TW201113312A - Thermosetting composition for protective film for wiring board - Google Patents

Abstract

Disclosed is a thermosetting composition for a protective film for a wiring board, which has excellent low warpage properties, flexibility, and long-term insulation reliability. The thermosetting composition for a protective film for a wiring board comprises, as essential components, an epoxy group-containing compound having a tricyclodecane structure, polyurethane having a structural unit represented by formula (1) and having a functional group which can react with an epoxy group, and a solvent. In formula (1), R1 represents an alkylene group having 3 to 18 carbon atoms, and n represents an integer of 1 or more. As the epoxy group-containing compound having a tricyclodecane structure, a compound represented by formula (2) is preferably used.

Description

[Technical Field] The present invention relates to a thermosetting composition for a protective film of a wiring board of a new standard, a protective film for a wiring board obtained by curing the protective film with a thermosetting composition, A flexible wiring board covered with the protective film and a method of manufacturing the flexible wiring board covered by the protective film. More specifically, it is a thermosetting composition for a protective film of a wiring board which is excellent in low warpage, flexibility, and long-term electrical insulation reliability, and a wiring board obtained by curing the protective film with a thermosetting composition. A protective film, a flexible wiring board in which a part or all of the protective film is covered, and a method of manufacturing a flexible wiring board covered with the protective film. [Prior Art] Conventionally, a surface protective film of a flexible wiring circuit is formed by a mold having a pattern, and a polyimine film called a cover is punched and then adhered using an adhesive. The type or the type of the ultraviolet curable type or the thermosetting type protective film which is flexible by the screen printing method, especially the latter is useful in workability. The hardening type protective film agent is mainly composed of, for example, an epoxy resin type, an acrylic resin type, or a resin composition composed of these composite systems. In particular, many of the resins which have been modified, such as a butadiene skeleton, a decane skeleton, a polycarbonate diol skeleton, and a long-chain aliphatic skeleton, are mainly used as a main component, thereby suppressing the original surface protective film as much as possible. It has reduced heat resistance, chemical resistance, and electrical insulation, and at the same time improves flexibility or suppresses warpage caused by hardening shrinkage. 201113312 However, in recent years, with the miniaturization and miniaturization of electronic equipment, the flexible substrate is also light and thin, so that the influence of the softness or hardening shrinkage of the over-coated resin composition becomes more remarkable. Therefore, at present, the hardened type protective film agent fails to satisfy the required properties in terms of flexibility or warpage caused by hardening shrinkage. For example, JP-A No. 1 1-6 1 03 (Patent Document 1) discloses a resin composition using a block isocyanate of polybutadiene and a polyol, and the cured product is excellent in flexibility or shrinkage, but is excellent in flexibility or shrinkage. Insufficient heat resistance. JP-A-2004-135A 70 (Patent Document 2) discloses a reaction of a terminal diisocyanate polyurethane and a trimellitic acid obtained by reacting a polycarbonate diol with a diisocyanate compound. A composition of a polyamide-imine resin and an amine-type epoxy resin, but a cured product obtained from a polyamide-imide resin and an amine-type epoxy resin has a disadvantage of insufficient long-term reliability of electrical properties. JP-A-2006-307 1 83 (Patent Document 3) discloses a composition containing a carboxyl group-containing polyurethane polyethylenimine and an epoxidized polybutadiene, but the composition is dried to remove the solvent. At the same time, the carboxyl group-containing polyurethane polyethylenimine and the epoxidized polybutadiene are likely to have a phase separation structure and have a disadvantage that it is difficult to form a uniform film. Further, JP-A-2004-1 82792 (Patent Document 4) discloses a polyamidoximine resin having an organic siloxane skeleton, but the cured product and the substrate have poor adhesion and must be used. A special solvent such as N-methyl-2-pyrrolidone, especially in screen printing, sometimes has to dissolve the emulsion, which is problematic. Further, JP-A-2006-3 48278 (Patent Document 5) discloses that it contains a polybutadiene polyol, a polyisoprene polyol, a hydrogenated polybutadiene polyol, and a hydrogenation polymerization. A composition of a residue-containing polyurethane and an epoxy compound in a polyol unit in which the isoprene polyol is grouped. For example, when focusing on the circuit pattern forming method used in the COF (Chip On Film) assembly method, the wiring system widely used in the C Ο F assembly method is currently produced by the removal method (s u b t r a c t i v e m e t h 〇 d ). The insulating film for wiring produced by such a removal method has sufficient insulating properties as the cured product obtained by the composition disclosed in Patent Document 5. Further, a solder containing a carboxyl group-containing polyurethane and an epoxy compound having an organic residue derived from a dimer diol is disclosed in Japanese Laid-Open Patent Publication No. Hei 2-7-003 (Patent Document 6). Photoresist ink. With respect to the cured product obtained by the composition, the insulating film for wiring produced by the removal method, the solder resist ink disclosed in Patent Document 6 has sufficient insulating properties. PRIOR ART DOCUMENT Patent Document Patent Document 1 1 - 6 1 0 3 No. 2 Patent Publication No. 2 0 0 4 - 1 3 7 3 7 0 Patent Document 3 Special Opening 2 0 0 6 - 3 0 7 1 8 No. 3 Patent Document 4 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, with the semi-additive process (Semi Additive Process), the method of the present invention is disclosed in the Japanese Patent Application Publication No. JP-A-2006-348278. In development, the wiring distance between flexible wiring boards may be narrow (for example, 20 μm or less). With the narrower pitch, it is necessary to develop a resin having better electrical insulating properties. The object of the present invention is to provide a protective film for a wiring board which is soft and can obtain a protective film having good electrical insulating properties even in a semi-additive process. A curable composition, a protective film of a wiring board obtained by curing the composition, a flexible wiring board covered with the protective film, and a method of producing a flexible wiring board. Means for Solving the Problems As a result of careful study of the above-mentioned problems, the present inventors have found that when a curable composition containing a specific structural unit of a polyurethane and a solvent having a specific structure and an epoxy group-containing compound and a solvent is used, The cured product obtained by curing the curable composition is small in warpage, and the cured product obtained by curing the curable composition is excellent in flexibility and electrical insulating properties, and the present invention has been completed. In other words, the present invention (I) is a thermosetting composition for a protective film for a wiring board, which is an epoxy group-containing compound having a tricyclodecane structure, a functional group reactive with an epoxy group, and The polyurethane having a structural unit represented by the formula (1) and a solvent are essential components. 201113312

(wherein R1 represents a stretching group having a carbon number of 3 to 18, and η represents an integer of 1 or more). The present invention is a protective film for a wiring board obtained by curing a protective film of a wiring board of the present invention with a thermosetting composition. The present invention (III) is a flexible wiring board covered with a protective film, which is characterized in that part or all of the surface of the flexible wiring board on which the wiring is formed on the flexible substrate is formed by the present invention (11). ) The protective film of the wiring board is covered. The present invention (IV) is a method for producing a flexible wiring board covered with a protective film, which is characterized in that a protective film for a wiring board of the invention (I) is printed on a flexible wiring board with a thermosetting composition. In the wiring pattern portion of the tin treatment, a printing film is formed on the pattern, and the printing film is heat-cured at 80 to 130 ° C to form a protective film. More specifically, the present invention is a thermosetting composition for a protective film of a wiring board of the following [1] to [1 2], a protective film for a wiring board of [13], a flexible wiring board of [I4], and [1 5 ] Manufacturing method of flexible wiring board. [1] A thermosetting composition for a protective film for a wiring board, characterized by comprising an epoxy group-containing compound having a tricyclodecane structure, a functional group reactive with an epoxy group, and having the formula (1) The structural unit of the polyurethane and the solvent are essential components. [2] The thermosetting composition of the protective film of the wiring board of the item [1], wherein the epoxy group-containing compound having a tricyclodecane structure has a tricyclic ring [5.2.1.02, 6]. An epoxy-containing compound having a decane structure or a tricyclo[3.3.1.1'7]decane structure and having an aromatic ring structure. [3] The thermosetting composition for a protective film of a wiring board according to the item [2], wherein the epoxy group-containing compound having a three-ring brothel structure is a compound represented by the formula (2).

(In the formula, 1 represents 〇 or an integer of 1 or more). [4] The thermosetting composition for a protective film of a wiring board according to any one of [1] to [3], which has a functional group which can react with an epoxy group and has a formula (1) The structural unit of the polyurethane is a polyurethane having a functional group which can react with an epoxy group and having a structural unit represented by the formula (1), and further having a quinone bond. amine. [5] The thermosetting composition for a protective film of a wiring board according to any one of [1] to [4] wherein the functional group reactive with the epoxy group is a carboxyl group [6] as in [1]. The thermosetting composition for a protective film of a wiring board according to any one of the items 4 to 4, wherein the functional group reactive with the epoxy group is an acid anhydride group. [7] The thermosetting composition for a protective film of a wiring board according to the item [4] or [5], which has a functional group reactive with an epoxy group, and has a -10-201113312 represented by the formula (1) The structural unit, the Bsc vinegar polyglycol having the quinone imine bond is a polyurethane polyethylenimine obtained by the following components (a) to (d), component (a) diisocyanate And component (b) has a (poly)carbonate polyol derived from a diol having 3 to 18 carbon atoms, a diol having a carboxyl group as component (c), and a difunctional compound represented by formula (3) (3) Hydroxyl end

(wherein R 2 and R 3 each independently represent a divalent aliphatic anthracene hydrocarbon group, and Y 1 means a 4-base derived from a tetracarboxylic acid or an anhydride group thereof. X 1 represents a derivative derived from a diamine or a diisocyanate 2 f| , 111 is an integer from 0 to 20). [8] The protective composition of the wiring board of the item [4] or [6], which has a functional group reactive with an epoxy group, a structural unit represented by the formula (1), and further has a hydrazine The imine bond ethyl sulphate polyethylenimine is a polyamidoethylamine having a structure selected from the group consisting of formula (4) to formula (6) / at least one structural unit, and the amine group A reaction machine Residual imine, (3) Aromatic valence organic organic group with thermosetting and having a group of amine groups -11 - (4) 201113312

(wherein, a plurality of R4 groups are each independently an alkylene group having a carbon number of 3 to 18, and a plurality of R5 groups are each independently an alkylene group having a carbon number of 3 to 18, and each of a and b is independently an integer of 1 to 20 , a plurality of X2 systems are each independently a divalent organic group

(wherein, the plurality of R6 groups are each independently an alkylene group having a carbon number of 3 to 18, and the plurality of R7 groups are each independently an alkylene group having a carbon number of 3 to 18, and the c and d systems are each independently 1 to 2 0. Integer, a plurality of X3 systems are each independently a divalent organic group, and Y2 is a CH2, S02 or 0.)

