curable composition of the present invention may preferably include a hardening accelerator. The hardening accelerator is not particularly limited as long as it is a compound that promotes the reaction between an epoxy group and a carboxyl group, and examples thereof include melamine, acetamidine melamine, benzomelamine, and 2,4-diamine. Methyl-6-methacryloxyethyl-S-triazine, 2,4-methacryloxyethyl-s-triazine, 2,4-diamino-6-vinyl-s -Triazine, 2,4-diamino-6-vinyl-s-triazine, isotricyanic acid adducts, triazine compounds, imidazole, 2-methylimidazole, 2-ethyl- 4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4methylimidazole, 1-amine Ethyl-2-methylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N- [2- (2-methyl-1-imidazolyl) ethyl] urea, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitic acid Ester, 1-cyanoethyl-2-ethyl-4-methylimidazole cumene Carboxylate, l-cyanoethyl-2-undecyl imidazolium trimellitate, 2,4-diamino-6- [2 '- methyl imidazolyl - (1')] - ethyl yl -s- triazine, 2,4-diamino-6- [2 '- undecyl imidazolyl - (1')] - ethyl -s- triazine, 2,4-diamino -6 - [2 '- ethyl-4' - methyl imidazolyl - (1 ')] - ethyl -s- triazine, 1-dodecyl-2-methyl-3-benzyl-imidazolium chloride , N, N '- bis (2-methyl-imidazol-yl-ethyl) urea, N, N' - bis (2-methyl-imidazol-yl-ethyl) Amides adipic, 2-phenyl 4-methyl-5-hydroxymethylimidazole, 2-phenyl-4.5-dihydroxymethylimidazole, 2-methylimidazole‧isotricyanic acid adduct, 2-phenylimidazole‧isotrimer cyanate adduct, 2,4-diamino-6- [2 '- methyl imidazolyl - (1')] - ethyl isobutyl ‧ -s- triazine cyanuric adduct, 2- Methyl-4-methylimidazole, 2-ethyl-4-methyl-5-methylimidazole, 2-phenyl-4-methylmethylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 1- (2-hydroxyethyl) imidazole, vinylimidazole, 1-methylimidazole, 1-allylimidazole, 2-ethylimidazole, 2-butylimidazole 2-butyl-5-hydroxymethyl imide Azole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-benzyl-2-phenylimidazole hydrogen bromide, 1-dodecyl-2-methyl Imidazole compounds such as 3-benzylimidazolium chloride, 1,5-diazabicyclo (4.3.0) nonene-5 and its salts, 1,8-diazabicyclo (5.4.0) 11 Cyclopentamidine compounds such as diazabicyclic olefins such as alkenes-7 and their salts, and derivatives of cyclic amidine compounds, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng ( Amine compounds such as dimethylaminomethyl) phenol, triphenylphosphine, diphenyl (p-tolyl) phosphine, gins (alkylphenyl) phosphine, gins (alkoxyphenyl) phosphine, Phen (alkyl‧alkoxyphenyl) phosphine, Phen (dialkylphenyl) phosphine, Phen (trialkylphenyl) phosphine, Phen (tetraalkylphenyl) phosphine, Phen (dialkoxybenzene) Phosphine compounds such as phosphine, phosphine (trialkoxyphenyl) phosphine, para (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc. Cyanodiazide and so on.

此等之硬化促進劑可單獨使用，亦可併用2種以上。 These hardening accelerators may be used alone or in combination of two or more.

此等之硬化促進劑之中，若考慮兼具硬化促進作用及電氣絕緣性能，較佳為三聚氰胺、咪唑化合物、環脒化合物、環脒化合物之衍生物、膦系化合物及胺系化合物，更佳為三聚氰胺、1,5-二氮雜雙環(4.3.0)壬烯-5及其鹽、1,8-二氮雜雙環(5.4.0)十一烯-7及其鹽。 Among these hardening accelerators, melamine, an imidazole compound, a cyclofluorene compound, a derivative of a cyclofluorene compound, a phosphine compound, and an amine compound are more preferable in consideration of both the hardening promoting effect and the electrical insulation performance. It is melamine, 1,5-diazabicyclo (4.3.0) nonene-5 and its salt, 1,8-diazabicyclo (5.4.0) undecene-7 and its salt.

此等之硬化促進劑的摻合量，若可達成硬化促進效果，並無特別限制。但是，從本發明之硬化性組成物的硬化性及硬化本發明之硬化性組成物所得的被覆膜之電氣絕緣特性或耐水性之觀點來看，相對於本發明之硬化 性組成物中作為本發明之必須成分的(成分A)與(成分B)之總量100質量份，係以0.05~5質量份的範圍進行摻合者為佳，更佳為0.1~3質量份。摻合量相對於(成分A)與(成分B)之總量100質量份，若為0.05~5質量份的範圍，則可短時間使其硬化且將本發明之硬化性組成物硬化所得之被覆膜的電氣絕緣特性或耐水性會變佳。 The blending amount of these hardening accelerators is not particularly limited as long as the hardening promoting effect can be achieved. However, from the viewpoint of the hardenability of the hardenable composition of the present invention and the electrical insulation properties or water resistance of the coating film obtained by hardening the hardenable composition of the present invention, it is compared with the hardening of the present invention. 100 parts by mass of the total amount of (ingredient A) and (ingredient B) in the sexual composition as an essential component of the present invention is preferably blended in a range of 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass Serving. The blending amount is based on 100 parts by mass of the total amount of (component A) and (component B), and if it is in the range of 0.05 to 5 parts by mass, it can be cured in a short time and the curable composition of the present invention can be cured. The coating film has better electrical insulation properties and water resistance.

又，有必要抑制樹脂的酸價劣化及加熱時的變色時，可於本發明之硬化性組成物中添加苯酚系抗氧化劑、亞磷酸鹽系抗氧化劑、硫代醚系抗氧化劑等之抗氧化劑。 When it is necessary to suppress deterioration of the acid value of the resin and discoloration during heating, antioxidants such as phenol-based antioxidants, phosphite-based antioxidants, and thioether-based antioxidants can be added to the curable composition of the present invention. .

再者，本發明之硬化性組成物中，為了使塗工時的作業性及被膜形成前後的膜特性提昇，係可添加調平劑或者染料或顏料等之著色劑類、難燃劑、潤滑劑。 Furthermore, in the hardening composition of the present invention, in order to improve workability during coating work and film characteristics before and after film formation, coloring agents such as leveling agents, dyes, pigments, flame retardants, and lubricants may be added. Agent.

本發明之硬化性組成物之製造方法，若為(成分A)、(成分B)及(成分C)與因應所需的其他成分可溶解或分散於有機溶劑中之方法，並無特別限制。例如，本發明之硬化性組成物，係可製造至少包含(成分A)之主劑與至少包含(成分B)之硬化劑，且接著摻合主劑與硬化劑來製造。 The method for producing the curable composition of the present invention is not particularly limited as long as it is a method in which (component A), (component B), and (component C) and other components required can be dissolved or dispersed in an organic solvent. For example, the curable composition of the present invention can be produced by producing a main agent including at least (component A) and a hardener including at least (component B), and then mixing the main agent and the hardener.

又，本發明之硬化性組成物係在使網版印刷性良好且印刷了硬化性組成物之後，為了避免該組成物會流動而導致無法成為一定的膜厚，希望搖改性指數在25℃時為1.1以上，更佳為1.1~3.0的範圍，特別佳為1.1~2.5的範圍。為了使搖改性指數在25℃時為1.1以上，雖有使用 前述無機微粒子或有機微粒子來調整搖改性指數之方法、使用高分子添加劑來調整搖改性指數之方法等，其中以使用無機微粒子或有機微粒子來調整搖改性指數之方法者為佳。 In addition, after the hardenable composition of the present invention has good screen printing properties and the hardenable composition is printed, in order to prevent the composition from flowing and preventing it from becoming a certain film thickness, it is desirable that the shake modification index be 25 ° C. It is 1.1 or more, more preferably in the range of 1.1 to 3.0, and particularly preferably in the range of 1.1 to 2.5. In order to make the shake modification index 1.1 or higher at 25 ° C, The method of adjusting the shake modification index of the inorganic fine particles or organic fine particles, the method of adjusting the shake modification index using a polymer additive, and the like are preferably a method of adjusting the shake modification index using an inorganic fine particle or an organic fine particle.

此外，本說明書中記載之「搖改性指數」係以使用錐板式黏度計(Brookfield公司製，型式：DV-II+Pro，主軸的型號：CPE-52)來測定，且為25℃中的回轉數1rpm時的黏度與主軸25℃中的回轉數10rpm時的黏度之比來定義。 In addition, the "shake modification index" described in this specification was measured using a cone-plate viscometer (manufactured by Brookfield, type: DV-II + Pro, model of spindle: CPE-52), and it was measured at 25 ° C. The ratio of the viscosity at 1 rpm and the viscosity at 10 rpm at 25 ° C of the spindle is defined.

又，有必要抑制樹脂的酸價劣化及加熱時的變色時，可於本發明之硬化性組成物中添加苯酚系抗氧化劑、亞磷酸鹽系抗氧化劑、硫代醚系抗氧化劑等之抗氧化劑。 When it is necessary to suppress deterioration of the acid value of the resin and discoloration during heating, antioxidants such as phenol-based antioxidants, phosphite-based antioxidants, and thioether-based antioxidants can be added to the curable composition of the present invention. .

再者，本發明之硬化性組成物中，為了使塗工時的作業性及被膜形成前後的膜特性提昇，係可添加調平劑或者染料或顏料等之著色劑類、難燃劑、潤滑劑。 Furthermore, in the hardening composition of the present invention, in order to improve workability during coating work and film characteristics before and after film formation, coloring agents such as leveling agents, dyes, pigments, flame retardants, and lubricants may be added. Agent.

硬化性組成物，藉由回轉型黏度計所測定之25℃中的黏度係以20Pa‧s~80Pa‧s者為佳，30Pa‧s~50Pa‧s者更佳。該黏度若未達20Pa‧s，印刷後的組成物之流出變大，同時有膜厚薄膜化之傾向，若超過80Pa‧s，則該組成物對基材之轉印性降低，同時有印刷膜中之孔隙及針孔增加的傾向。 For the hardening composition, the viscosity at 25 ° C. measured by a rotary viscometer is preferably 20 Pa · s to 80 Pa · s, and more preferably 30 Pa · s to 50 Pa · s. If the viscosity is less than 20Pa‧s, the outflow of the composition after printing will increase, and at the same time, the film thickness will tend to be thin. If it exceeds 80Pa‧s, the transferability of the composition to the substrate will be reduced, and printing will also occur. Pore and pinhole tendency in the membrane.

接著，就本發明之硬化膜、本發明之被覆膜、可撓性配線板及可撓性配線板之製造方法進行說明。 Next, the manufacturing method of the cured film of this invention, the coating film of this invention, a flexible wiring board, and a flexible wiring board is demonstrated.

本發明之硬化膜乃是包含將本發明之硬化性組成物予以硬化而得之硬化物。又，本發明之電子零件具有上述硬化膜。 The cured film of the present invention includes a cured product obtained by curing the curable composition of the present invention. Moreover, the electronic component of this invention has the said hardened film.

又，本發明之被覆膜乃是包含本發明之硬化性組成物的硬化物之可撓性配線板用被覆膜，更詳言之，乃是藉由將本發明之硬化性組成物塗佈於在可撓性基板上形成有配線而成的可撓性配線板之形成有配線的表面之一部分或全部並予以硬化所得之可撓性配線板用被覆膜。 In addition, the coating film of the present invention is a coating film for a flexible wiring board including a cured product of the curable composition of the present invention. More specifically, the coating film is applied by coating the curable composition of the present invention. A coating film for a flexible wiring board, which is formed by hardening a part or all of a surface on which a wiring is formed on a flexible wiring board having wiring formed on a flexible substrate.