(6) (wherein, the plurality of R8 systems are each independently an alkylene group having a carbon number of 3 to 18, and the plurality of R9 groups are each independently an alkylene group having a carbon number of 3 to 18, and the e and f systems are each independently 1 to 1). An integer of 20, a plurality of X4 systems are each independently a divalent organic group, and Y3 is a group of any one of the following formulas (7) to (33).) -12- (7) 201113312

-13- (12) 201113312

(13)

(14)

(15>

(16) -14- (17) 201113312

(18)

(19)

(2 0)

(2 1) -15 - 201113312

(twenty two)

(twenty three)

(twenty four)

(2 5)

(2 7) -16- 201113312

(2 8)

(2 9)

(3 0)

(3 1)

(3) The thermosetting composition for a protective film of a wiring board according to any one of the items [1] to [3], which has a functional group reactive with an epoxy group, Further, the polyurethane having the structural unit shown by the formula (1) of the formula (1) is subjected to the following components (a), -17-201113312 (b), component (c), and component (e). The polyurethane obtained by the reaction, the (a) diisocyanate of the component (a), the (poly)carbonate polyol having the organic residue derived from the diol having 3 to 18 carbon atoms, and the component (c) A diol having a carboxyl group and a compound having three or more hydroxyl groups in the molecule of the component (e). [10] The thermosetting composition for a protective film of a wiring board according to any one of [1] to [6], which has a reactivity with an epoxy group. The functional group and the polyurethane having the structural unit represented by the formula (1) are polyurethanes further containing an organic residue derived from the dimer diol. [1] The thermosetting composition for a protective film of a wiring board according to any one of [1] to [1], wherein the solvent is contained at atmospheric pressure and has a temperature of 170 ° C or more. a mixed solvent of at least one solvent having a boiling point of 200 ° C and at least one solvent having a boiling point of 200 ° C to 220 ° C under atmospheric pressure [1 2] as in [1] to [1 1] The thermosetting composition for a protective film of a wiring board according to any one of the invention, wherein a solvent selected from at least one selected from the group A below and a solvent selected from at least one selected from the group B below are essential components. Mixed solvent, 3-methoxybutyl acetate group A: diethylene glycol dimethyl ether (boiling point 162t:), diethylene glycol diethyl ether (boiling point 189. (:), diethylene glycol B Methyl ether (boiling point 176t), dipropylene glycol dimethyl ether (boiling point 171 °C) -18- 201113312 (boiling point 173 °C), ethylene glycol monobutyl ether acetate (boiling point 1 92. (: Group B: diethylene glycol butyl methyl ether (boiling point 2 1 2 ° C), tripropylene glycol dimethyl ether (boiling point 2 15 ° C), triethylene glycol dimethyl ether (boiling point 2 16 6 ), ethylene Dibutyl ether (boiling point 20 3 ° C), diethylene glycol di-monoethyl ether acetate (boiling point 2 17 ° C), r - butyrolactone (boiling point 2 0 4 ° C). [13] A protective film for wiring boards A protective film for a wiring board obtained by curing a protective film for a wiring board according to any one of the items [1] to [1 2], which is cured by a thermosetting composition. [14] A scratch coated with a protective film The wiring board is characterized in that part or all of the surface of the flexible wiring board on which the wiring is formed on the flexible substrate is covered by the protective film of the wiring board of the item [1 3]. And a method for producing a flexible wiring board coated with a protective film, wherein the protective film for a wiring board according to any one of the items [1] to [1 2] is printed with a thermosetting composition to A printed wiring film is formed on the patterned wiring pattern portion of the flexible wiring board, and the printed film is heat-cured at 8 〇 to 130 ° C to form a protective film. Advantageous Effects of the Invention The cured product of the present invention is Non-adhesive, good usability, good flexibility and moisture resistance, and high level of long-term electrical insulation reliability, and It has low warpage, good adhesion to the substrate or the bottom enamel, and good solvent resistance. Therefore, the present invention is coated on a flexible substrate such as a flexible wiring board or a polyimide film. When the thermosetting composition is formed by a hardening reaction to a cured film (protective film), the flexible wiring board with a protective film or the flexible substrate with a protective film has a small warpage and is easy to be used. In addition, since the cured product of the present invention has flexibility, it is possible to provide a flexible wiring board with an electrical insulating protective film that is less likely to be cracked (for example, flexibility such as COF) Printed wiring board). [Mode for Carrying Out the Invention] Hereinafter, the present invention will be specifically described. First, the invention (I) will be described. The present invention is a polyurethane and a solvent having an epoxy group-containing compound having a tricyclodecane structure, a functional group reactive with an epoxy group, and having a structural unit represented by the formula (1) A thermosetting composition for a protective film of a wiring board which is an essential component.

(wherein R1 represents an alkylene group having 3 to 18 carbon atoms, and η represents an integer of 1 or more). The present invention is a protective film for a wiring board obtained by curing a protective film for a wiring board of the invention (I) with a thermosetting composition. The epoxy group-containing compound having a tricyclodecane structure, which is one of the essential components of the composition of the invention (I), is not particularly limited as long as it is a compound having a tricyclodecane structure and an epoxy group in the molecule. -20- 201113312 Tricyclodecane structure means, for example, a tricyclic [5.2.丨.02'6] decane structure or a tricyclo[3.3.1.13,7] decane structure. The epoxy group-containing compound having a tricyclo[5.2.1.02,6]nonane structure, for example, a compound of the following formula (2) or the following formula (34).

(wherein g represents 〇 or an integer of 1 or more). Further, the epoxy group-containing compound having a tricyclo[3.3.1.I3'7]decane structure is, for example, a compound of the following formula (3 5 ) to the following formula (3 8 ). Ο η

(3 5) -21 - 201113312

(3 6)

(3 7)

Among these bicyclo[5·2·1·02'6]decane structures or tricyclo[33113'decane structures and compounds having an epoxy group, it is preferred to lower the water absorption rate, specifically, preferably. It is an epoxy group-containing compound having a tricyclic [5.2J.02,6]decane structure or a tricyclic [3.3_1_13'7] brothel structure" and having an aromatic ring structure. In the above formula (2) and formulas (34) to (38), the compounds represented by the formula (2) and the formula (35) to the formula (38) are as follows. In the epoxy group-containing compound having a tricyclo[5.2.1·〇2'6]decane structure or a tricyclo[3.3.1.I3,7]decane structure and having an aromatic ring structure, when the ease of availability is considered 'Specially a compound represented by the formula (2). The compound represented by the formula (2) is commercially available from DIC Corporation (trade name: EPICLONHP-7200L, EPICLONHP-7200, -22-201113312 EPICLONHP-7200H, EPICL Ο Η Η P - 7 2 0 Ο Η Η ), 'Nippon Chemical Co., Ltd. is also commercially available under the trade names of XDd〇00-2L and XD_1000, and is easy to obtain. The use amount of the epoxy group-containing compound having a tricyclodecane structure as an essential component of the invention (I) can have a functional group reactive with an epoxy group as an essential component of the invention (1) to be described later, and has The ratio of the number of functional groups reactive with an epoxy group contained in the structural unit of the ethyl carbamate represented by the formula (1) to the number of epoxy groups is represented by the formula (1). When the functional group reactive with an epoxy group and the epoxy group are reacted at a ratio of 1:1, the number of functional groups reactive with the epoxy group contained in the thermosetting composition of the invention (I) is The ratio of the number of epoxy groups containing an epoxy group having a tricyclodecane structure is preferably in the range of 1/3 to 2/1, more preferably in the range of 1/2.5 to 1.5/1. When the ratio is less than 1/3, there is a possibility that many unreacted epoxy groups are likely to remain, which is not preferable. Further, when the ratio is more than 2/1, many unreacted functional groups which can react with the epoxy group remain, and the electrical insulating properties are not good. For example, a carboxyl group can be used as a functional group which reacts with an epoxy group at a ratio of 1:1. One of the essential components of the composition of the invention (I), which has a functional group reactive with an epoxy group and has a structural unit represented by the formula (1), as long as it is intramolecularly compatible When the functional group of the epoxy group reaction and the polyurethane of the structural unit represented by the formula (1) are not particularly limited. -23- (1) 201113312