又，本發明之可撓性配線板係在可撓性基板上形成有配線而成的可撓性配線板之形成有配線的表面之一部分或全部係被前述被覆膜所被覆之可撓性配線板。 In addition, the flexible wiring board of the present invention is a part or all of the surface of the flexible wiring board of the flexible wiring board in which wiring is formed on a flexible substrate, which is covered by the coating film. Wiring board.

此外，被此被覆膜所被覆之配線若考慮配線的抗氧化及經濟層面的話，係以錫鍍敷銅配線者為佳。 In addition, if the wiring covered by this coating film considers the oxidation resistance and economic aspects of the wiring, it is better to use tin-plated copper wiring.

再者，本發明之可撓性配線板之製造方法係包含下述之步驟1'及步驟2'之藉由被覆膜所被覆之可撓性配線板之製造方法。 Furthermore, the method for manufacturing a flexible wiring board of the present invention is a method for manufacturing a flexible wiring board covered with a coating film in the following steps 1 ' and 2 ' .

(步驟1')藉由將本發明之硬化性組成物印刷於可撓性配線板之配線圖型部的至少一部分，而於該圖型上形成印刷膜之步驟 (Step 1 ' ) A step of forming a printed film on the pattern by printing the curable composition of the present invention on at least a part of a wiring pattern portion of a flexible wiring board.

(步驟2')步驟1'所得之印刷膜、將步驟1'所得之印刷膜置於40~100℃之氛圍下藉此使印刷膜中之溶劑的一部份蒸發之一部份溶劑被去除而成的印刷膜、或將步驟1'所得之印刷膜置於40~100℃之氛圍下而使印刷膜中之溶劑全量蒸發之全量溶劑被去除而成之印刷膜，藉由在100~170 ℃加熱而使其硬化並形成被覆膜之步驟。 (Step 2 ' ) The printing film obtained in step 1 ', and the printing film obtained in step 1 'is placed in an atmosphere of 40 ~ 100 ° C, thereby a part of the solvent in the printing film is evaporated, and a part of the solvent is removed. The printed film produced, or the printed film obtained by placing the printed film obtained in step 1 ′ in an atmosphere of 40 to 100 ° C., and the solvent in the printed film is completely evaporated, and the entire amount of the solvent is removed. A step of heating at a temperature of ℃ to form a coating film.

本發明之硬化性組成物，例如可使用作為配線的絕緣保護用被覆膜用的油墨，且本發明之硬化物可使用作為絕緣保護用被覆膜。特別是藉由被覆例如覆晶壓合薄膜(COF)般之可撓性配線板的配線的全部或一部份而得以用作為配線的絕緣保護用被覆膜。 For the curable composition of the present invention, for example, an ink for a coating film for insulating protection can be used, and the cured product of the present invention can be used as a coating film for insulating protection. In particular, by covering all or part of the wiring of a flexible wiring board such as a chip-on-film (COF), it can be used as a covering film for insulation protection of wiring.

以下記述以本發明之可撓性配線板之製造方法所實施的具體步驟。例如，經以下的步驟1及步驟3與因應需要而經步驟2，係可形成可撓性配線板的被覆膜。 Specific steps carried out by the method for manufacturing a flexible wiring board of the present invention are described below. For example, a coating film for a flexible wiring board can be formed through the following steps 1 and 3 and step 2 as necessary.

(步驟1) (step 1)

藉由將本發明之硬化性組成物印刷於可撓性配線板之配線圖型部的至少一部分，而於該圖型上形成印刷膜之步驟 A step of forming a printed film on the pattern by printing the curable composition of the present invention on at least a part of a wiring pattern portion of a flexible wiring board

(步驟2) (Step 2)

藉由將步驟1所得之印刷膜置於40~100℃之氛圍下，而使印刷膜中之溶劑的一部分或全量蒸發之步驟 A step of evaporating a part or all of the solvent in the printed film by placing the printed film obtained in step 1 in an atmosphere of 40 to 100 ° C

(步驟3) (Step 3)

藉由將步驟1所得之印刷膜或步驟2所得之印刷膜於100~170℃加熱，使其硬化並形成被覆膜之步驟。 The step of heating the printed film obtained in step 1 or the printed film obtained in step 2 at 100 to 170 ° C. to harden and form a coating film.

步驟2所實施之藉由將步驟1所得之印刷膜置於40~100℃之氛圍下使印刷膜中之溶劑蒸發時的溫度，若考慮溶劑的蒸發速度及對接下來的操作(以100~170℃進行加熱而使其硬化之操作)快速的移行，通常為40~100℃，較佳為60~100℃，更佳為70~90℃。步驟2所實施的藉 由將步驟1所得之印刷膜置於40~100℃之氛圍下，使印刷膜中之溶劑蒸發的時間雖無特別限制，但較佳為10~120分、更佳為20~100分。 The temperature in step 2 is implemented by placing the printing film obtained in step 1 under an atmosphere of 40 ~ 100 ° C to evaporate the solvent in the printing film. If the evaporation rate of the solvent and the next operation (100 ~ 170) are considered The operation of heating at ℃ to harden it) is rapid transition, usually 40 to 100 ° C, preferably 60 to 100 ° C, and more preferably 70 to 90 ° C. Borrowing implemented in step 2 The time for evaporating the solvent in the printed film by placing the printed film obtained in step 1 under an atmosphere of 40 to 100 ° C is not particularly limited, but it is preferably 10 to 120 minutes, and more preferably 20 to 100 minutes.

此外，此藉由將步驟1所得之印刷膜置於40~100℃之氛圍下，使印刷膜中之溶劑蒸發的操作，乃是因應需要所實施的操作，步驟1的操作之後，立刻移行至步驟3而以100~170℃進行加熱，藉此使其硬化，並實施形成被覆膜之操作，亦可同時進行硬化反應與溶劑的去除。在此所實施的熱硬化條件，從防止鍍敷層的擴散且得到作為保護膜較佳的低翹曲性、柔軟性之觀點來看，熱硬化溫度係以105~160℃為佳，更佳為110~150℃。藉由加熱而使其硬化，形成被覆膜時的熱硬化時間並無特別限制，較佳為10~150分、更佳為15~120分。 In addition, the operation of evaporating the solvent in the printed film by placing the printed film obtained in step 1 in an atmosphere of 40 to 100 ° C is an operation performed as required. After the operation in step 1, immediately move to In step 3, heating is performed at 100 to 170 ° C. to harden it, and the operation of forming a coating film is performed. The hardening reaction and the removal of the solvent may be performed at the same time. The thermal curing conditions implemented here are from the viewpoint of preventing diffusion of the plating layer and obtaining low warpage and softness as a protective film, and the thermal curing temperature is preferably 105 to 160 ° C, and more preferably 110 ~ 150 ℃. It is hardened by heating, and the heat curing time when forming a coating film is not particularly limited, but is preferably 10 to 150 minutes, and more preferably 15 to 120 minutes.

藉由上述的方法可獲得可撓性配線板，該可撓性配線板係在可撓性基板上形成有配線而成的可撓性配線板之形成有配線的表面之一部分或全部被前述被覆膜所被覆者。 A flexible wiring board can be obtained by the above-mentioned method. The flexible wiring board is a part or all of the wiring-forming surface of a flexible wiring board formed by wiring formed on a flexible substrate. Covered by the film.

又，本發明之硬化性組成物係可因應需要而摻合前述的任意成分，並可均一地混合，且被膜形成材料方面，除了可用於半導體元件或各種電子零件用被覆油墨、阻焊劑油墨、層間絕緣膜之外，亦可使用作為塗料、塗佈劑、接著劑等。 In addition, the hardenable composition of the present invention can be blended with any of the aforementioned components as required, and can be uniformly mixed. In addition to the film-forming material, it can be used for coating inks, solder resist inks for semiconductor devices or various electronic parts, In addition to the interlayer insulating film, it can also be used as a coating material, a coating agent, an adhesive, and the like.

〔實施例〕 [Example]

雖可藉由以下實施例來進一步具體地說明本發明，本發明並不受限於以下的實施例。 Although the present invention can be further specifically explained by the following examples, the present invention is not limited to the following examples.

<酸價的測定> <Measurement of acid value>

本發明中使用的包含(成分A)之溶液乃藉由以下的方法來測定酸價，使用式(α)來求得(成分A)之酸價。惟，用於前述溶液之溶劑中，係使用酸價為「0」者。 The solution containing (component A) used in the present invention measures the acid value by the following method, and uses the formula (α) to obtain the acid value of (component A). However, the solvents used in the aforementioned solutions are those having an acid value of "0".

首先，精秤包含(成分A)之溶液約1g。之後，相對於此，添加異丙基醇/甲苯=1/2(質量比)之混合溶劑30g，均一地溶解。於所得的溶液中適量地添加作為指示劑之酚酞，並使用0.1N之KOH溶液(醇性)進行滴定。然後，由滴定結果以下述式(α)：A=10×Vf×56.1/(Wp×I)‧‧‧‧‧式(α)來算出酸價。式(α)中，A表示酸價(mgKOH/g)，Vf表示0.1N之KOH溶液的滴定量(mL)，Wp表示包含(成分A)之溶液的質量(g)，I表示包含(成分A)之溶液的成分(A)之比例(質量%)。 First, the fine scale contains about 1 g of the solution of (component A). Thereafter, 30 g of a mixed solvent of isopropyl alcohol / toluene = 1/2 (mass ratio) was added thereto, and the mixture was uniformly dissolved. To the obtained solution, an appropriate amount of phenolphthalein was added as an indicator, and titration was performed using a 0.1N KOH solution (alcoholic). Then, the acid value was calculated from the result of the titration using the following formula (α): A = 10 × Vf × 56.1 / (Wp × I) ‧ ‧ ‧ ‧ ‧ formula (α). In the formula (α), A represents an acid value (mgKOH / g), Vf represents a titer (mL) of a 0.1N KOH solution, Wp represents a mass (g) of a solution containing (component A), and I represents a component containing (component The ratio (% by mass) of the component (A) of the solution of A).

<羥基價的測定> <Determination of hydroxyl value>

依據JIS K0070來測定羥基價。 The hydroxyl value was measured in accordance with JIS K0070.

<數平均分子量的測定> <Determination of number average molecular weight>

數平均分子量係以GPC測定之聚苯乙烯換算的數平均 分子量，GPC的測定條件係如以下所述。 Number average molecular weight is the number average of polystyrene conversion measured by GPC The measurement conditions of molecular weight and GPC are as follows.

裝置名：日本分光股份公司製HPLC單元HSS-2000 Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation

管柱：Shodex(註冊商標)管柱LF-804×3本(直列) Column: Shodex (registered trademark) column LF-804 × 3 (in-line)

移動相：四氫呋喃 Mobile phase: tetrahydrofuran

流速：1.0mL/min Flow rate: 1.0mL / min

檢出器：日本分光股份公司製RI-2031Plus Detector: RI-2031Plus, manufactured by JASCO Corporation

溫度：40.0℃ Temperature: 40.0 ℃

試料量：樣品環100μL Sample volume: 100 μL of sample loop

試料濃度：調整至0.1質量%前後。 Sample concentration: before and after adjustment to 0.1% by mass.

<搖改性指數的測定> <Determination of Shake Modification Index>

硬化性組成物之搖改性指數乃是藉由以下的方法來測定。 The shake modification index of the hardenable composition is measured by the following method.

使用硬化性組成物約0.8g，用錐板式黏度計(Brookfield公司製 型式；DV-II+Pro主軸的型號；CPE-52)，以溫度25.0℃、回轉數10rpm之條件，測定從測定開始經過7分鐘後的黏度。之後，以溫度25.0℃、回轉數1rpm之條件，測定從測定開始經過7分鐘後的黏度。 Using a hardening composition of about 0.8 g, use a cone-plate viscometer (type manufactured by Brookfield; DV-II + Pro spindle model; CPE-52) at a temperature of 25.0 ° C and a number of revolutions of 10 rpm. Viscosity after 7 minutes. Thereafter, the viscosity was measured after 7 minutes from the start of the measurement under the conditions of a temperature of 25.0 ° C and a number of revolutions of 1 rpm.

此外，搖改性指數乃是藉由以下的計算來求得。 The shake modification index was obtained by the following calculation.

搖改性指數的求取方法： 搖改性指數=〔1rpm的黏度〕÷〔10rpm的黏度〕 How to get the modification index: Shaking modification index = [viscosity at 1 rpm] ÷ [viscosity at 10 rpm]

<聚酯多元醇的合成> <Synthesis of Polyester Polyols>

(參考合成例1) <聚酯二醇(α)> (Reference Synthesis Example 1) <Polyester diol (α)>

於具備有攪拌裝置、溫度計及附蒸餾裝置之電容器的反應容器中，添加無水苯二甲酸1684.6g(11.56mol)、1,6-己烷二醇1484.5g(12.55mol)，將反應容器的內溫使用油浴昇溫至140℃，繼續攪拌4小時。之後，一邊繼續攪拌，一邊添加單-n-丁基錫氧化物2.96g，緩慢地將反應容器的內溫昇溫，接續真空幫浦，逐漸少量地減去反應容器內的壓力，藉由減壓蒸餾將水去除至反應容器外。最終是將內溫昇溫至220℃為止，將壓力減至133.32Pa為止。經過15小時之後確認水完全餾去而將反應結束。所得之聚酯多元醇(以下記為聚酯二醇(α))乃具有前述式(1)之構造，n=1~20。測定其羥基價的結果，羥基價為35.4mg-KOH/g。 To a reaction container provided with a stirring device, a thermometer, and a capacitor with a distillation device, 1684.6 g (11.56 mol) of anhydrous phthalic acid and 1484.5 g (12.55 mol) of 1,6-hexanediol were added. The temperature was raised to 140 ° C using an oil bath, and stirring was continued for 4 hours. After that, while continuing to stir, 2.96 g of mono-n-butyltin oxide was added, and the internal temperature of the reaction vessel was gradually raised, followed by vacuum pumping, and the pressure in the reaction vessel was gradually reduced by a small amount. Water was removed outside the reaction vessel. Finally, the internal temperature was raised to 220 ° C. and the pressure was reduced to 133.32 Pa. After 15 hours, it was confirmed that water was completely distilled off and the reaction was completed. The obtained polyester polyol (hereinafter referred to as polyester diol (α)) has a structure of the aforementioned formula (1), and n = 1 to 20. As a result of measuring the hydroxyl value, the hydroxyl value was 35.4 mg-KOH / g.

<(成分A)之合成> <Synthesis of (component A)>

(合成例1) <A-1溶液> (Synthesis example 1) <A-1 solution>

於裝置有攪拌機、冷却管、氮導入管及溫度計的四口燒瓶中，加入作為四羧酸二酐之3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)270.7質量份與作為溶劑之γ-丁內酯964.4質量份，於120℃攪拌、溶解。朝其中，添加作為二異氰酸酯化合物之4,4'-二苯基甲烷二異氰酸酯(MDI)142.6質量份並予以攪拌，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，在氮氣流下使其於120℃反應3小時。之後，藉由冷卻至室溫為止，得到固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物。 In the apparatus with a stirrer, condenser four-neck flask, a nitrogen inlet tube and a thermometer, was added as a tetracarboxylic dianhydride of 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride (BTDA) 270.7 Mass parts and 964.4 mass parts of γ-butyrolactone as a solvent were stirred and dissolved at 120 ° C. Towards wherein the diisocyanate was added as an ester compound of 4,4 '- diphenylmethane diisocyanate (MDI) 142.6 parts by mass to be stirred and, as added to the catalyst of 1,8-diazabicyclo [5.4.0] 0.1-parts of 7-undecene (DBU) was reacted at 120 ° C for 3 hours under a nitrogen stream. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

接著，將所得的固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物加熱並攪拌至100℃為止，添加聚酯二醇(α)950.8質量份、9,9-雙〔4-(2-羥基乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)82.7質量份、γ-丁內酯1200.5質量份，並予以攪拌。於其中添加作為觸媒之4-二甲基胺基吡啶(DMAP)2.4質量份，並使其於100℃反應8小時。之後，藉由冷卻至室溫為止，得到固形分濃度40質量%之具有醯亞胺鍵與羥基之化合物(以下記為「化合物(A-1)」)之溶液。化合物(A-1)之數平均分子量為15000、分散度為4.0、固形分的酸價為25mgKOH/g、由置入比算出之芳香環濃度為5.0mmol/g。 Next, the obtained sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was heated and stirred to 100 ° C, and 950.8 parts by mass of polyester diol (α), 9,9-bis [4 -(2-hydroxyethoxy) phenyl] pyrene (manufactured by Osaka Gas Chemical Co., Ltd .: BPEF) 82.7 parts by mass and γ-butyrolactone 1200.5 parts by mass, and stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-1)") having a solid content concentration of 40% by mass was obtained. The number average molecular weight of the compound (A-1) was 15,000, the degree of dispersion was 4.0, the acid value of the solid content was 25 mgKOH / g, and the aromatic ring concentration calculated from the insertion ratio was 5.0 mmol / g.

(合成例2) <A-2溶液> (Synthesis example 2) <A-2 solution>

於裝置有攪拌機、冷却管、氮導入管及溫度計的四口燒瓶中，加入作為四羧酸二酐之3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)270.7質量份與作為溶劑之γ-丁內酯964.4質量份，於120℃攪拌、溶解。朝其中，添加作為二異氰酸酯化合物之4,4'-二苯基甲烷二異氰酸酯(MDI)142.6質量份並予以攪拌，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，在氮氣流下使其於120℃反應3小時。之後，藉由冷卻至室溫為止，得到固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物。 In the apparatus with a stirrer, condenser four-neck flask, a nitrogen inlet tube and a thermometer, was added as a tetracarboxylic dianhydride of 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride (BTDA) 270.7 Mass parts and 964.4 mass parts of γ-butyrolactone as a solvent were stirred and dissolved at 120 ° C. Towards wherein the diisocyanate was added as an ester compound of 4,4 '- diphenylmethane diisocyanate (MDI) 142.6 parts by mass to be stirred and, as added to the catalyst of 1,8-diazabicyclo [5.4.0] 0.1-parts of 7-undecene (DBU) was reacted at 120 ° C for 3 hours under a nitrogen stream. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

接著，將所得的固形分濃度30質量%之末端含 酸酐基之醯亞胺預聚物加熱並攪拌至100℃為止，添加3-甲基-1,5-戊烷二醇：異苯二甲酸的聚酯多元醇(KURARAY公司製 商品名：KURARAY多元醇P-3030(※))950.8質量份、9,9-雙〔4-(2-羥基乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)82.7質量份、γ-丁內酯1200.5質量份，並予以攪拌。於其中添加作為觸媒之4-二甲基胺基吡啶(DMAP)2.4質量份，並使其於100℃反應8小時。之後，藉由冷卻至室溫為止，得到固形分濃度40質量%之具有醯亞胺鍵與羥基之化合物(以下記為「化合物(A-2)」)之溶液。化合物(A-2)之數平均分子量為15000、分散度為4.0、固形分的酸價為25mgKOH/g、芳香環濃度為5.0mmol/g。 Next, the end of the obtained solid content concentration of 30% by mass was contained. The anhydride-based sulfonium imine prepolymer was heated and stirred to 100 ° C, and 3-methyl-1,5-pentanediol: a polyester polyol of isophthalic acid (KURARAY company product name: KURARAY poly Alcohol P-3030 (*)) 950.8 parts by mass, 9,9-bis [4- (2-hydroxyethoxy) phenyl] osmium (manufactured by Osaka Gas Chemical Co., Ltd., trade name: BPEF) 82.7 parts by mass, γ-butyl 1200.5 parts by mass of lactone was stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-2)") having a solid content concentration of 40% by mass was obtained. The compound (A-2) had a number average molecular weight of 15,000, a degree of dispersion of 4.0, an acid value of 25 mgKOH / g as a solid content, and an aromatic ring concentration of 5.0 mmol / g.

(※具有前述之式(1)之構造的聚酯多元醇、n之平均為12.0~12.1) (* The average value of the polyester polyol having the structure of the above formula (1), n is 12.0 ~ 12.1)

(合成例3) <A-3溶液> (Synthesis example 3) <A-3 solution>

於裝置有攪拌機、冷却管、氮導入管及溫度計的四口燒瓶中，加入作為四羧酸二酐之3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)270.7質量份、作為溶劑之γ-丁內酯863.2質量份，於120℃攪拌、溶解。朝其中，添加作為二異氰酸酯化合物之2,4-三氯乙烯二異氰酸酯與2,6-三氯乙烯二異氰酸酯之質量比80：20的混合物之COSMONATE T-80(三井化學聚胺基甲酸酯股份公司製)(TDI)99.3質量份並予以攪拌，於其中添加作為觸媒之1,8-二氮雜雙環〔 5.4.0〕-7-十一烯(DBU)0.1質量份，在氮氣流下使其於120℃反應3小時。之後，藉由冷卻至室溫為止，得到固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物。 In the apparatus with a stirrer, condenser four-neck flask, a nitrogen inlet tube and a thermometer, was added as a tetracarboxylic dianhydride of 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride (BTDA) 270.7 863.2 parts by mass of γ-butyrolactone as a solvent was stirred and dissolved at 120 ° C. To this, COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound in a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. 99.3 parts by mass (TDI) (TDI) and stirred, and 0.1 part by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added thereto under a nitrogen stream It was made to react at 120 degreeC for 3 hours. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

接著，將所得的固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物加熱並攪拌至100℃為止，添加聚酯二醇(α)950.8質量份與9,9-雙〔4-(2-羥基乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)82.7質量份、γ-丁內酯1239.4質量份並予以攪拌。於其中添加作為觸媒之4-二甲基胺基吡啶(DMAP)2.4質量份，並使其於100℃反應8小時。之後，藉由冷卻至室溫為止，得到固形分濃度40質量%之具有醯亞胺鍵與羥基之化合物(以下記為「化合物(A-3)」)之溶液。化合物(A-3)之數平均分子量為15000、分散度為4.0、固形分的酸價為26mgKOH/g、芳香環濃度為4.8mmol/g。 Next, the obtained ammonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was heated and stirred to 100 ° C, and 950.8 parts by mass of polyester diol (α) and 9,9-bis [4] were added. -(2-hydroxyethoxy) phenyl] pyrene (manufactured by Osaka Gas Chemical Co., Ltd .: BPEF) 82.7 parts by mass and γ-butyrolactone 1239.4 parts by mass and stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-3)") having a solid content concentration of 40% by mass was obtained. The compound (A-3) had a number average molecular weight of 15,000, a dispersion degree of 4.0, an acid value of a solid content of 26 mgKOH / g, and an aromatic ring concentration of 4.8 mmol / g.