(wherein R1 represents an integer of a alkylene group having a carbon number of 3 to 18). In the formula (1), R1 represents a polycondensation of the alkyl group having a carbon number of 3 to 18 or less. Ethyl carbamate cannot be aqueous, so it is not preferable. Further, the amount of the solvent of the polyurethane having a carbon number of 19 or more is very small, and the adhesion is sometimes lowered, which is not preferable. η is preferably an integer of from 1 to 20. The structural unit of the formula (1) is derived from a structural unit having a (poly)carbonate diol raw material having a carbon number of 3 to 18 units, but in the case of water resistance, the dimer diol can be used as a functional group in the production. The component having the ethyl ester of the structural unit represented by the formula (1) is used. The (poly) carbon number of the raw material can be used as an average molecular weight of 400 to 1 0000. The description of the acid ester in (poly)carbonic acid diol described in the present specification means that one or more carbonic acids are contained in the molecule, and "(poly)carbonate" means monocarbonate and polycarbonate. Therefore, the present specification The "poly"carbonate diol has one or more carbonated vinegar bonds, and the two alcoholic groups represent one or more groups. The carbon number 2 is sufficiently resistant to dissolve the diol of the polyimine. The structure is to increase the "(poly)carbonate bond of the epoxy-reactive polyurethane diol. In other words, the ester." refers to the molecular-based compound-24-201113312 Manufacture (poly)carbonate diol In the case where the diol component of the raw material may remain, in the present specification, the remaining diol component is defined as not included in the "(poly)carbonate diol". For example, when 1,9-nonanediol and diethyl carbonate are used as a raw material, a (poly)carbonate diol is produced by a transesterification reaction in the presence of a catalyst, and the raw material is 1,9-壬2 When the alcohol remains in the (poly)carbonate diol in an amount of 5% by mass, the remaining 1,9-nonanediol is not contained in the "(poly)carbonatediol". The functional group reactive with the epoxy group may, for example, be a functional group such as an amine group, a carboxyl group, a carboxylic anhydride group, a thiol group, an isocyanate group or a hydroxyl group. Among these functional groups, a reaction rate with an epoxy group-containing compound having a tricyclodecane structure is preferably within a certain range. Therefore, a carboxyl group or a carboxylic anhydride group is preferred. Further, it is preferred to use the odor of the compound or the stability of the functional group in a normal atmosphere in a normal temperature atmosphere. When considering this problem, it is most preferred to be a carboxyl group. In order to suppress warpage at the time of curing of the composition of the present invention (I), the increase in crosslinking density at the time of hardening is less in the range which does not impair the solvent resistance of the cured product or the long-term electrical insulating property and heat resistance. Better. In order to suppress the increase in bridging density at the time of hardening to a certain extent, and have good solvent resistance or long-term electrical insulating property and heat resistance of the cured product, it has a functional group reactive with an epoxy group, and has the formula (1) It is preferable that the structure of the polyurethane-based molecule of the structural unit represented by the following three structures is at least one of the following three structures. First, a group having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) further has a quinone imine-25-201113312 constructor. In other words, the polyurethane having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) preferably has a functional group reactive with an epoxy group, and has the formula (1) A structural unit represented by a polyamidourethane having a quinone bond. The other structure is within the range of the solvent to be dissolved, and it is preferred that the molecule has a certain branching structure. The other structure has a functional group reactive with an epoxy group, and has a structural unit represented by the formula (1), and further preferably contains a polyurethane having an organic residue derived from a dimer diol. . First, a polyurethane having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) is a functional group having a reactive group with an epoxy group, and has a formula (1). The structural unit, in the case of a polyamidourethane having a quinone imine bond. An example of a polyurethane having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and having a quinone imine bond, for example, Japanese Patent Publication No. 2000 A functional group which is reactive with an epoxy group and has a structural unit represented by the formula (1), and has a structural unit represented by the formula (1), and has a structural unit of the formula (1) Polyamidourethane, a quinone imine bond. First, a polyurethane polycondensate having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and having an oximine bond is described in JP-A-2003-198105. A polyaminocarbamic acid having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and having an indole bond of 醯-26-201113312, as described in JP-A-2003-198105 The ester polyimine is a polyethyl urethane having a structural unit represented by the following formulas (4) to (6) in the molecule.

(4) (wherein, a plurality of R4 groups are each independently an alkylene group having a carbon number of 3 to 18, and a plurality of R5 groups each of which are b and each independently have a carbon number of 3 to 18, and the alkyl group is independently 1 An integer of ～20, a plurality of X2 systems are each independently a divalent organic group -x3—N—C—〇-^R®-〇—c—〇^-r7-〇—c- c=o

ο (5) (wherein, the plurality of R6 systems are each independently an alkylene group having a carbon number of 3 to 18, and the plurality of R7 groups are each independently an alkylene group having a carbon number of 3 to 18, and the c and d systems are each independently An integer from 1 to 20, the plurality of X3 systems are each independently a divalent organic group, Y2 is a CH2, S02 or Ο.) ---X-N-c-〇-(-R8-〇-c-〇i-R9 -〇—c—N-丨丨\ II 4 II 〇0 〇Ο 0 people

; X~VY "0" 0 0 (6) where a plurality of R8 systems are independently alkylene groups having a carbon number of 3 to 18 and a plurality of R9 systems each having an independent carbon number of 3 to 18 carbon atoms. KI-27 - 201113312 From the independent integer of 1 to 2 0, a plurality of X4 systems are each independently a divalent organic group, and Υ3 is a group of any one of the following formulas (7) to (33).

(7)

-28- (12) 201113312

(15)

(16) -29- (17)201113312

, C II ο (2 0)

(2 1) -30- 201113312

(twenty two)

(twenty three)

(twenty four)

(2 5)

(2 7) -31 - 201113312

(2 8)

(2 9)

(3 0)

(3 1)

(3 2) (3 3) Polyurethane polyethylenimine having a structure represented by formula (4) or formula (5), usually consisting of a trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof One or more selected compounds are obtained by reacting an isocyanate compound or an amine compound. -32-201113312 The trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof are not particularly limited. For example, when the polyethylenimine having the structure represented by the formula (4) is used, the formula (39) can be used. ) the compound indicated. From the viewpoint of heat resistance, cost, and the like, trimellitic anhydride is particularly preferred. Ο

(In the formula, R14 represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group.) Further, in the case of a polyurethane having a structure represented by the formula (5), a formula (40) can be used. ) the compound indicated.

(4 0) (wherein R15 represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and Y2 is CH2, CO, S〇2, or fluorene.) A polyamine having a structure represented by formula (6) When ethyl carbazate is used, the compound represented by the formula (4 1 ) can be used.

(In the formula, Y3 is a group of any one of the above formulas (7) to (33).) a These tetracarboxylic dianhydrides may be used singly or in combination of two or more types -33-201113312. In addition to these, an aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, azelaic acid, decane dicarboxylic acid, or the like) may be used as necessary. An aromatic diacid (isophthalic acid, terephthalic acid, phthalic acid, naphthalene dicarboxylic acid, oxydibenzoic acid) or the like. At this time, a guanamine bond can also be formed in the molecular chain. As the isocyanate compound, for example, a diisocyanate compound represented by the formula (42) can be used. OCN-fX—N—C—〇-^R16*〇—C—〇)-R17-〇—C—N—〇 o h ο

-Xs-NCO (4 2) (wherein, a plurality of R16 systems are each independently an alkylene group having a carbon number of 3 to 18, and a plurality of R17 groups are each independently an alkylene group having a carbon number of 3 to 18, h and i Each of them is independently an integer of 1 to 2 〇, and the plurality of X5 groups are each independently a divalent organic group.) The diisocyanate compound of the formula (42) is a compound of the formula (43) represented by a (poly)carbonate diol. (44) is obtained by reacting a diisocyanate.