(合成例4) <A-4溶液> (Synthesis example 4) <A-4 solution>

於裝置有攪拌機、冷却管、氮導入管及溫度計的四口燒瓶中，加入作為四羧酸二酐之3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)270.7質量份、作為溶劑之γ-丁內酯863.2質量份，於120℃攪拌、溶解。朝其中，添加作為二異氰酸酯化合物之2,4-三氯乙烯二異氰酸酯與2,6-三氯乙烯二異氰酸酯之質量比80：20的混合物之COSMONATE T-80(三井化學聚胺基甲酸酯股份公司製)(TDI)99.3質量份並予以攪拌，於其中添加作為觸媒之1,8-二氮雜雙環〔 5.4.0〕-7-十一烯(DBU)0.1質量份，在氮氣流下使其於120℃反應3小時。之後，藉由冷卻至室溫為止，得到固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物。 In the apparatus with a stirrer, condenser four-neck flask, a nitrogen inlet tube and a thermometer, was added as a tetracarboxylic dianhydride of 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride (BTDA) 270.7 863.2 parts by mass of γ-butyrolactone as a solvent was stirred and dissolved at 120 ° C. To this, COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound in a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. 99.3 parts by mass (TDI) (TDI) and stirred, and 0.1 part by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added thereto under a nitrogen stream It was made to react at 120 degreeC for 3 hours. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

接著，將所得的固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物加熱並攪拌至100℃為止，添加3-甲基-1,5-戊烷二醇：異苯二甲酸的聚酯多元醇(KURARAY公司製 商品名：KURARAY多元醇P-3030)950.8質量份與9,9-雙〔4-(2-羥基乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)82.7質量份、γ-丁內酯1239.4質量份並予以攪拌。於其中添加作為觸媒之4-二甲基胺基吡啶(DMAP)2.4質量份，並使其於100℃反應8小時。之後，藉由冷卻至室溫為止，得到固形分濃度40質量%之具有醯亞胺鍵與羥基之化合物(以下記為「化合物(A-4)」)之溶液。化合物(A-4)之數平均分子量為15000、分散度為4.0、固形分的酸價為26mgKOH/g、芳香環濃度為4.8mmol/g。 Next, the obtained hydrazone imine prepolymer having a terminal acid anhydride group at a solid concentration of 30% by mass was heated and stirred to 100 ° C, and 3-methyl-1,5-pentanediol: isophthalic acid was added. 950.8 parts by mass of polyester polyol (KURARAY Co., Ltd. product name: KURARAY Polyol P-3030) and 9,9-bis [4- (2-hydroxyethoxy) phenyl] pyrene (manufactured by Osaka Gas Chemical Co., Ltd., product Name: BPEF) 82.7 parts by mass and γ-butyrolactone 1239.4 parts by mass and stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-4)") having a solid content concentration of 40% by mass was obtained. The compound (A-4) had a number average molecular weight of 15,000, a dispersion degree of 4.0, an acid value of a solid content of 26 mgKOH / g, and an aromatic ring concentration of 4.8 mmol / g.

(合成例5) <A-5溶液> (Synthesis example 5) <A-5 solution>

於具備有攪拌裝置、溫度計、電容器之反應容器中，放入聚酯二醇(α)567.4g(0.1mol)與9,9-雙〔4-(2-羥基乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)34.65g(0.08mol)，置入作為4,4'-二苯基甲烷二異氰酸酯之MILLIONATE MT(日本聚胺基甲酸酯工業股份公司製)53.65g(0.214mol)及2,4-三氯乙烯二異氰酸 酯與2,6-三氯乙烯二異氰酸酯之質量比80：20的混合物之COSMONATE T-80(三井化學聚胺基甲酸酯股份公司製)24.89g(0.143mol)與γ-丁內酯1021g，於150℃使全部的原料溶解，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，並使其反應4小時，使其生成具有胺基甲酸酯鍵之聚異氰酸酯。 In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, 567.4 g (0.1 mol) of polyesterdiol (α) and 9,9-bis [4- (2-hydroxyethoxy) phenyl] 茀(Osaka gas chemical Co., trade name: BPEF) 34.65g (0.08mol), placed as 4,4 '- MILLIONATE MT-diisocyanate diphenylmethane bis (Japan industrial polyurethane AG Ltd.) 53.65 (0.214mol) and a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20 COSMONATE T-80 (Mitsui Chemical Polyurethane Co., Ltd.) 24.89 g (0.143 mol) and 1021 g of γ-butyrolactone, all the raw materials were dissolved at 150 ° C, and 1,8-diazabicyclo [5.4.0] -7-undecene (5.4.0) as a catalyst was added thereto. DBU) 0.1 parts by mass and allowed to react for 4 hours to produce a polyisocyanate having a urethane bond.

接著，使反應液之溫度降至60℃為止，加入無水偏苯三甲酸63.71g(0.332mol)使其完全溶解之後，加入MILLIONATE MT 23.00g(0.092mol)及COSMONATE T-80 10.67g(0.061mol)與γ-丁內酯146.07g，昇溫至120℃使全部的原料溶解，並反應1小時。 Next, the temperature of the reaction solution was reduced to 60 ° C, 63.71 g (0.332 mol) of anhydrous trimellitic acid was added to completely dissolve, and MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) were added. ) And 146.07 g of γ-butyrolactone, heated to 120 ° C. to dissolve all the raw materials, and reacted for 1 hour.

之後，將反應液的溫度提昇至180℃為止，使其於180℃反應2小時。接著，將反應液的溫度降至120℃為止，加入2-丁酮肟(和光純藥股份公司製)5.61g，使反應結束，冷卻至室溫為止，得到固形分濃度40質量%的具有醯胺鍵及醯亞胺鍵與羧基之化合物(以下記為「化合物(A-5)」)之溶液。 Thereafter, the temperature of the reaction solution was raised to 180 ° C, and the reaction was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction solution was lowered to 120 ° C, 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction was completed, and the mixture was cooled to room temperature to obtain a solid content concentration of 40% by mass. A solution of a compound (hereinafter referred to as "compound (A-5)") having an amine bond, a hydrazone bond, and a carboxyl group.

所得之化合物(A-5)之數平均分子量為10500、分散度為3.1、固形分的酸價為24mgKOH/g、芳香環濃度為4.7mmol/g。 The number average molecular weight of the obtained compound (A-5) was 10,500, the degree of dispersion was 3.1, the acid value of the solid content was 24 mgKOH / g, and the aromatic ring concentration was 4.7 mmol / g.

(合成例6) <A-6溶液> (Synthesis example 6) <A-6 solution>

於具備有攪拌裝置、溫度計、電容器之反應容器中，放入3-甲基-1,5-戊烷二醇：異苯二甲酸的聚酯多元醇 (KURARAY公司製 商品名：KURARAY多元醇P-3030)567.4g(0.1mol)與9,9-雙〔4-(2-羥基乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)34.65g(0.08mol)，置入作為4,4'-二苯基甲烷二異氰酸酯之MILLIONATE MT(日本聚胺基甲酸酯工業股份公司製)53.65g(0.214mol)及2,4-三氯乙烯二異氰酸酯與2,6-三氯乙烯二異氰酸酯之質量比80：20的混合物之COSMONATE T-80(三井化學聚胺基甲酸酯股份公司製)24.89g(0.143mol)與γ-丁內酯1021g，於150℃使全部的原料溶解，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，並使其反應4小時，使其生成具有胺基甲酸酯鍵之聚異氰酸酯。 In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, 3-methyl-1,5-pentanediol: a polyester polyol of isophthalic acid (KURARAY company product name: KURARAY Polyol P -3030) 567.4g (0.1mol) and 9,9-bis [4- (2-hydroxyethoxy) phenyl] pyrene (manufactured by Osaka Gas Chemical Co., Ltd., trade name: BPEF) 34.65g (0.08mol), put in as 4,4 '- MILLIONATE MT-diisocyanate diphenylmethane bis (Japan industrial polyurethane AG Ltd.) 53.65g (0.214mol) and 2,4-diisocyanate trichlorethylene 2,6 three COSMONATE T-80 (Mitsui Chemical Polyurethane Co., Ltd.) 24.89 g (0.143 mol) and γ-butyrolactone 1021 g of a mixture of vinyl chloride diisocyanate in a mass ratio of 80:20, and all the The raw materials were dissolved, and 0.1 part by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added thereto, and reacted for 4 hours to form an aminomethyl group. Polyester isocyanate.

接著，使反應液之溫度降至60℃為止，加入無水偏苯三甲酸63.71g(0.332mol)使其完全溶解之後，加入MILLIONATE MT 23.00g(0.092mol)及COSMONATE T-80 10.67g(0.061mol)與γ-丁內酯146.07g，昇溫至120℃使全部的原料溶解，並反應1小時。 Next, the temperature of the reaction solution was reduced to 60 ° C, 63.71 g (0.332 mol) of anhydrous trimellitic acid was added to completely dissolve, and MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) were added. ) And 146.07 g of γ-butyrolactone, heated to 120 ° C. to dissolve all the raw materials, and reacted for 1 hour.

之後，將反應液的溫度提昇至180℃為止，使其於180℃反應2小時。接著，將反應液的溫度降至120℃為止，加入2-丁酮肟(和光純藥股份公司製)5.61g，使反應結束，冷卻至室溫為止，得到固形分濃度40質量%的具有醯胺鍵及醯亞胺鍵與羧基之化合物(以下記為「化合物(A-6)」)之溶液。 Thereafter, the temperature of the reaction solution was raised to 180 ° C, and the reaction was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction solution was lowered to 120 ° C., 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction was completed, and the mixture was cooled to room temperature to obtain 40% by mass of A solution of a compound (hereinafter referred to as "compound (A-6)") having an amine bond, a sulfonimine bond, and a carboxyl group.

所得之化合物(A-6)之數平均分子量為10500、分散度為3.1、固形分的酸價為24mgKOH/g、芳香環濃度為 4.7mmol/g。 The number average molecular weight of the obtained compound (A-6) was 10,500, the degree of dispersion was 3.1, the acid value of the solid content was 24 mgKOH / g, and the aromatic ring concentration was 4.7 mmol / g.

(合成例7) <A-7溶液> (Synthesis example 7) <A-7 solution>

於具備有攪拌裝置、溫度計、電容器之反應容器中，置入聚酯二醇(α)369.85g(0.117mol)與9,9-雙〔4-(2-羥基乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)25.58g(0.058mok)、作為4,4'-二環己基甲烷二異氰酸酯之Desmodule-W(住化BAYER胺基甲酸酯股份公司製)91.70g(0.350mol)與作為溶劑之γ-丁內酯(三菱化學股份公司製)730.6g，於150℃使全部的原料溶解，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，並使其反應4小時，使其生成具有胺基甲酸酯鍵之聚異氰酸酯。 In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, 369.85 g (0.117 mol) of polyesterdiol (α) and 9,9-bis [4- (2-hydroxyethoxy) phenyl] 茀 were placed. (Osaka gas chemical Co., trade name: BPEF) 25.58g (0.058mok), as 4,4 '- diisocyanate, dicyclohexylmethane of Desmodule-W (manufactured by Sumika urethane BAYER AG Ltd.) 91.70g ( 0.350 mol) and 730.6 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent, all the raw materials were dissolved at 150 ° C, and 1,8-diazabicyclo [5.4.0] as a catalyst was added thereto. ] -7-undecene (DBU) 0.1 parts by mass and reacted for 4 hours to form a polyisocyanate having a urethane bond.

接著，將反應液的溫度降至80℃為止，加入Desmodule-W 45.85g(0.175mol)、無水偏苯三甲酸(三菱瓦斯化學股份公司製)33.60g(0.175mol)與γ-丁內酯(三菱化學股份公司製)119.18g，昇溫至150℃，使全部的原料溶解，並使其反應3小時。 Next, the temperature of the reaction solution was lowered to 80 ° C, and 45.85 g (0.175 mol) of Desmodule-W, 33.60 g (0.175 mol) of anhydrous trimellitic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone ( 119.18 g (manufactured by Mitsubishi Chemical Corporation) was heated to 150 ° C. to dissolve all the raw materials and allowed to react for 3 hours.

將反應液的溫度降至80℃為止，加入作為二醇之新戊二醇(關東化學股份公司製)16.40g(0.158mol)，昇溫至120℃，使全部的原料溶解，並使其反應4小時。之後將反應液的溫度降至80℃為止，加入作為三醇之丙三醇(關東化學股份公司製)9.67g(0.105mol)與γ-丁內酯(三菱化學股份公司製)39.10g，昇溫至110℃之 後使反應進行。藉由IR測定邊確認反應液中之異氰酸基的存在邊進行反應，當反應系中之異氰酸基無法被確認的時間點使反應終了，藉由冷卻至室溫為止，得到固形分濃度40質量%的具有羥基、醯胺鍵及醯亞胺鍵與羥基之化合物(以下記為「化合物(A-7)」)之溶液。 The temperature of the reaction solution was lowered to 80 ° C, 16.40 g (0.158 mol) of neopentyl glycol (manufactured by Kanto Chemical Co., Ltd.) was added as a diol, and the temperature was raised to 120 ° C to dissolve all the raw materials and react them 4 hour. Thereafter, the temperature of the reaction solution was lowered to 80 ° C, and glycerin (manufactured by Kanto Chemical Co., Ltd.) 9.67 g (0.105 mol) and γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as triols were added, and the temperature was raised. Up to 110 ° C The reaction was then allowed to proceed. The reaction was performed while confirming the existence of the isocyanate group in the reaction solution by IR measurement. When the isocyanate group in the reaction system could not be confirmed, the reaction was completed. The solid content was obtained by cooling to room temperature. A solution having a concentration of 40% by mass of a compound (hereinafter referred to as "compound (A-7)") having a hydroxyl group, an amido bond, and an imine bond and a hydroxyl group.

所得之化合物(A-7)之數平均分子量為10000、分散度為4.3、固形分的酸價為15mgKOH/g、羥基價為10mgKOH/g、芳香環濃度為3.3mmol/g。 The number average molecular weight of the obtained compound (A-7) was 10,000, the degree of dispersion was 4.3, the acid value of the solid content was 15 mgKOH / g, the hydroxyl value was 10 mgKOH / g, and the aromatic ring concentration was 3.3 mmol / g.

(合成例8) <A-8溶液> (Synthesis example 8) <A-8 solution>

於裝置有攪拌機、冷却管、氮導入管及溫度計的四口燒瓶中，加入作為四羧酸二酐之3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)270.7質量份與作為溶劑之γ-丁內酯964.4質量份，於120℃攪拌、溶解。朝其中，添加作為二異氰酸酯化合物之4,4'-二苯基甲烷二異氰酸酯(MDI)142.6質量份並予以攪拌，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，在氮氣流下使其於120℃反應3小時。之後，藉由冷卻至室溫為止，得到固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物。 In the apparatus with a stirrer, condenser four-neck flask, a nitrogen inlet tube and a thermometer, was added as a tetracarboxylic dianhydride of 3,3 ', 4,4' - benzophenone tetracarboxylic dianhydride (BTDA) 270.7 Mass parts and 964.4 mass parts of γ-butyrolactone as a solvent were stirred and dissolved at 120 ° C. Towards wherein the diisocyanate was added as an ester compound of 4,4 '- diphenylmethane diisocyanate (MDI) 142.6 parts by mass to be stirred and, as added to the catalyst of 1,8-diazabicyclo [5.4.0] 0.1-parts of 7-undecene (DBU) was reacted at 120 ° C for 3 hours under a nitrogen stream. Thereafter, by cooling to room temperature, a sulfonium imine prepolymer having an acid anhydride group at the terminal having a solid content concentration of 30% by mass was obtained.

接著，將所得的固形分濃度30質量%之末端含酸酐基之醯亞胺預聚物加熱並攪拌至100℃為止，添加包含來自3-甲基-1,5-戊烷二醇：1,6-己烷二醇之構成單位的聚碳酸酯多元醇(KURARAY公司製 商品名：KURARAY多元醇C-3090(※))950.8質量份、9,9-雙〔4-(2-羥基 乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)82.7質量份與γ-丁內酯1200.5質量份並予以攪拌。於其中添加作為觸媒之4-二甲基胺基吡啶(DMAP)2.4質量份，並使其於100℃反應8小時。之後，藉由冷卻至室溫為止，得到固形分濃度40質量%之具有醯亞胺鍵與羥基之化合物(以下記為「化合物(A-8)」)之溶液。化合物(A-8)之數平均分子量為15000、分散度為4.0、固形分的酸價為25mgKOH/g、芳香環濃度為1.8mmol/g。 Next, the obtained hydrazone imide prepolymer having a terminal acid anhydride group at a solid content concentration of 30% by mass was heated and stirred to 100 ° C, and 3-methyl-1,5-pentanediol-containing: Polycarbonate polyol (KURARAY Co., Ltd. product name: KURARAY Polyol C-3090 (*)), a constituent unit of 6-hexanediol, 950.8 parts by mass, 9,9-bis [4- (2-hydroxy 82.7 parts by mass of ethoxy) phenyl] phosphonium (manufactured by Osaka Gas Chemical Co., Ltd .: BPEF) and 1200.5 parts by mass of γ-butyrolactone were stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond and a hydroxyl group (hereinafter referred to as "compound (A-8)") having a solid content concentration of 40% by mass was obtained. The compound (A-8) had a number average molecular weight of 15,000, a dispersion degree of 4.0, an acid value of 25 mgKOH / g as a solid content, and an aromatic ring concentration of 1.8 mmol / g.

(※具有前述之式(1)之構造的聚酯多元醇、n之平均為12.0~12.1) (* The average value of the polyester polyol having the structure of the above formula (1), n is 12.0 ~ 12.1)

(合成例9) <A-9溶液> (Synthesis example 9) <A-9 solution>

於具備有攪拌裝置、溫度計、電容器之反應容器中，放入3-甲基-1,5-戊烷二醇：1,6-己烷二醇的聚碳酸酯多元醇(KURARAY公司製 商品名：KURARAY多元醇C-3090)567.4g(0.1mol)與9,9-雙〔4-(2-羥基乙氧基)苯基〕茀(大阪氣體化學製、商品名：BPEF)34.65g(0.08mol)，置入作為4,4'-二苯基甲烷二異氰酸酯之MILLIONATE MT(日本聚胺基甲酸酯工業股份公司製)53.65g(0.214mol)及2,4-三氯乙烯二異氰酸酯與2,6-三氯乙烯二異氰酸酯之質量比80：20的混合物之COSMONATE T-80(三井化學聚胺基甲酸酯股份公司製)24.89g(0.143mol)與γ-丁內酯1021g，於150℃使全部的原料溶解，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，並 使其反應4小時，使其生成具有胺基甲酸酯鍵之聚異氰酸酯。 In a reaction vessel provided with a stirring device, a thermometer, and a capacitor, a polycarbonate polyol (trade name, manufactured by Kuraray Co., Ltd.) of 3-methyl-1,5-pentanediol: 1,6-hexanediol was placed. : KURARAY Polyol C-3090) 567.4 g (0.1 mol) and 9,9-bis [4- (2-hydroxyethoxy) phenyl] pyrene (manufactured by Osaka Gas Chemical Co., Ltd., trade name: BPEF) 34.65 g (0.08 mol), placed as 4,4 '- MILLIONATE MT-diisocyanate diphenylmethane bis (Japan industrial polyurethane AG Ltd.) 53.65g (0.214mol) and 2,4-diisocyanate trichlorethylene and COSMONATE T-80 (Mitsui Chemical Polyurethane Co., Ltd.) 24.89g (0.143mol) and γ-butyrolactone 1021g in a mixture of 2,6-trichloroethylene diisocyanate with a mass ratio of 80:20, in All the raw materials were dissolved at 150 ° C, and 0.1 part by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added thereto, and reacted for 4 hours to allow A polyisocyanate having a urethane bond is formed.

接著，使反應液之溫度降至60℃為止，加入無水偏苯三甲酸63.71g(0.332mol)使其完全溶解之後，加入MILLIONATE MT 23.00g(0.092mol)及COSMONATE T-80 10.67g(0.061mol)與γ-丁內酯146.07g，昇溫至120℃使全部的原料溶解，並反應1小時。 Next, the temperature of the reaction solution was reduced to 60 ° C, 63.71 g (0.332 mol) of anhydrous trimellitic acid was added to completely dissolve, and MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) were added. ) And 146.07 g of γ-butyrolactone, heated to 120 ° C. to dissolve all the raw materials, and reacted for 1 hour.

之後，將反應液的溫度提昇至180℃為止，使其於180℃反應2小時。接著，將反應液的溫度降至120℃為止，加入2-丁酮肟(和光純藥股份公司製)5.61g，使反應結束，冷卻至室溫為止，得到固形分濃度40質量%的具有醯胺鍵及醯亞胺鍵與羧基之化合物(以下記為「化合物(A-9)」)之溶液。 Thereafter, the temperature of the reaction solution was raised to 180 ° C, and the reaction was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction solution was lowered to 120 ° C, 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the reaction was completed, and the mixture was cooled to room temperature to obtain a solid content concentration of 40% by mass. A solution of a compound (hereinafter referred to as "compound (A-9)") having an amine bond, a sulfonimine bond, and a carboxyl group.

所得之化合物(A-9)之數平均分子量為10500、分散度為3.1、固形分的酸價為24mgKOH/g、芳香環濃度為1.8mmol/g。 The number average molecular weight of the obtained compound (A-9) was 10,500, the degree of dispersion was 3.1, the acid value of the solid content was 24 mgKOH / g, and the aromatic ring concentration was 1.8 mmol / g.

(比較合成例1) <CA-1溶液> (Comparative Synthesis Example 1) <CA-1 solution>

於裝置有攪拌機、冷却管、氮導入管及溫度計的四口燒瓶中，加入作為四羧酸二酐之1,2,3,4-丁烷四羧酸酐(製品名：RIKACID BT-100、新日本理化製)166.4質量份與作為溶劑之γ-丁內酯398.4質量份，於120℃攪拌、溶解。朝其中，添加作為二異氰酸酯化合物之2,4-三氯乙烯二異氰酸酯與2,6-三氯乙烯二異氰酸酯之質量比80：20的混合物之COSMONATE T-80(三井化學聚胺基甲酸酯股份公司製) 99.18質量份並予以攪拌，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，在氮氣流下使其於120℃反應3小時。之後，藉由冷卻至室溫為止，得到固形分濃度40質量%之末端含酸酐基之醯亞胺預聚物。 To a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, add 1,2,3,4-butanetetracarboxylic anhydride (product name: RIKACID BT-100, new 166.4 parts by mass and 398.4 parts by mass of γ-butyrolactone as a solvent, stirred and dissolved at 120 ° C. To this, COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound in a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. Joint-stock company system) 99.18 parts by mass was stirred, and 0.18 parts by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added thereto, and reacted at 120 ° C under a nitrogen stream. 3 hour. Thereafter, by cooling to room temperature, a terminal imidium imine prepolymer having an acid anhydride group at a solid content concentration of 40% by mass was obtained.

接著，將所得之固形分濃度40質量%之末端含酸酐基之醯亞胺預聚物加熱並攪拌至100℃為止，添加並攪拌作為多元醇化合物之聚碳酸酯二醇化合物(商品名：DURANOL T5650E：旭化成化學(股)製、Mn=500)100.0質量份、及己二酸/新戊二醇/1,6-己烷二醇的聚酯二醇(商品名：OD-X-688 DIC(股)製、數平均分子量約2,000)460.0質量份與γ-丁內酯147.5質量份。於其中添加作為觸媒之4-二甲基胺基吡啶(DMAP)2.4質量份，並使其於100℃反應8小時。之後，藉由冷卻至室溫為止，得到固形分濃度40質量%的具有醯亞胺鍵與羧基及羥基之化合物(以下記為「化合物(CA-1)」)之溶液。化合物(CA-1)之數平均分子量為10500、分散度為4.0、固形分的酸價為44mgKOH/g、芳香環濃度為0.7mmol/g。 Next, the obtained fluorene imine prepolymer having a terminal acid anhydride group with a solid content concentration of 40% by mass was heated and stirred to 100 ° C, and a polycarbonate diol compound (trade name: DURANOL) as a polyol compound was added and stirred. T5650E: Polyester diol (trade name: OD-X-688 DIC, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn = 500) 100.0 parts by mass, and adipic acid / neopentyl glycol / 1,6-hexanediol (Number-average molecular weight: about 2,000) (460.0 parts by mass) and 147.5 parts by mass of γ-butyrolactone. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a fluorene imine bond, a carboxyl group, and a hydroxyl group (hereinafter referred to as "compound (CA-1)") having a solid concentration of 40% by mass was obtained. The compound (CA-1) had a number average molecular weight of 10,500, a degree of dispersion of 4.0, an acid value of 44 mgKOH / g as a solid content, and an aromatic ring concentration of 0.7 mmol / g.