HO R18*0—C—II 〇

O^-R18-OH (4 3) (wherein, a plurality of R18 systems are each independently an alkylene group having 3 to 18 carbon atoms, and j is an integer of 1 to 2 Å.) OCN-X-NCO (4 4) -34-201113312 (wherein X6 is a divalent organic group.) The oxime 6 of the formula (44) represented by diisocyanate has, for example, a carbon number of 丨~2〇, or an unsubstituted or methyl group. The lower alkyl group having a carbon number of 取代 is substituted with an extended aryl group such as a phenyl group. The carbon number of the alkyl group is more preferably. More preferably, it is a group having two aromatic rings such as a group of methane-4,4,-diyl, diphenyl maple-4,4,-diyl. The (poly)carbonate diol represented by the above formula (43), for example, ^^, ω-poly(1,6-hexene carbonate) diol, ^...-poly(3_methyl-oxime, 5 pentylene Dilute carbonated vinegar)-alcohol, α,ω-poly[(ι,6-hexene:3-methyl-pentylene) carbonate]diol, α,ω-poly[(丨,9_pinene: [2-methyl-anthracene, 8 octene) Carbonate] diols and the like are commercially available, for example, under the trade names of PLACCEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220 manufactured by Daicel Chemical Industry Co., Ltd. 220PL, 220HL, and the company's kuraray product name kuraray polyols C-590, C-1065N, C-1015N, C-2015N, etc. These may be used alone or in combination of two or more. When the (poly)carbonate diol is produced as described above, the diol component of the remaining raw material may be contained. However, in the present specification, the remaining diol component is defined as not contained in the "(poly)carbonate diol. "By. Therefore, the product names such as PLACCEL, CD-20 5, 20 5PL, 205HL, 2 1 0, 210PL, 210HL, 2 2 0, 220PL, 22 0HL, and kuraray, which are manufactured by Daicel Chemical Industry Co., Ltd., are included in the product name of kuraray. The raw material diol contained in the commercially available (poly)carbonate diol such as polyols C-590, C-1065N, C-1015N, C-20 1 5N, etc. is not contained in "(poly)carbonate diol" in. These raw material diol components are -35 - 201113312 and are included in (w) which will be described later. Further, the diisocyanate represented by the above formula (44) is, for example, dimethane·2,4'-diisocyanate; 3,2'-, 3,3'-, 4,2'-, 4,3'-, 5,3,-,6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diiso-slip; 3,2'-,3,3,-,4,2, -, 4,3'-, 5,2'-, 5,3,-, 6,2,- or diethyldiphenylmethane·2,4'-diisocyanate; 3,2'-, 3, 3'-, 4,3,-, 5,2'-, 5,3,-, 6,2'- or 6,3,-dimethoxydiphenyl-2,4'-diisocyanate; Diphenylmethane-4,4'-diisocyanate; methane-3,3'-diisocyanate; diphenylmethane-3,4'-diisocyanate diphenyl ether-4,4'-diisocyanate Dibenzophenone-4,4'-diisocyanate-4,4'-diisocyanate; benzylidene-2,4-diisocyanate benzylidene-2,6- Diisocyanate; m-phenylene diisocyanate, benzodimethyl diisocyanate; naphthalene-2,6-diisocyanate; 4,4'-I bis(4-phenoxyphenyl)propane The formula (44) of a diisocyanate or the like is preferably an aromatic polyisocyanate having an aromatic ring. These can be used individually or in combination of 2 or more types. The diisocyanate represented by the formula (44) is within the object of the present invention, and hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate '4,4 can be used. An aliphatic or aliphatic isocyanate such as dicyclohexylmethyl isocyanate, trans cyclohexane-I,4-diisocyanate, water-added methyl-diisocyanate, lysine diisocyanate, or a trifunctional or higher poly Isocyanate. The diisocyanate represented by the formula (44) is used for stabilization of the necessary blocker in order to avoid diurnal variation. Blocking agents are, for example, alcohols, phenyl 5,2,-acid esters, 6,3'-4,2,-yldiphenyl esters; esters; esters; P-2,2-, such ranges The alkylbenzene diphenyl ring type can be used for phenol, -36-201113312, etc., without particular limitation. As the raw material of the polyethylenimine polyimide, a diol component other than the (poly)carbonate diol represented by the formula (43) (hereinafter referred to as the component (w)) can be used. The component (w) is, for example, hydrazine, 2-propanediol, hydrazine, 3:propylene glycol, L2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, hydrazine, 6_hexanediol '3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanyl-methanol, ι,9 -decanediol, 2-methyl-1,8-octanediol, 1,10-nonanediol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentane Alcohol, 2·butyl-2-ethylpropanediol, i, 3-cyclohexyl dimethanol, hydrazine, 3-benzenedimethanol, 1,4-benzenedimethanol, and the like. The raw material diol contained in the above-mentioned commercially available (poly)carbonate diol is contained in the component (w). The ratio of the (poly)carbonate diol and the component (w) represented by the above formula (43) to the diisocyanate represented by the formula (44) is preferably such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is an isocyanate group / a hydroxyl group = 1.01 or more. . The reaction of the (poly)carbonate diol represented by the above formula (43) and the component (w) with the diisocyanate represented by the formula (44) can be carried out in the absence of a solvent or an organic solvent. The reaction temperature is preferably from 60 to 2,000 ° C, more preferably from 80 to 180 ° C. The reaction time is appropriately selected by the scale of the batch, the reaction conditions employed, and the like. For example, a flask size of 1 to 5 L is 2 to 5 hours. The number average molecular weight of the diisocyanate compound represented by the formula (42) thus obtained is preferably from 500 to 10,000, more preferably from 1, 〇〇〇 to 9,500, particularly preferably from 1,500 to 9,000. When the number average molecular weight is less than 500, the warpage-37-201113312 tends to deteriorate. When the number average molecular weight is less than 10,000, the reactivity with the isocyanate compound is lowered, and the formation of the polyimine resin tends to be difficult. In the present specification, the number average molecular weight is measured by a gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. The isocyanate compound of the raw material component of the polyurethane polyamide of the formula (4) to the formula (6) can be a polyisocyanate compound other than the diisocyanate compound represented by the formula (42). When the polyisocyanate compound other than the diisocyanate compound represented by the formula (42) is not particularly limited, the compound is, for example, a diisocyanate represented by the formula (44) or a polyisocyanate having a trivalent or higher value. These may be used alone or in combination of two or more. The preferred range of the number average molecular weight of the polyisocyanate compound other than the diisocyanate compound represented by the formula (42) is the same as the diisocyanate compound represented by the formula (42). In particular, from the viewpoint of heat resistance, a polyisocyanate compound other than the diisocyanate compound represented by the formula (42) and a polyisocyanate compound represented by the formula (42) are preferably used. When the diisocyanate compound represented by the formula (42) and the polyisocyanate compound other than the diisocyanate compound represented by the formula (42) are used alone, from the viewpoints of flexibility, warpage, and the like of the protective film for a flexible wiring board, It is preferred to use a diisocyanate compound represented by the formula (42). When the polyisocyanate compound other than the diisocyanate compound represented by the formula (42) is 50 to 1% by mass based on the total amount of the aromatic polyisocyanate, it is preferable to consider the balance between heat resistance, solubility, mechanical properties, cost surface, and the like. 'Specially good is 4,4'-diphenylmethane diisocyanate. -38-201113312 When a diisocyanate compound represented by the formula (42) and a polyisocyanate compound other than the diisocyanate compound represented by the formula (42) are used, the diisocyanate compound represented by the formula (42) / the diisocyanate represented by the formula (42) The equivalent ratio of the polyisocyanate compound other than the compound is preferably from 0.1 to 0.9 to 0.9/0.1, more preferably from 0.2/0.8 to 0.8/0.2, particularly preferably from 0.3/0.7 to 0.7/0.3. When the equivalent ratio is within this range, film properties such as good warpage, adhesion, and good heat resistance can be obtained. An amine compound having a raw material component of a polyurethane urethane having a structural unit represented by the formula (4) to the formula (6), for example, a compound obtained by converting an isocyanate group of the above-mentioned iso cyanate compound into an amine group . The conversion of an isocyanate group to an amine group can be carried out by a known method. The preferred range of the number average molecular weight of the amine compound is the same as the diisocyanate compound represented by the formula (42). a trivalent polycarboxylic acid or a derivative thereof having an acid anhydride group as a raw material component of a polyurethane urethane having a structural unit represented by the formula (4) to the formula (6), and/or having an acid anhydride group When the blending ratio of the tetravalent polycarboxylic acid is the total number of isocyanate groups of the above isocyanate compound (polyisocyanate compound other than the diisocyanate compound represented by the formula (42) and the polyisocyanate compound represented by the formula (42)), the carboxyl group and the carboxyl group are The ratio of the total number of the acid anhydride groups is preferably from 0.6 to 1/4, more preferably from 0.7 to 1.3, particularly preferably from 0.8 to 1.2. This ratio is less than 〇6 or more than 1.4. It is difficult to increase the molecular weight of the resin containing a polyimide bond. a trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and/or a tetravalent polycarboxylic acid having an acid anhydride group, wherein a compound represented by the formula (39) is used, and an isocyanide-39-201113312 acid ester compound is used. When the diisocyanate compound is represented by 42), a polyamidoquinone imine having a structural unit represented by the formula (4) can be obtained.

(4) (wherein R4, R5, a, b, and χ2 are as described above.) A trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and/or a tetravalent polycarboxylic acid having an acid anhydride group is used. When the diisocyanate compound represented by the formula (42) is used as the compound represented by the formula (40), a polyamidoquinone imine having a structural unit represented by the formula (5) can be obtained.

(wherein R6, R7, c, d, X3, and Υ2 are as described above.) A trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and/or a tetravalent polycarboxylic acid having an acid anhydride group is used ( 41) Compound represented by the formula (42), when the isocyanate compound is a diisocyanate compound represented by the formula (6), a polyamidoquinone imine having a structural unit represented by the formula (6) can be obtained.

(wherein, R8, R9, e, f, X4 'Y3 are as described above.) -40- (6) 201113312 Polyamine ethyl ester polyimine having a structural unit represented by formula (4) to formula (6) In the production method, a reaction of a compound selected from a trivalent acid having an acid anhydride group and a derivative thereof and a tetravalent polycarboxylic acid having an acid anhydride group with an isocyanate compound or an amine compound is generated by the presence of a free When the carbon dioxide gas is removed to the reaction body, it is heated and condensed to carry out the reaction. By this method, a carboxyl group, an acid anhydride or an isocyanate polyethylenimine may be produced at the terminal. When the terminal group is considered to have epoxy group properties, it is preferably a residue and/or an acid anhydride. As the solvent for the above synthesis, a solvent having a boiling point of from 150 ° C to 25 ° C under atmospheric pressure is generally used. In order to obtain the balance of the volatility and the like of the solvent of the polyurethane polyethylenimine having the structural unit represented by the formula (4), it is possible to use two or more types in the atmosphere of 1500-1500. A solvent having a boiling point of C is preferred. More preferably, it has a temperature of more than 170 ° C or less than 200 ° under atmospheric pressure. (: the boiling point of the solvent at atmospheric pressure 'having a boiling point of 200 t to 220 t. Under atmospheric pressure, with 170 ° C or more, less than 200. (: Solvent 'for example, diethylene glycol dimethyl ether ( Boiling point 1 6 21 ), diethyl ether (boiling point 889 ° C), diethylene glycol ethyl methyl ether (boiling point), dipropylene glycol dimethyl ether (boiling point 171. 〇), 3-methoxybutyl ester ( Boiling point of 1 7 1 ° C), ethylene glycol monobutyl ether acetate (boiling point; [etc. at atmospheric pressure] has 200. (: ~220. (: the boiling point of the solvent is diethylene glycol butyl methyl ether (boiling point 2 1 2 t ), tripropylene glycol dicarboxylic acid polycarboxylate above the solvent system, the reaction with the ester group, has ~ formula (6 solution or pressure, 倂 used in solvent and boiling point of ethylene glycol 176〇 C-based acetic acid 9 2〇C), such as methyl ether (-41 - 201113312 boiling point 215 ° C), triethylene glycol dimethyl ether (boiling point 216 < t), ethylene glycol - butyric acid (boiling point 203 〇 C), Diethylene glycol di-monoethyl ether acetate (boiling point 217 C), r, butyrolactone (boiling point 204t), etc. $ $ @ 'suitable as a solution of the thermosetting composition of the present invention The user is preferred, has high volatility, can impart low-temperature hardenability, and is excellent in efficiency, and can be used in a homogeneous reaction, preferably a combination of the following solvents. Specifically, at atmospheric pressure, it has 170^~20〇. The solvent having a boiling point of π2 is at least one selected from the group consisting of diethylene glycol diethyl ether (boiling point 189. hydrazine, diethylene glycol ethyl formate (boiling point 176t:), dipropylene glycol dimethyl ether (boiling point mt:)) The solvent having a boiling point of 200〇c~220<>C2 is preferably a combination of r-butyrolactone (boiling point 204〇C), and the optimum combination is 170〇c-20 (rC2 boiling point) at atmospheric pressure. The solvent is diethylene glycol diethyl ether (boiling point 189. (:) and a combination of a solvent having a boiling point of 20 (TC to 220 eC) of 7-butyrolactone (boiling point 2〇4〇c) at atmospheric pressure. When a combination of a preferred solvent is used, since it has a low hygroscopicity and a high boiling point and a low volatility, it is also suitable as a solvent for a screen printing ink. In order to fully exhibit the above effects, it has a temperature of 170 ° C to 200 ° C under atmospheric pressure. The solvent of the boiling point of °C and 2 〇〇 at atmospheric pressure. 〇~220 t The ratio of the solvent of the boiling point is expressed by the mass ratio in the range of 5: 9 5 to 8 0 : 20, more preferably 1 〇: 90 to 60: 40. The polyurethane is not damaged. In the range of the solubility of the polyimine, a solvent having a boiling point of from 1 7 〇 t to 2001 and a solvent other than a solvent having a boiling point of from 200 ° C to 22 ° C at atmospheric pressure can be used. Reactive monomers or reactive diluents can also be used as solvents. The amount of the solvent to be used is preferably from 0.8 to 5.0 times (mass ratio) of the produced polyurethane melamine. When it is less than 8 times, the viscosity at the time of synthesis is too high, and it is difficult to synthesize because it cannot be stirred, and when it is more than 5. The reaction speed tends to decrease. The reaction temperature is preferably from 80 to 210 ° C, more preferably from 1 to 19 Torr. 〇, especially good is 120~180°C. When the temperature is less than 80 ° C, the reaction time is too long, and when it exceeds 21 Torr, a ternary reaction occurs in the reaction, which is liable to cause gelation. The reaction time can be appropriately selected by the size of the batch and the reaction conditions employed. Further, if necessary, the reaction may be carried out in the presence of a catalyst such as a metal such as a tertiary amine, a metal such as a metal, a tin, a zinc, a titanium or a cobalt, or a semi-metal compound. The number average molecular weight of the polyurethane polyethylenimine thus obtained is preferably 4,000 to 40, more preferably 5,000 to 38,000, particularly preferably 6,000 to 36,000. When the number average molecular weight is less than 4, the film properties such as heat resistance tend to be lowered, and when it exceeds 40,000, it is not easily dissolved in a solvent, and insolubilization tends to occur during the synthesis. In addition, there is a tendency to be inferior in workability. After the end of the synthesis, the isocyanate group at the end of the resin may be blocked with a block agent such as an alcohol, an indoleamine or an anthracene. Next, a polyamine group having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and having an oxime bond is described in JP-A No. 2 006-3 07 1 8 3 Ethyl formate polyimine. JP-A-2006-3-07 1 8 3 discloses a functional group having a functional group which can react with an epoxy group and having a structural unit represented by the formula (1), and further having a quinone bond The quinone imine is obtained by the following raw materials of the components (a) -43 to 201113312, the component (b), the component (c'), and the component (d). Component (a) diisocyanate, component (b) having a (poly)carbonate polyol derived from a diol having 3 to 18 carbon atoms, and component (c') having a functional group reactive with an epoxy group And the difunctional hydroxy terminal 醯 represented by the formula (d) (3)

(wherein R2 and R3 each independently represent a divalent aliphatic or hydrocarbyl group] Y1 represents a 4-base derived from a tetracarboxylic acid or an anhydride group thereof. X1 represents a divalent value derived from a diamine or a diisocyanate. , m is an integer from 0 to 20). The diisocyanate may be any diisocyanate as long as it has two isocyanates in the oxime molecule. For example, an aliphatic, alicyclic or diisocyanate is preferably an aliphatic, alicyclic or aromatic diisocyanate which does not contain an isocyanate group and has a carbon number; specifically, such as 1,4-tetra Methyl diisocyanate, iota, 5-pentamethylene diiso, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate 3 - isocyanate methyl trimethylcyclohexyl isocyanate (isophorone diisocyanate), (isocyanate methyl)-cyclohexane, 4,4'-dicyclohexylmethane di-reacting machine residue imine. (3) Aromatic valence organic organic based aromatics 2~30 words, cyanate methylene-3,5,5-1,3-bisisocyanate • 44- 201113312 Ester, phenylene Methyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, benzoyl diisocyanate, and the like. As the diisocyanate, a block diisocyanate in which an isocyanate group is blocked with a blocking agent can be used. Examples of the blocking agent include an alcohol system, a phenol system, an active methylene group, a thiol type acid amide type, a ruthenium amide type, an imidazole type, a urea type, an anthraquinone type, an amine type, and an imide type. The bisulfite type, the pyridine type, etc. can be used individually or in combination of 2 or more types. Specific blocking agents, such as alcohols, for example, methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexyl Examples of the phenols include alcohols, phenols, cresols, ethyl phenols, butyl phenols, nonyl phenols, decyl phenols, styrenated benzoyl benzoates, and the like. Examples of the thiol such as dimethyl sulphate, diethyl malonate, ethyl acetoacetate, ethyl acetate, and ethyl ketone, such as butyl thiol and dodecyl thiol. Examples of the acid amides include acetanilide, decylamine acetate, ε-caprolactam' quinone-valeramine, 7-butylidene, and the like, and the acid quinone imide is, for example, succinic acid succinate. Ammonium maleate, imidazole is, for example, imidazole or 2-methylimidazole, and urea is, for example, urea, thiourea, ethylene urea, etc., such as formaldehyde, acetaldehyde, acetone, methyl Examples of the ketone oxime, cyclohexanone oxime, etc., and the amine type are, for example, diphenylamine, aniline or carbazole, and the imide is, for example, ethyleneimine or polyethyleneimine, and the bisulfite is, for example. Sodium bisulfite and the like, for example, a pyridine 2 - hydroxypyridine, 2 - hydroxyquinoline. The (poly)-45 - 201113312 carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms has a function of imparting flexibility to the intended polyurethane polyamide. The (poly)carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms preferably has an average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight is less than 500, it is difficult to obtain preferable flexibility, and when the number average molecular weight exceeds 10,000, heat resistance or solvent resistance is deteriorated. Therefore, the above-described degree is preferred. (Poly)carbonate polyol having an organic residue derived from a diol having a carbon number of 3 to 18, and specifically, for example, UH-CARB, UN-CARB, UD-CARB manufactured by Ube Industries Co., Ltd. UC-CARB, PLACEL CD-PL, PLACEL CD-Η, manufactured by DAICEL Chemical Industry Co., Ltd., kuraray polyol C series manufactured by Kuraray Co., Ltd., etc. These polycarbonate polyols may be used alone or in combination of two or more. When a (poly)carbonate polyol is produced, the polyol component of the remaining raw material may be contained. However, in the present specification, the remaining polyol component is defined as not included in the "(poly)carbonate polyol". For example, when 1,9-nonanediol and diethyl carbonate are used as a raw material, and a (poly)carbonate polyol is produced by a transesterification reaction in the presence of a catalyst, the raw material is 1,9-壬2 When the alcohol remains in the (poly)carbonate polyol of the product in an amount of 5% by mass, the remaining 1,9-nonanediol is not contained in the "(poly)carbonate polyol", and is included in the following. In the ingredient (X). The raw material of the polyurethane urethane may be a (poly)carbonate polyol having one type of organic residue derived from a diol having 3 to 18 carbon atoms, or may be used in two or more types. . -46- 201113312 Cross-linking polyurethane urethane by introducing a diol compound having a functional group reactive with an epoxy group into a molecule of polyethylammonium polyethylenimine In this case, crosslinking can be effectively carried out to further enhance the heat resistance or solvent resistance of the resulting hardened insulating film. The diol compound having a functional group reactive with an epoxy group is not particularly limited to a diol compound having an active hydrogen as a substituent, and is preferably, for example, a diol compound having a carboxyl group or a phenolic hydroxyl group, particularly preferably A diol compound having a carboxyl group. Among the compounds having a carboxyl group or a phenolic hydroxyl group as a substituent, a diol compound having a carbon number of 1 to 3 Å is preferable, and a diol compound having a carbon number of 2 to 20 is more preferable. Specifically, 'a diol compound having a phenolic hydroxyl group, for example, 2,6 bis(hydroxymethyl)-phenol, 2,6-bis(hydroxymethyl)-P-cresol, etc., a diol having a carboxyl group The compound may, for example, be 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dihydroxymethyl-n-butyric acid or the like. JP-A No. 2006-3〇7183, which has a functional group which can react with an epoxy group and has a structural unit represented by the formula (1), and further has a quinone bond. The 2-functional hydroxy-terminal quinone imine used in the synthesis of an amine can be represented by the following formula (3).