(比較合成例2) <CA-2溶液> (Comparative Synthesis Example 2) <CA-2 solution>

於具備有攪拌裝置、溫度計、電容器之反應容器中，放入3-甲基-1,5-戊烷二醇：1、6-己烷二醇的聚碳酸酯多元醇(KURARAY公司製 商品名：KURARAY多元醇C-3090)567.4g(0.179mol)，置入作為4,4'-二環己基甲烷二異氰酸酯之Desmodule-W(住化BAYER胺基甲酸酯股份 公司製)56.07g(0.214mol)及1,3-雙(異氰酸基甲基)環己烷(商品名：Takenate600、三井化學聚胺基甲酸酯股份公司製)27.77g(0.143mol)與γ-丁內酯976.9g，於150℃使全部的原料溶解，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，並使其反應4小時，使其生成具有胺基甲酸酯鍵之聚異氰酸酯。 In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, a 3-methyl-1,5-pentanediol: 1,6-hexanediol polycarbonate polyol (trade name, manufactured by Kuraray Corporation) was placed. : KURARAY polyol C-3090) 567.4g (0.179mol) , placed as 4,4 '- bis iso-cyanate dicyclohexylmethane Desmodule-W (manufactured by Sumika urethane BAYER AG Ltd.) 56.07g (0.214 mol) and 1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate600, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 27.77 g (0.143 mol) and γ-butyrolactone 976.9 g, dissolve all the raw materials at 150 ° C, add 0.1 parts by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst, and react for 4 hours To form a polyisocyanate having a urethane bond.

接著，使反應液之溫度降至60℃為止，加入無水偏苯三甲酸63.71g(0.332mol)使其完全溶解之後，加入MILLIONATE MT 23.00g(0.092mol)及COSMONATE T-80 10.67g(0.061mol)與γ-丁內酯154.2g，昇溫至120℃使全部的原料溶解，並反應1小時。 Next, the temperature of the reaction solution was reduced to 60 ° C, 63.71 g (0.332 mol) of anhydrous trimellitic acid was added to completely dissolve, and MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) were added. ) And 154.2 g of γ-butyrolactone, heated to 120 ° C. to dissolve all the raw materials, and reacted for 1 hour.

之後，將反應液的溫度提昇至180℃為止，使其於180℃反應2小時。接著，將反應液的溫度降至120℃為止，加入2-丁酮肟(和光純藥股份公司製)3.13g，使反應終了，冷卻至室溫為止，得到固形分濃度40質量%的具有醯胺鍵及醯亞胺鍵與羧基之化合物(以下記為「化合物(CA-2)」)之溶液。 Thereafter, the temperature of the reaction solution was raised to 180 ° C, and the reaction was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction solution was lowered to 120 ° C, and 3.13 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added to complete the reaction, and the mixture was cooled to room temperature to obtain a solid content concentration of 40% by mass. A solution of a compound (hereinafter referred to as "compound (CA-2)") having an amine bond, a hydrazone bond, and a carboxyl group.

所得之化合物(CA-2)之數平均分子量為12200、分散度為3.1、固形分的酸價為14mgKOH/g、芳香環濃度為0.6mmol/g。 The number average molecular weight of the obtained compound (CA-2) was 12,200, the degree of dispersion was 3.1, the acid value of the solid content was 14 mgKOH / g, and the aromatic ring concentration was 0.6 mmol / g.

(比較合成例3) <CA-3溶液> (Comparative Synthesis Example 3) <CA-3 solution>

於具備有攪拌裝置、溫度計、電容器之反應容器中，置入以3：1之莫耳比包含來自1,4-環己烷二甲醇之構成單 位與來自1,6-己烷二醇之構成單位的聚碳酸酯二醇(UM-CARB90(3/1)、宇部興產股份公司製、平均分子量：約900)156.98g(0.175mol)與作為4,4'-二環己基甲烷二異氰酸酯之Desmodule-W(住化BAYER胺基甲酸酯股份公司製)91.70g(0.350mol)與作為溶劑之γ-丁內酯(三菱化學股份公司製)165.80g，於150℃使全部的原料溶解，於其中添加作為觸媒之1,8-二氮雜雙環〔5.4.0〕-7-十一烯(DBU)0.1質量份，並使其反應4小時，使其生成具有胺基甲酸酯鍵之聚異氰酸酯。 In a reaction vessel provided with a stirring device, a thermometer, and a capacitor, a unit containing 1,4-cyclohexanedimethanol and 1,6-hexanediol in a molar ratio of 3: 1 was placed. polycarbonate diol units (UM-CARB90 (3/1), Ube Kosan Co., Ltd .; average molecular weight: about 900) 156.98g (0.175mol) with a 4,4 '- dicyclohexylmethane diisocyanate of 91.70 g (0.350 mol) of Desmodule-W (manufactured by BAYER Urethane Co., Ltd.) and 165.80 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as solvents. To this, 0.1 part by mass of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst was added and reacted for 4 hours to form a urethane bond. Of polyisocyanate.

接著，將反應液的溫度降至80℃為止，加入Desmodule-W 45.85g(0.175mol)、無水偏苯三甲酸(三菱瓦斯化學股份公司製)33.60g(0.175mol)與γ-丁內酯(三菱化學股份公司製)162.33g，昇溫至150℃，使全部的原料溶解，並使其反應3小時。 Next, the temperature of the reaction solution was lowered to 80 ° C, and 45.85 g (0.175 mol) of Desmodule-W, 33.60 g (0.175 mol) of anhydrous trimellitic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone ( 162.33 g (manufactured by Mitsubishi Chemical Corporation) was heated to 150 ° C. to dissolve all the raw materials and allowed to react for 3 hours.

將反應液的溫度降至80℃為止，加入作為二醇之新戊二醇(關東化學股份公司製)16.40g(0.158mol)，昇溫至120℃，使全部的原料溶解，並使其反應4小時。之後將反應液的溫度降至80℃為止，加入作為三醇之丙三醇(關東化學股份公司製)9.67g(0.105mol)與γ-丁內酯(三菱化學股份公司製)26.07g，昇溫至110℃之後使反應進行。藉由IR測定邊確認反應液中之異氰酸基的存在邊進行反應，在反應系中直到異氰酸基無法被確認之時機點使反應終了，並加入γ-丁內酯177.1g，得到固形分濃度40質量%具有羥基、醯胺鍵及醯亞胺鍵與羥基之化合 物(以下記為「化合物(CA-3)」)之溶液。 The temperature of the reaction solution was lowered to 80 ° C, 16.40 g (0.158 mol) of neopentyl glycol (manufactured by Kanto Chemical Co., Ltd.) was added as a diol, and the temperature was raised to 120 ° C to dissolve all the raw materials and react them 4 hour. Thereafter, the temperature of the reaction solution was lowered to 80 ° C, and glycerol (manufactured by Kanto Chemical Co., Ltd.) 9.67 g (0.105 mol) and γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as triols were added, and the temperature was increased. After reaching 110 ° C, the reaction was allowed to proceed. The reaction was carried out while confirming the presence of an isocyanate group in the reaction solution by IR measurement, and the reaction was terminated until the isocyanate group could not be confirmed in the reaction system, and 177.1 g of γ-butyrolactone was added to obtain The solid content concentration is 40% by mass. It has a hydroxyl group, an amido bond, and a combination of an ammonium bond and a hydroxyl group. (Hereinafter referred to as "compound (CA-3)").

所得之化合物(CA-3)之數平均分子量為8000、分散度為4.4、固形分的酸價為27mgKOH/g、羥基價為16mgKOH/g、芳香環濃度為0.5mmol/g。 The obtained compound (CA-3) had a number average molecular weight of 8000, a dispersion of 4.4, a solid content of an acid value of 27 mgKOH / g, a hydroxyl value of 16 mgKOH / g, and an aromatic ring concentration of 0.5 mmol / g.

<主劑摻合物之製造> <Manufacturing of main agent blend>

(主劑摻合物1) (Base Agent Blend 1)

混合化合物(A-1)160.0質量份、氧化矽粉(日本AEROSIL®股份公司製，商品名：AEROSIL®R-974)6.3質量份、作為硬化促進劑之三聚氰胺(日產化學工業股份公司製)0.72質量份及二乙二醇二乙基醚8.4質量份，使用三輥式滾軋機(股份公司井上製作所製，型式：S-4 3/4×11)，對化合物(A-1)實施氧化矽粉、硬化促進劑的混合。之後，添加消泡劑(Momentive Performance Materials公司製，商品名：TSA750S)2.0質量份，使用刮勺予以混合。將此摻合物作為主劑摻合物C1。 160.0 parts by mass of the compound (A-1), 6.3 parts by mass of silicon oxide powder (manufactured by Japan AEROSIL ® Co., Ltd., trade name: AEROSIL ® R-974), and 0.72 parts by mass of melamine as a hardening accelerator (manufactured by Nissan Chemical Industries, Ltd.) Parts by mass and 8.4 parts by mass of diethylene glycol diethyl ether. Using a three-roll rolling mill (manufactured by Inoue Co., Ltd., type: S-4 3/4 × 11), silicon oxide was applied to the compound (A-1). Mixing of powder and hardening accelerator. Thereafter, 2.0 parts by mass of a defoaming agent (manufactured by Momentive Performance Materials, trade name: TSA750S) was added, and mixed using a spatula. This blend was used as the main ingredient blend C1.

(主劑摻合物2~9及比較主劑摻合物1~3) (Base agent blends 2-9 and comparative base agent blends 1 ~ 3)

藉由與主劑摻合物1同樣的方法，依表1所示之摻合組成進行摻合。各自作為主劑摻合物2~9、比較主劑摻合物比1~比3。 In the same manner as the main agent blend 1, blending was performed according to the blending composition shown in Table 1. Each was used as a main agent blend 2-9, and the main agent blend ratios 1 to 3 were compared.

此外，表中之數值代表「質量份」。 The values in the table represent "mass parts".

<硬化劑溶液之製造> <Manufacture of hardener solution>

(硬化劑溶液之摻合例1) <B-1溶液> (Mixing Example 1 of Hardener Solution) <B-1 Solution>

於具備有攪拌機、溫度計及電容器的容器中，添加具有下述式(7)之構造的環氧樹脂(三菱化學公司製，規格名：JER604，環氧當量120g/eqv)16.85質量份、二乙二醇二乙基醚18.25質量份，開始攪拌。 To a container provided with a stirrer, a thermometer, and a capacitor, 16.85 parts by mass of epoxy resin (manufactured by Mitsubishi Chemical Corporation, specification name: JER604, epoxy equivalent 120g / eqv), and diethyl ether having a structure of the following formula (7) were added. 18.25 parts by mass of glycol diethyl ether, stirring was started.

一邊繼續攪拌，使用油浴，將容器內的溫度昇溫至40℃。將內溫昇溫至40℃後，繼續攪拌30分鐘。之後，確認JER604完全溶解後，冷卻至室溫為止，取得濃度48質量%含JER604之溶液。將此溶液作為硬化劑溶液B-1。 While continuing to stir, the temperature in the container was raised to 40 ° C using an oil bath. After the internal temperature was raised to 40 ° C, stirring was continued for 30 minutes. Then, after confirming that JER604 was completely dissolved, it was cooled to room temperature to obtain a solution containing JER604 at a concentration of 48% by mass. This solution was used as a hardener solution B-1.