(wherein R and R3 each independently represent a divalent aliphatic or aromatic-47-201113312 hydrocarbon group, Υ1 represents a tetravalent organic group derived from a tetracarboxylic acid or an anhydride group thereof, and X 1 represents two A divalent organic group derived from an amine or a diisocyanate, m being an integer of 0 to 20). The bifunctional hydroxyl terminal quinone imine is obtained from a tetracarboxylic acid component and an amine component composed of a diamine compound and a monoamine compound having one hydroxyl group. In the formula (3), m is an integer of 0 to 20, preferably 〇~1 〇, more preferably 0 to 5, particularly preferably 1 to 5. When m is 20 or more, the bending resistance of the obtained insulating film may be deteriorated. Therefore, the above-described degree is preferred. A tetracarboxylic acid component of a raw material component of a bifunctional hydroxyl terminated quinone imine, for example, an aromatic tetracarboxylic acid ' or an acid dianhydride or an ester of a lower alcohol, and the obtained polyurethane polycondensate obtained The imine is preferred because it has excellent heat resistance. Specifically '2,3,3',4'-biphenyltetracarboxylic acid, 3,3,4,4,-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylate Acid, 3,3,,4,4,-diphenyl ether tetracarboxylic acid, 3,3',4,4'-diphenyl maple tetracarboxylic acid '3,3',4,4'-diphenyl Methyl ketone tetracarboxylic acid, 2,2-bis(3,4-benzenedicarboxylic acid) hexafluoropropane, pyromellitic acid, hydrazine, 4-bis(3,4-benzenedicarboxylic acid) benzene, 2, 2 - bis[4-(3,4-phenoxydicarboxylic acid)phenyl]propane, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1, An aromatic tetracarboxylic acid such as 2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid or 1,1-bis(2,3-dicarboxyphenyl)ethane; Such acid dianhydride or ester of lower alcohol, and cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3-methylcyclohexan-1,2,4, An alicyclic tetracarboxylic acid such as 5-tetradecanoic acid, or an esterified product of the same or an acid dianhydride or a lower alcohol. Among these, especially 2,3,3,,4,-biphenyltetracarboxylic acid, 3,3',4,4,-diphenyl ether tetracarboxylic acid, and 2, 2, 3, 3, The biphenyl tetraresidic acid or the acid dianhydride or the esterified product of the lower alcohol is preferably used as the polyaminomethyl-48-201113312 ethyl acrylate polyimine, which is excellent in solubility in a solvent. The tetracarboxylic acid component is preferably a diamine compound which is used as a raw material of a bifunctional hydroxy-terminal quinone which is easily reacted with a diamine, and is not particularly limited. Alicyclic and aliphatic diamines. Specifically, the aromatic diamine is, for example, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 1,4-diamino-2,5-di a diamine such as a halogenated benzene, which is a diamine such as bis(4-aminophenyl)ether, bis(3-aminophenyl)ether, bis(4-aminophenyl)anthracene or bis( 3-aminophenyl)anthracene, bis(4-aminophenyl)methane, bis(3-aminophenyl)methane, bis(4-aminophenyl) sulfide, bis(3-aminobenzene) Sulfide, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoro Diamines containing two benzene rings, 1,4-bis(4-aminophenoxy)benzene, 1,4, such as propane, hydrazine-dianisidine, hydrazine-tolidine, and toluidinesulfonic acid - bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, hydrazine, £^'-double (4-Aminophenyl)-1,4-diisopropylbenzene, hydrazine:, 〇'-bis(4-aminophenyl)-1,3-diisopropylbenzene, etc. containing 3 benzenes Ring diamines, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-dual 4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 4,4'-(4-amino group a phenoxy)biphenyl, 9,9-bis(4-aminophenyl)anthracene, 5,10-bis(4-aminophenyl)anthracene or the like containing four or more benzene rings Amine compound. The alicyclic diamine is preferably an alicyclic diamine having 1 or more aliphatic rings in the molecule and having a carbon number of 5 to 30, -49 - 201113312, for example, isophorone diamine, norbornene diamine 1,2-diaminocyclohexane '1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, and the like. The aliphatic diamine is preferably an aliphatic diamine having a carbon number of 2 to 30, for example, hexamethylenediamine or diaminododecane. Among the diamine compounds, the solubility of the bifunctional hydroxy terminal imipenem using an alicyclic diamine to the solvent is increased. Therefore, when the R18 of the above formula (43) is a (poly)carbonate polyol composed of a long-chain methylene group having a carbon number of 9 to 18, a polyurethane polyalkylene resin is obtained. The ethyl urethane polyamine is also particularly suitable because it can be easily dissolved uniformly in a solvent and has good heat resistance. The monoamine compound having one hydroxyl group in the amine component of the bifunctional hydroxyl terminated quinone imine is not particularly limited as long as it is a compound having one hydroxyl group and one amine group in the molecule, and is, for example, an aminoethanol. An aliphatic monoamine compound having a hydroxyl group such as an aminopropanol or an aminobutanol, particularly an aliphatic monoamine compound having a hydroxyl group of 1 to 10 and having a hydroxyl group; an alicyclic group having a hydroxyl group such as an aminocyclohexanol a monoamine compound, particularly an alicyclic monoamine compound having a hydroxyl group of 3 to 20, an amine hydrazine, an amino cresol, a 4-hydroxy-4'-aminodiphenyl ether, a 4-hydroxy group - An aromatic monoamine compound having a hydroxyl group such as 4'-aminobiphenyl, aminobenzyl alcohol or aminophenethyl alcohol, particularly an aromatic monoamine compound having a hydroxyl group of 6 to 20 and having a hydroxyl group. The bifunctional hydroxy-terminal quinone imine is an amine component composed of a dicarboxylic acid component and a monoamine compound having one hydroxyl group, and an acid anhydride group of the tetracarboxylic acid component (or two adjacent carboxyl groups) The equivalent number of the amine group and the amine group of the amine component are in a similar amount, and the polymerization is carried out in a solvent of -50-201113312 and a ruthenium imidization reaction. Specifically, a tetracarboxylic acid component (particularly a tetracarboxylic dianhydride) and an amine component composed of a diamine compound and a monoamine compound having a hydroxyl group, in an acid anhydride group (or a contiguous dicarboxylic acid group) and an amine The amine group of the component is used in a ratio of a slight equivalent, and each component is reacted in an organic polar solvent at a reaction temperature of about 100 ° C or less, particularly 8 CTC or less, to form an oligomer having a guanamine-acid bond, and then Adding the guanamine-acid bond oligomer (also known as valeric acid oligomer) to the hydrazine imidizing agent at a low temperature of about 0 ° C to 140 ° C, or at 1 40 ° C ~ 2 5 0 °c high temperature heating, dehydration · hydrazine imidization method derived. In the dehydration/hydrazine imidization reaction, toluene or xylene may be added, and the condensation water may be removed by azeotropy while reacting. The solvent used in the production of the bifunctional hydroxy-terminal quinone imine, for example, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, N-methyl-2.pyrrolidone驴-methyl-mercaptoamine and other guanamine solvents, dimethyl hydrazine, hexamethylphosphonamide, dimethyl maple, tetramethylene fluorene, dimethyltetramethylene hydrazine, etc. a solvent of a sulfur atom, a phenolic solvent such as cresol, phenol or xylenol; diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether, etc. a glycol solvent such as a glycol dimethyl ether solvent or a lactone solvent such as 7-butyrolactone, a ketone solvent such as isophorone, cyclohexanone or 3,3,5-trimethylcyclohexanone; Other solvents such as ethylene glycol 'dioxane and tetramethyl urea, if necessary, aromatic hydrocarbon solvents such as benzene, toluene and xylene. These organic solvents may be used alone or in combination of two or more. The bifunctional hydroxy-terminal quinone imine produced as described above may sometimes be a mixture of a plurality of bifunctional hydroxy-terminal quinone imines in which m in the above formula (3) is different. In the clock of the present invention, a mixture of difunctional 2-51-201113312 hydroxy-terminal quinone imine oligomers having different m numbers can be separated into individual polyimines, but it can also be used in a state in which it is not separated. It is used directly in the state of the mixture. The m of the bifunctional hydroxy-terminal quinone imine (the average enthalpy of m in the mixture) can be controlled by the ratio of the ratio of the diamine compound to the monoamine compound (mole ratio) in the amine component at the time of production. The reaction solution of the bifunctional hydroxy-terminal quinone imine prepared as described above can be used as a modified quinone imine oligomer solution directly or appropriately concentrated or diluted. Further, the reaction solution is poured into an insoluble solvent such as water, and is isolated in the form of a powdery product. If necessary, the powder product may be dissolved in a solvent and used. The polyurethane polyethylenimine is a (poly)carbonate having an organic residue derived from a component (a) diisocyanate and component (b) having a diol having 3 to 18 carbon atoms as described above. The polyol and the component (c') have a functional group reactive with an epoxy group, and the component (d) is obtained by reacting a bifunctional hydroxy-terminal quinone imine represented by the formula (3) as an essential component. When necessary, a polyol other than the component (b), the component (c,), and the component (d) (hereinafter, this component is referred to as a component (χ)) may be used. For example, the component (X) may have 1, 2-propanediol, 1,3-propanediol, 1,2-butanediol 'oxime, 3-butanediol, hydrazine, 4·butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, iota, 8-octanediol, hydrazine, 3_cyclohexanedimethanol, 1,4-cyclohexanedimethanol, iota, 9-decanediol, 2 _Methyl-oxime, 8-octanediol, -52- 201113312 1 , 1 0 -decanediol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol 2-butyl-2-ethylpropanediol, 1,3-cyclohexanedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, and the like. As described above, when the (poly)carbonate polyol is produced, the polyol component of the raw material may remain. However, in the present specification, the remaining polyol component is not contained in the "(poly)carbonate polyol" but includes In the ingredient (X). The composition ratio of each component of the component (a), the component (b), the component (c'), and the component (d) is the total number of hydroxyl groups/isocyanate groups of each component, and is represented by a specific component [component (b) + component ( c,) + component (d) + component (X)] / component (a) has a molar ratio of 0.5 to 3.0, preferably 0.8 to 2 _ 5 , particularly preferably 〇 9 to 2 · 0. When the amount of the component (a) is too large, the polymerization solution sometimes becomes thick, which is not preferable. Further, the molar ratio of [component (b) + component (c,) + component (X)] / component (d) is 〇. 〇 1 to 100, preferably 0.1 to 10 ratio. When the component (b) + component (c,) + component (X) is too large, the heat resistance is poor, and when the component (d) is too large, the flexibility is poor. The combination of the above component (b) and the component (c') of the raw material component in the production of the polyethylene urethane polyimide is the same as the carbon number of 3 to 18 which has a number average molecular weight of 500 to 1 0000. When the (poly)carbonate polyol (component (b)) of the organic residue derived from the alcohol is composed of the combination of the component (c,), the component (a) and the component (b) + component (c,) + The ratio of the component (X)] [component (b) + component (c') + component (X)] / component (a) is 〇·5 to 2.5, preferably 〇·8 to 2.5. Further, the molar ratio of the component (b) and the component (c') component (c') / component (b) is -53 to 201113312 0.1 to 10, preferably 0.1 to 5. [Component (b) + component (c') + component (x)] / component (a) is too small, the content of component (d) is increased, 'softness is poor, and [component (b) + component (c,) When the component (x)]/component (a) is too large, the content of the component (d) is small, and the heat resistance is poor. Therefore, the ratio of the range is preferably. In the ratio of the component (b) to the component (c,), when the ratio of the component (c ') is too large, the viscosity of the obtained polyethyl urethane solution of the polyurethane is too high, or the obtained cured film is sucked. The wetness is too big, so it is not good. On the other hand, when the ratio of the component (C ') is too small, the crosslinking density is lowered, and the heat resistance of the obtained cured film is liable to lower, which is not preferable. The component (X) is preferably used in a smaller amount than the component (b) or the component (C'), and more preferably a polyaminocarboxylic acid obtained by using only the polyol component remaining in the synthesis of the component (b). The ethyl ester polyimine is preferably composed of a structural unit containing the following formula 45) to formula (47). X—N—C—〇—^R20*OCO^-R20-〇_C—N- Ο ο (4 5) (wherein χ6 is a divalent group from which an isocyanate group is removed by a diisocyanate, and a plurality of R2G Each of which is an integer representing the number of the divalent group of the hydroxy group having a carbon number of 3 to 18, which is an integer of 1 to 4 ', and an integer of 1 to 100. -54- 201113312