(硬化劑溶液之摻合例2) <B-2溶液> (Blend Example 2 of Hardener Solution) <B-2 Solution>

於具備有攪拌機、溫度計及電容器的容器中，添加以N,N-二環氧丙基-4-(環氧丙基氧基)苯胺作為主成分之環氧樹脂(三菱化學股份公司製，規格名：JER630，環氧當量98g/eqv)16.85質量份、二乙二醇二乙基醚18.25質 量份，開始攪拌。 To a container equipped with a stirrer, a thermometer, and a capacitor, an epoxy resin (manufactured by Mitsubishi Chemical Corporation, specifications, with N, N-diglycid-4- (glycidoxy) aniline) as the main component is added. Name: JER630, epoxy equivalent 98g / eqv) 16.85 parts by mass, diethylene glycol diethyl ether 18.25 parts Measure and start stirring.

一邊繼續攪拌，使用油浴，將容器內的溫度昇溫至40℃。將內溫昇溫至40℃後，繼續攪拌30分鐘。之後，確認JER630完全溶解，冷卻至室溫為止，取得濃度48質量%含JER630之溶液。將此溶液作為硬化劑溶液B-2。 While continuing to stir, the temperature in the container was raised to 40 ° C using an oil bath. After the internal temperature was raised to 40 ° C, stirring was continued for 30 minutes. After that, it was confirmed that JER630 was completely dissolved, and the solution was cooled to room temperature to obtain a solution containing JER630 at a concentration of 48% by mass. This solution was used as a hardener solution B-2.

<含主劑摻合物與硬化劑之溶液的混合> <Mix of solution containing main agent blend and hardener>

(硬化性組成物之實施例1) (Example 1 of hardening composition)

將主劑摻合物C1 88.71質量份與硬化劑溶液B-1 3.51質量份放入塑膠容器。再者，為了配合後述其他摻合例、比較摻合例之硬化性組成物與黏度，乃添加作為溶劑之二乙二醇二乙基醚3.0質量份及二乙二醇乙基醚乙酸酯1.5質量份。混合係使用刮勺，在室溫攪拌5分鐘來實施，得到硬化性組成物(以下記為「硬化性組成物F1」)。 88.71 parts by mass of the main agent blend C1 and 3.51 parts by mass of the hardener solution B-1 were placed in a plastic container. In addition, in order to match the hardening composition and viscosity of other blending examples described later and comparative blending examples, 3.0 parts by mass of diethylene glycol diethyl ether and diethylene glycol ethyl ether acetate were added as a solvent. 1.5 parts by mass. The mixing system was carried out by using a spatula and stirring at room temperature for 5 minutes to obtain a curable composition (hereinafter referred to as "curable composition F1").

(硬化性組成物之實施例2~10及比較例1~3) (Examples 2 to 10 and Comparative Examples 1 to 3 of the hardening composition)

藉由與硬化性組成物之實施例1同樣的方法，依表1所示之摻合組成進行摻合。將實施例2~9調製之摻合物分別作為主劑摻合物F2~F10，將硬化性組成物之比較例1~3調製之摻合物分別作為比較主劑摻合物G1~G3。在此，硬化性組成物F8、G3中，也進一步摻合相當於(成分B)之Baxenden公司製封端異氰酸酯「7950」。此外，表中之數值代表「質量份」。 In the same manner as in Example 1 of the curable composition, blending was performed according to the blending composition shown in Table 1. The blends prepared in Examples 2 to 9 were used as the main agent blends F2 to F10, and the blends prepared in Comparative Examples 1 to 3 of the hardening composition were used as the comparative main agent blends G1 to G3, respectively. Here, the curable compositions F8 and G3 are further blended with a blocked isocyanate "7950" manufactured by Baxenden Co., which corresponds to (component B). The values in the table represent "mass parts".

此外，硬化性組成物F1~F10、硬化性組成物 G1~G3之摻合組成記於表2中。 In addition, the hardening composition F1 to F10, the hardening composition The blended composition of G1 ~ G3 is shown in Table 2.

又，前述硬化性組成物F1~F10、硬化性組成物G1~G3的每種成分之質量份彙整的，係記於表3。又，表2、3中的環氧基數/羧基數係由酸價計算求得的。 In addition, the mass fraction of each component of the said hardenable composition F1-F10 and hardenable composition G1-G3 is put together in Table 3. The numbers of epoxy groups / carboxyl groups in Tables 2 and 3 were obtained by calculation of acid value.

(實施例1~10及比較例1~3) (Examples 1 to 10 and Comparative Examples 1 to 3)

使用硬化性組成物F1~F10、硬化性組成物G1~G3，藉由以下說明之方法，進行可撓性、斷線抑制性、翹曲性的評價及長期電氣絕緣信賴性的評價。將其結果記於表4。 Using the hardenable compositions F1 to F10 and the hardenable compositions G1 to G3, the evaluation of flexibility, disconnection suppression, warpage and long-term electrical insulation reliability were performed by the methods described below. The results are shown in Table 4.

<可撓性的評價> <Evaluation of flexibility>

於貼有可撓性銅之積層板(住友金屬礦山股份公司製，規格名：ESPERFLEX，銅厚：8μm、聚醯亞胺厚：38μm)之銅上，以成為寬幅75mm、長度110mm之大小、硬化後的塗膜厚度為15μm之方式將硬化性組成物F1藉由網版印刷進行塗佈，室溫下保持10分鐘，置入120℃之熱風循環式乾燥機中60分鐘藉此使其硬化。剝離製作之試驗片的後盾之保護PET薄膜，以裁紙刀切出寬幅10mm之條狀後，以塗膜面成為外側般約180度彎曲，並使用壓縮機以0.5±0.2MPa壓縮3秒鐘。以彎曲之狀態用30倍的顯微鏡觀察彎曲部，確認裂縫有無產生。將結果記於表4。 Laminated with flexible copper (made by Sumitomo Metal Mining Co., Ltd., specification name: ESPERFLEX, copper thickness: 8 μm, polyimide thickness: 38 μm) on copper to a width of 75 mm and a length of 110 mm 2. The hardening composition F1 is applied by screen printing so that the thickness of the cured coating film is 15 μm. It is held at room temperature for 10 minutes, and placed in a hot air circulation dryer at 120 ° C. for 60 minutes to make it. hardening. The protective PET film, which is the backing of the produced test piece, was peeled. After cutting a strip with a width of 10 mm with a paper cutter, it was bent about 180 degrees so that the coating film surface became the outer side, and compressed using a compressor at 0.5 ± 0.2 MPa for 3 seconds. bell. The bent portion was observed with a 30-fold microscope in a bent state to confirm the occurrence of cracks. The results are shown in Table 4.

又，使用硬化性組成物F2~F10、硬化性組成物G1~G3，進行同樣的評價。該等之結果也一併記於表4。 The same evaluations were performed using the curable compositions F2 to F10 and the curable compositions G1 to G3. These results are also shown in Table 4.

<配線板的配線的斷線抑制性的評價(MIT試驗)> <Evaluation of disconnection suppression of wiring of a wiring board (MIT test)>

對蝕刻貼有可撓性銅之積層板(住友金屬礦山股份公司製，規格名：ESPERFLEXUS，銅厚：8μm、聚醯亞胺厚：38μm)所製造之JPCA-ET01中記載之微細梳子形圖型 形狀的基板(銅配線寬幅/銅配線間寬幅=15μm/15μm)實施錫鍍敷處理，於該可撓性配線板上將硬化性組成物F1藉由網版印刷法，以由塗膜的聚醯亞胺面算起之厚度成為10μm之厚度(乾燥後)的方式來進行塗佈。將所得之塗膜形成配線板，放入80℃的熱風循環式乾燥機中30分鐘，之後，藉由置入120℃的熱風循環式乾燥機中120分鐘，使前述塗膜硬化。 A fine comb-shaped figure as described in JPCA-ET01, manufactured by etching a laminated copper plate (manufactured by Sumitomo Metal Mining Corporation, specification name: ESPERFLEXUS, copper thickness: 8 μm, polyimide thickness: 38 μm) type The substrate (copper wiring width / copper wiring width = 15μm / 15μm) is subjected to tin plating, and the hardening composition F1 is screen-printed on the flexible wiring board to apply a coating film. Coating was performed so that the thickness of the polyimide surface was 10 μm (after drying). The obtained coating film was formed into a wiring board and placed in a hot-air circulation type dryer at 80 ° C for 30 minutes, and then the coating film was hardened by being placed in a hot-air circulation type dryer at 120 ° C for 120 minutes.

使用此試驗片，以JIS C-5016中記載之方法用下述的試驗條件實施。 Using this test piece, the method described in JIS C-5016 was carried out under the following test conditions.

(試驗條件) (Test conditions)

試驗機：TESTER產業股份公司製MITTESTERBE202 Testing machine: MITTESTERBE202 manufactured by TESTER Industry Co., Ltd.

彎曲速度：10次/分 Bending speed: 10 times / minute

荷重：200g Load: 200g

彎曲角度：±90° Bending angle: ± 90 °

夾具先端部的半徑：0.5mm Radius of the tip of the clamp: 0.5mm

以上述試驗條件每次增加10次地增加彎曲次數，以目視觀察配線的裂縫有無，紀錄裂縫產生時的彎曲次數。將結果記於表4。 Under the above test conditions, the number of bends was increased by 10 each time, the presence or absence of cracks in the wiring was visually observed, and the number of bends when cracks occurred was recorded. The results are shown in Table 4.

又，使用硬化性組成物F2~F10、硬化性組成物G1~G3，進行同樣的評價。該等之結果也一併記於表4。 The same evaluations were performed using the curable compositions F2 to F10 and the curable compositions G1 to G3. These results are also shown in Table 4.

<翹曲性的評價> <Evaluation of Warpage>

以# 180網目聚酯版藉由網版印刷塗佈硬化性組成物 F1於基板上，將該基板放入80℃的熱風循環式乾燥機30分鐘。之後，藉由將前述基板放入120℃的熱風循環式乾燥機60分鐘，使塗佈的硬化性組成物F1硬化。前述基板方面，係使用25μm厚聚醯亞胺薄膜〔Kapton®(註冊商標)100EN、DU PONT-TORAY股份公司製〕。 The hardening composition F1 was applied to a substrate by screen printing using a # 180 mesh polyester plate, and the substrate was placed in a hot air circulation dryer at 80 ° C for 30 minutes. Thereafter, the coated substrate was placed in a hot-air circulation dryer at 120 ° C. for 60 minutes to harden the applied curable composition F1. Aspect of the substrate, using the 25μm thick polyimide-based film [Kapton ® (registered trademark) 100EN, DU PONT-TORAY Co., Ltd .;].

以切圓器在每片基板切割已硬化的塗膜成直徑50mmφ。被裁成圓形者中心附近呈現翹曲成凸狀或凹狀之變形。以切圓器所裁切之基板上形成有硬化膜者，將其於1小時後以下方為凸的狀態，即以基板上形成有硬化膜者的中心附近接觸水平面之方式予以靜置，測定從水平面起的翹曲高度之最大、最小值，求取其平均值。符號表示翹曲的方向，下方以凸的狀態靜置時，對銅基板或聚醯亞胺薄膜而言，硬化膜成為上側時記為「+」、硬化膜成為下側時記為「-」。然後，翹曲若未達+3.0mm則給予合格。 The hardened coating film was cut on each substrate with a circular cutter to a diameter of 50 mmφ. The shape of the person who is cut into a circle is warped into a convex or concave shape near the center. If the hardened film is formed on the substrate cut by the circle cutter, it will be in a convex state below 1 hour later, that is, let the vicinity of the center of the hardened film formed on the substrate contact the horizontal surface and measure. The maximum and minimum values of the warpage height from the horizontal plane are averaged. The symbol indicates the direction of warpage. When the lower part is left standing in a convex state, the copper substrate or the polyimide film is described as "+" when the cured film becomes the upper side and "-" when the cured film becomes the lower side. . Then, if the warpage does not reach +3.0 mm, a pass is given.