X—N—C—0—W—Ο— (wherein, X6 is a divalent group from which an isocyanate group is removed by a diisocyanate, and W is a diol removed by a functional group reactive with an epoxy group. A divalent group of a hydroxyl group, and V is an integer of 1 to 4 Å.)

(wherein X6 is a divalent group in which an isocyanate group is removed by a diisocyanate, and a plurality of R21 and R22 each independently represent a divalent aliphatic or aromatic hydrocarbon group, and Υ4 means a tetravalent value of a carboxyl group from which a tetracarboxylic acid is removed. The group, X7 represents a divalent group from which the amine group of the diamine is removed, w represents an integer of 〇~2〇, and X represents an integer of 1 to 100.) Polyethyl urethane polyimide a urethane bond, a (poly)carbonate unit derived from a diol having 3 to 18 carbon atoms, a diol unit having a functional group reactive with an epoxy group, and a bifunctional hydroxy terminal quinone imide unit For the copolymerization, u, ν' and X represent the degree of polymerization and the composition ratio of the units. However, each of the foregoing units is not limited to a block copolymerizer. (Poly)carbonate units derived from a diol having a carbon number of 3 to 18, an alcohol monohydric oxime having a functional group reactive with an epoxy group, and a block copolymerizable unit of a 2-mical nonionic trans-terminally-branched imine unit Or random copolymerization. Although the terminal is not specifically shown, it is an isocyanate group or a hydroxyl group at the terminal -55-201113312 due to the terminal diisocyanate compound or the above-mentioned respective units. The method for producing the polyurethane polyethylenimine can be simultaneously dissolved in a solvent to carry out a reaction, but the bifunctional hydroxy-terminated amine unit forms a continuous molecular chain and is insoluble in a solvent to precipitate. Therefore, the diisocyanate and the (poly)carbonate polyol having an organic residue derived from carbon atoms 3 to 18 are reacted in an excessive state with isocyanic acid for the hydroxyl group, and then with 2 hydroxyl end groups. The amine reaction ensures solubility and performs better and better. DETAILED DESCRIPTION OF THE INVENTION The polyisocyanate compound of the polyurethane is prepared by using a polyisocyanate compound and a (poly)carbonate polyol having a residue derived from a diol having 3 to 18 carbon atoms or having an epoxy group. The diol reaction of the radix group can be carried out without solvent or dissolved in a solvent. The reaction temperature is 30 ° C to 150 ° C, preferably 30 ° C to 120 ° C, and the reverse is usually 1 to 1 Torr. In order to prevent the isocyanate from being deactivated by water, the reaction is preferably carried out under a nitrogen atmosphere. a diisocyanate compound obtained by reacting a diisocyanate compound with a (poly)carbonate polyol having an organic residue of a diol having 3 to 18 carbon atoms or a diol having a functional group capable of reacting with an epoxy group, an energy hydroxyl terminal The reaction of the quinone imine is preferably carried out in a solvent at a temperature of from 30 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and a reaction time of from 1 to 15 in a nitrogen atmosphere. In this reaction, the ratio of the number of hydroxyl groups at the bifunctional hydroxyl group to the number of isocyanate groups of the diisocyanate compound / the number of isocyanate groups is 0.5 to 2.5, preferably 1.5 to 2.5. The functionality of the glycol ester phase should be such that when the method is used, the reaction of the reaction should be time-divided. The reaction of the derivative reaction should be carried out at a temperature of 2 minutes, and the imine (hydroxyl.5 or less -56-201113312) The obtained polyurethane urethane resin has low heat resistance, and when it is 2 or more, it is too hard as a cured film, so the above range is preferable. The solvent to be used for the reaction of the quinone imine may be a solvent used in the synthesis of polyethyl urethane having a structural unit represented by the formula (4) to the formula (6), for example, paragraph [0191]~ In order to obtain the thermosetting composition of the present invention, the polyurethane urethane is at least 3% by mass or more, preferably 5 to 60% by mass. High concentration dissolved in solvent, the solution is 2 5 °C The viscosity of the solution (E-type rotary viscometer) is 1000 to 1000OOmPa's, particularly preferably 1000 to 600000 mPa*s. When the molecular weight of the polyurethane polyethylenimine becomes too large, the viscosity of the solution is too high, and the composition In the preparation of the material, it is difficult to stir. When the composition is too high in viscosity, workability in forming a coating film by a method such as screen printing is lowered. Therefore, the polyurethane which constitutes the resin composition of the invention The number average molecular weight of the polyimine is preferably from 3,000 to 50,000, more preferably from 4,000 to 40,000, particularly preferably from 4,000 to 30,000. When the number average molecular weight is less than 3,000, the heat resistance or mechanical properties of the obtained hardened insulating film When the component (c ') of the raw material component of the polyurethane quinone imine is used as a diol having a carboxyl group, the acid value of the polyurethane urethane is preferably 5 〜. 120 mgKOH/g, more preferably 10 to 50 mgKOH/g. When the acid value is less than 5 mgKOH/g, the reactivity with the epoxy group-containing compound having a tricyclodecane structure is reduced to -57-201113312, and the heat hardening will be described later. Sex composition The heat resistance of the protective film of the sheet may be lowered. When it exceeds 120 mgKOH/g, the protective film may become too hard and brittle. The ethyl urethane preferably has a number average molecular weight of 3,000 to 50,000 and an acid. The valence is 5 to 120 mgKOH/g, more preferably the number average molecular weight is 4,000 to 30,000, and the acid value is 10 to 50 mgKOH/g. The functional group having a reactive group with an epoxy group and having the structure represented by the formula (1) In the unit, the polyethylenimine of the polyimine bond having a quinone imine bond, the stability of the synthesized polyamidiamine urethane is emphasized, compared with the above-mentioned special opening 2003 - Polyurethane polyethylenimine having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and having a quinone bond, as described in JP-A No. 1 98 1 05, It is preferably a polyamine group having a functional group represented by the formula (1) and having a quinone imine bond, which is described in JP-A-2006-3 0 7 1 3, having a functional group which can react with an epoxy group. Ethyl formate polyimine. Particularly preferred is a polyurethane urethane obtained by reacting the following raw materials (a), (b), (c) and (d) as essential materials. Component (a) diisocyanate, component (b) (poly)carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, component (c) a diol having a carboxyl group, component (d) The bifunctional hydroxy terminal quinone imine represented by the formula (3). Next, a polyaminocarbamate having a certain branched structure in a molecule and having a functional group reactive with an epoxy group and having a structural unit represented by the formula (-58-201113312 1) in the range of a solvent will be described. ester. In the range dissolved in the solvent, the molecule has a certain function and has a functional group reactive with an epoxy group, and has a structural unit of a polyurethane to make the following component (a (b) And component (c) and component (e) are obtained by reacting. Component (a) diisocyanate, component (b) having (poly)carbonate polyol derived from a diol having 3 to 18 carbon atoms, component (c) a diol having a carboxyl group, a component (e), and a diisocyanate having a chemical component (a) having three or more hydroxyl groups in one molecule, as long as it is one molecule; or a cyanate group, for example, an aliphatic group An alicyclic diisocyanate, preferably an isocyanate group, having an aliphatic, alicyclic or aromatic diisocyanate, specifically 1,4-cyclohexane diisocyanate, isophorone diisocyanate Bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethane, 1,4-bis(isocyanatomethyl)cyclohexane, phenyl phthalocyanate, 2,6-benzene Methyl diisocyanate 'diphenylmethyl isocyanate, 1,3-phenylene diisocyanate, 1,4_ Diisocyanate, lysine diisocyanate, hexamethylene diiso-2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethyl diisocyanate, norbornane diisocyanate, etc. The component (b) has a (poly)carbonate polyol having a group derived from a diol having 3 to 18 carbon atoms. The average molecular molecule 1 branched structure: 1) represents), the component organic residue, etc. 2 different Or an aromatic 2 to 30, for example, methylene group) cyclohexylmethyl diiso- 4,4,-diphenyldimethyl cyanate, the organic residue t of the hexamethine is preferably - 59- 201113312 400~1 0000, more preferably 45 0~5000, the best is 5 00~3 000. When the number average molecular