將結果記於表4。 The results are shown in Table 4.

又，使用硬化性組成物F2~F10、硬化性組成物G1~G3，進行同樣的評價。該等之結果也一併記於表4。 The same evaluations were performed using the curable compositions F2 to F10 and the curable compositions G1 to G3. These results are also shown in Table 4.

<長期電氣絕緣信賴性的評價> <Evaluation of long-term electrical insulation reliability>

對蝕刻貼有可撓性銅之積層板(住友金屬礦山股份公司製，規格名：ESPERFLEXUS，銅厚：8μm、聚醯亞胺厚：38μm)所製造之JPCA-ET01中記載之微細梳子形圖型形狀的基板(銅配線寬幅/銅配線間寬幅=15μm/15μm) 實施錫鍍敷處理，於該可撓性配線板上將硬化性組成物F1藉由網版印刷法，以由塗膜的聚醯亞胺面算起之厚度成為15μm之厚度(乾燥後)的方式來進行塗佈。將所得之塗膜形成配線板，放入80℃的熱風循環式乾燥機中30分鐘，之後，藉由置入120℃的熱風循環式乾燥機中120分鐘，使塗佈的硬化性組成物F1硬化。 A fine comb-shaped figure as described in JPCA-ET01, manufactured by etching a laminated copper plate (manufactured by Sumitomo Metal Mining Corporation, specification name: ESPERFLEXUS, copper thickness: 8 μm, polyurethane thickness: 38 μm) Substrate (wide copper wiring width / wide copper wiring width = 15μm / 15μm) A tin plating process was performed, and the curable composition F1 was subjected to screen printing to a thickness of 15 μm (after drying) from the polyimide surface of the coating film by screen printing on the flexible wiring board. Way to perform coating. The obtained coating film was formed into a wiring board, and it was placed in a hot air circulation type dryer at 80 ° C for 30 minutes. Then, it was placed in a hot air circulation type dryer at 120 ° C for 120 minutes to make the applied hardening composition F1. hardening.

使用此試驗片，施加偏壓電壓60V，以溫度120℃、濕度85%RH的條件使用MIGRATION TESTER MODEL MIG-8600(IMV公司製)來進行溫濕度定常試驗。將前述溫濕度定常試驗的起始初期及起始之後的100小時後、250小時後、400小時後的前述微細梳子型圖型形狀的基板之電阻值記於表4。 Using this test piece, a bias voltage of 60 V was applied, and a temperature and humidity steady test was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV) under the conditions of a temperature of 120 ° C and a humidity of 85% RH. Table 4 shows the resistance values of the substrates of the fine comb-type pattern in the initial stage of the temperature and humidity steady test and 100 hours, 250 hours, and 400 hours after the beginning of the tests.

又，使用硬化性組成物F2~F10、硬化性組成物G1~G3，進行同樣的評價。該等之結果也一併記於表4。 The same evaluations were performed using the curable compositions F2 to F10 and the curable compositions G1 to G3. These results are also shown in Table 4.

由表4的結果可知，本發明之硬化性組成物在可撓性、斷線抑制性及長期電氣絕緣信賴性方面表現優異，該硬化物可使用作為可撓性配線板用的絕緣保護膜。 From the results in Table 4, it can be seen that the curable composition of the present invention is excellent in flexibility, disconnection resistance, and long-term electrical insulation reliability, and the cured product can be used as an insulating protective film for a flexible wiring board.

〔產業上之可利用性〕 [Industrial availability]

本發明之硬化性組成物適合利用於可撓性配線板的絕緣保護。 The curable composition of the present invention is suitably used for insulation protection of a flexible wiring board.

Claims (17)

一種硬化性組成物，其特徵係含有：(成分A)下述至少具有1個以式(A)所示之構造單位，且具有醯亞胺鍵及醯胺鍵之至少1種鍵結，且具有與硬化劑反應之官能基的化合物、(成分B)硬化劑、及(成分C)有機溶劑， (波線表示位於該構造之末端與其他構造之鍵結部位)。 A hardenable composition comprising: (component A) the following having at least one structural unit represented by formula (A) and having at least one kind of bond of a sulfonium imine bond and a sulfonium bond, and A compound having a functional group that reacts with a hardener, (component B) a hardener, and (component C) an organic solvent, (The wave line indicates the bonding position between the end of the structure and other structures). 如第1項中記載之硬化性組成物，其中，前述與硬化劑反應之官能基係羧基、羥基、酸酐基、異氰酸基、醯胺基、胺基之至少1種。 The curable composition according to item 1, wherein the functional group that reacts with the curing agent is at least one of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, an amido group, and an amine group. 如第1或2項中記載之硬化性組成物，其中，(成分 A)係芳香環濃度為1.0~6.0mmol/g。 The hardening composition according to item 1 or 2, wherein (ingredient A) The aromatic ring concentration is 1.0 to 6.0 mmol / g. 如第1~3項中任一項記載之硬化性組成物，其中，(成分A)係含有：(原料a)具有酸酐基之3價及/或4價的聚羧酸衍生物、(原料b)下述一般式(1)、一般式(2)的至少1者所示之多元醇、(原料c)聚異氰酸酯、及(原料d)於原料中用下述式(A2)及/或(A3)使其反應所得之化合物， (式(1)中，(n+1)個的R1各自獨立地表示由碳數3~36之二醇所衍生的有機殘基、n個的R2各自獨立地表示芳香族系有機殘基、於芳香族系有機殘基上進一步具有取代基之有機殘基、由碳數3~36之二羧酸所衍生的有機殘基選出的至少1個、n獨立地表示1~60之整數) (式(2)中，(m+1)個的R3各自獨立地表示由碳數3~36之二醇所衍生的有機殘基、m獨立地表示1~60之整數) (式(A2)中，q各自獨立地表示1~10之整數) (式(A3)中，p各自獨立地表示1~10之整數)。 The curable composition according to any one of items 1 to 3, wherein (component A) contains: (raw material a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, and (raw material b) Polyols represented by at least one of the following general formula (1) and general formula (2), (raw material c) polyisocyanate, and (raw material d) use the following formula (A2) and / or (A3) a compound obtained by reacting, (In formula (1), (n + 1) R 1 each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n R 2 each independently represent an aromatic organic residue. At least one selected from the group consisting of an organic residue further having a substituent on an aromatic organic residue, an organic residue derived from a dicarboxylic acid having 3 to 36 carbon atoms, and n independently represents an integer of 1 to 60 ) (In formula (2), (m + 1) R 3 each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and m independently represents an integer from 1 to 60) (In formula (A2), q each independently represents an integer of 1 to 10) (In the formula (A3), p each independently represents an integer of 1 to 10). 如第1~4項中任一項記載之硬化性組成物，其中，(成分A)係具有前述以式(A)所示之構造單位，且具有醯亞胺鍵及醯胺鍵之至少1種鍵結，又進一步具有胺基甲酸酯鍵之化合物。 The curable composition according to any one of items 1 to 4, wherein (component A) has a structural unit represented by the formula (A), and has at least 1 This kind of bonding compound further has a urethane bond. 如第1~5項中任一項記載之硬化性組成物，其中，(成分A)之酸價為10~50mgKOH/g。 The curable composition according to any one of items 1 to 5, wherein the acid value of (component A) is 10 to 50 mgKOH / g. 如第1~6項中任一項記載之硬化性組成物，其中，(成分B)係包含每1分子具有2個以上環氧基之化合物。 The curable composition according to any one of items 1 to 6, wherein (component B) includes a compound having two or more epoxy groups per molecule. 如第1~7項中任一項記載之硬化性組成物，其中，(成分C)係由醚系溶劑、酯系溶劑、酮系溶劑及芳香族烴系溶劑所成之群選出的至少1種之有機溶劑。 The curable composition according to any one of items 1 to 7, wherein (component C) is at least 1 selected from the group consisting of an ether-based solvent, an ester-based solvent, a ketone-based solvent, and an aromatic hydrocarbon-based solvent. Organic solvents. 如第1~8項中任一項記載之硬化性組成物，其中，進一步包含(成分D)由無機微粒子及有機微粒子所成之群選出的至少1種之微粒子。 The curable composition according to any one of items 1 to 8, further comprising (component D) at least one kind of fine particles selected from the group consisting of inorganic fine particles and organic fine particles. 如第1~9項中任一項記載之硬化性組成物，其中，令成分(A)與成分(B)之合計量為100質量份時，包含1~55質量份之成分(B)。 The curable composition according to any one of items 1 to 9, wherein when the total amount of the component (A) and the component (B) is 100 parts by mass, 1 to 55 parts by mass of the component (B) is included. 如第1~10項中任一項記載之硬化性組成物，其中，令成分(A)、成分(B)、成分(C)及成分(D)之合計量(不含成分(D)時，成分(A)、成分(B)及成分(C)之合計量)為100質量份時，包含25~75質量份之成分(C)。 The curable composition according to any one of items 1 to 10, wherein a total amount of the component (A), the component (B), the component (C), and the component (D) is made (when the component (D) is not included) When the total amount of the component (A), the component (B), and the component (C) is 100 parts by mass, 25 to 75 parts by mass of the component (C) is included. 一種硬化膜，其特徵係包含如第1項~11中任一項記載之硬化性組成物的硬化物。 A cured film comprising a cured product of the curable composition according to any one of items 1 to 11. 一種可撓性配線板用被覆膜，其特徵係藉由於在可撓性基板上形成有配線而成的可撓性配線板之形成有配線的表面之一部分或全部塗佈如第1項~11中任一項記載之硬化性組成物並予以硬化所得。 A coating film for a flexible wiring board, which is characterized in that part or all of the wiring-forming surface of the flexible wiring board is formed by wiring formed on a flexible substrate, as described in item 1 ~ The hardening composition according to any one of 11 is obtained by hardening. 一種可撓性配線板，其特徵係在可撓性基板上形成有配線而成的可撓性配線板之形成有配線的表面之一部分或全部被如第13項中記載之被覆膜所被覆。 A flexible wiring board characterized in that part or all of the surface on which a wiring is formed on a flexible wiring board formed by wiring formed on a flexible substrate is covered with the coating film described in item 13 . 如第14項中記載之可撓性配線板，其中，配線係錫鍍敷銅配線。 The flexible wiring board according to item 14, wherein the wiring is tin-plated copper wiring. 一種經被覆膜所被覆之可撓性配線板之製造方法，其特徵係包含下述(步驟1)及(步驟3)與因應必要之(步驟2)：(步驟1)藉由將如第1項~11中任一項記載之硬化性組成物印刷於可撓性配線板之配線圖型部的至少一部分，而於該圖型上形成印刷膜之步驟(步驟2)藉由將步驟1所得之印刷膜置於40~100℃之氛圍下， 而使印刷膜中之溶劑的一部分或全量蒸發之步驟(步驟3)藉由將步驟1所得之印刷膜或步驟2所得之印刷膜於100~170℃加熱，使其硬化並形成被覆膜之步驟。 A method for manufacturing a flexible wiring board covered with a coating film, which is characterized by including the following (step 1) and (step 3) and the necessary (step 2): (step 1) The step (step 2) of printing the hardenable composition according to any one of items 1 to 11 on at least a part of a wiring pattern portion of a flexible wiring board, and forming a printed film on the pattern by step 1 The obtained printed film is placed in an atmosphere of 40 ~ 100 ° C, In the step of evaporating a part or the entire amount of the solvent in the printing film (step 3), the printing film obtained in step 1 or the printing film obtained in step 2 is heated at 100 to 170 ° C. to harden and form a coating film. step. 一種電子零件，其特徵係具有如第12項中記載之硬化膜。 An electronic component characterized by having a hardened film as described in item 12.
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