weight is less than 400, it is difficult to obtain a preferable flexibility, and when the number average molecular weight exceeds 1,000, the heat resistance or the solvent resistance is deteriorated. Therefore, the above-described degree is preferred. (Poly)carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, specifically, for example, UH-CARB, UN-CARB, UD-CARB manufactured by Ube Industries Co., Ltd. UC-CARB, DALACEL Chemical Industry Co., Ltd., PLACEL, C D-205, 2 05PL, 2 05HL ' 210, 210PL, 210HL, 220, 220PL, 220HL, kuraray polyol C-590, C- 1065N, C-1015N, C-2015N, etc. These polycarbonate polyols may be used alone or in combination of two or more. As described above, when a (poly)carbonate polyol is produced, the polyol component of the remaining raw material may be contained. However, in the present specification, the remaining polyol component is defined as not contained in the "(poly)carbonate polyol). "By. For example, when trimethylolpropane and 1,9-nonanediol and diethyl carbonate are used as a raw material, and a (poly)carbonate polyol is produced by a transesterification reaction in the presence of a catalyst, the raw material is used. When trimethylolpropane and 1,9-nonanediol are respectively 5% by mass in the (poly)carbonate polyol of the product, the remaining trimethylolpropane and 1,9-nonanediol are not contained. In the case of "(poly)carbonate polyol", when the polyol is a compound having three or more hydroxyl groups in one molecule (in this case, trimethylolpropane), the polyol belongs to the component (e). When the polyol is a compound having two hydroxyl groups in one molecule (in this case, 1,9-nonanediol), it is contained in the component (y) to be described later. a diol having a carboxyl group as component (c), for example, 2,2-dimethylol-60-201113312 propionic acid, 2,2-dihydroxymethylbutyric acid, hydrazine, hydrazine bis(hydroxyethyl)gan Amine acid, hydrazine, hydrazine-bis(hydroxyethyl)glycine, and the like. Among these, from the viewpoint of solubility in a solvent, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferred. These polyols having a carboxyl group may be used singly or in combination of two or more. The compound having three or more hydroxyl groups in one molecule of the component (e) is, for example, glycerin, trimethylolethane, trimethylolpropane, tris(2-hydroxyethyl)trimeric isocyanate, pentaerythritol or dipentaerythritol. , sorbitol, etc. Among these, in view of easiness in the synthesis, trimethylolethane, trimethylolpropane, and tris(2-hydroxyethyl)trimeric isocyanate are particularly preferred. When the (poly)carbonate polyol is produced as described above, the polyol component may remain in the raw material. However, when the remaining polyol component is a compound having three or more radicals in one molecule, it is included in the component ( e) inside. When necessary, 'except for the component (b), the component (c), and the component (e), the diol component which does not contain any of the component (b), the component (c), and the component (e) may be used (hereinafter referred to as Ingredient (y)). The component (y) is, for example, 1,2-propylene glycol, 1,3-propanediol, 1,2-dibutyl phthalate, 1,3 -butanediol, hydrazine, 4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, 3-methyl-1,5-pentanediol, hydrazine, 8-octanediol, hydrazine, 3-cyclohexanedimethanol, ^4-cyclohexanedimethanol, 1,9 -decanediol, 2-methyl-1,8-octanediol, llO-nonanediol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, 2·butyl-2-ethylpropanediol, 13-cyclohexanedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, and the like. -61 - 201113312 As described above, when a (poly)carbonate polyol is produced, the polyol component of the remaining raw material may be contained, but the remaining polyol component is a compound having two hydroxyl groups in one molecule (ie, a diol). It is contained in the component (y) mentioned later. The component of the thermosetting composition of the present invention having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) is used as the component (a) and the component ( b) When the component (c) and the component (e) are ethyl urethane obtained by reacting a necessary raw material component, the method for producing the polyurethane is, for example, produced by the following method. In the presence or absence of a known urethane such as dibutyltin dilaurate in the presence or absence of an esterification catalyst, a solvent is used to provide component (a), component (b), component (c) and component (e). It is synthesized by reacting a necessary raw material component (component [y) if necessary). When the reaction is carried out in the absence of a catalyst, the physical properties of the protective film of the wiring board of the present invention (hereinafter) will be improved, which is preferable. Although the order of the input of these raw materials is not particularly limited, it is usually the first component (M, component (c), component (e) and, if necessary, component (y), i is dissolved in the solvent after '20 to 1 4 〇 ° C, preferably at 60 ° to 120 ° C, while adding the added component (a), thereafter at 50 to 160, preferably at 6 ° ° C ~ l5 ° ° C The reaction is carried out. The molar ratio of the raw material to the molar ratio of the component (a), the component (b), the component (c) and the component (e) is a necessary raw material component, and the molecular weight and acid of the polyurethane. The molecular weight of the polyurethane can also be adjusted by using a monohydroxylated -62-201113312 compound. In other words, the number average molecular weight (or close to the objective number average molecule, the terminal isocyanate group) The chain is blocked by adding a monohydroxy compound for the purpose of suppressing the number average molecular weight. When the monohydroxy compound is used, even if the number of the polyisocyanate compound acid vine groups is less than or the same or more than the component (b), the component (c (e) ) and the total number of hydroxyl groups of the component (y), there is no problem. When a monohydroxy compound is used, the result of the formation of the unreacted compound remains, but in this case, the excess monohydric acid is directly used as a part of the solvent, or may be removed by distillation or the like. The monohydroxy compound is introduced into the component (a) ), the component (b (c) and the component (e) are reacted as essential raw material components, and the molecular weight of the ethyl urethane is inhibited in the ethyl urethane, that is, the reaction is stopped. The hydroxy compound is introduced into the ethyl urethane, and the monohydroxy compound can be added dropwise to the solution at 230 to 150 at 70 to 140 ° C, and then should be completed at the same temperature. The amount of use is preferably the mass% of the whole raw material component, more preferably 0.2 to 2.0% by mass, most preferably 〇.3 to 15. When it is less than 0.1% by mass, there is sometimes no effect of addition, so it is not good' When the amount is more than 5.0% by mass, the molecular weight adjustment during the synthesis may be poor. As described above, the reaction is carried out by reacting the component (a), the component (b), the component < component (e) as essential raw materials. Polyamine, when the amount is reached) The cyanide and the monohydroxyl compound) are preferably increased in polyamine, so that the reverse concentration is 0.1 to 5.0% by mass. In addition, it is difficult, so: the number average molecular weight of the ethyl ester of hydrazine and carboxylic acid-63-201113312 Preferably, it is from 100 〇 to 1,000,000, more preferably from 3 000 to 50,000 00', and particularly preferably from 5,000 to 30,000. The "number average molecular weight" described in the present specification is a gel permeation chromatography (hereinafter referred to as GPC). The number average molecular weight measured in terms of polystyrene. When the number average molecular weight is less than 1,000, the elongation, flexibility, and strength of the cured film may be impaired. When it exceeds 1 〇〇, the solvent is dissolved. Sex will decrease, and even if dissolved, the viscosity will become higher and it will be limited in use. In the present specification, unless otherwise specified, the measurement conditions of GPC are as follows. Device name: HPLC unit of Japan Spectrophotometer (HS) HSS-2000 Column: Shodex column LF-804 (3 in-line) Mobile phase: Tetrahydrofuran Flow rate: 1.0mL/min

Detector: RI-2031Plus manufactured by Japan Spectrophotometer Temperature: 4 0.0 °C Sample amount: sample loop lOOyL Sample concentration: prepared to about 0.1% by mass The acid value of the polyurethane is preferably 5 to 120 mgKOH/g. More preferably, it is 10 to 50 mgKOH/g. When the acid value is less than 5 mgKOH/g, the reactivity with the epoxy group-containing compound having a tricyclodecane structure is lowered, and the heat resistance of the protective film of the wiring board obtained by curing the protective film thermosetting composition may be reduce. When it exceeds 120 mgKOH/g, the protective film may become hard and brittle -64-201113312. The average molecular weight of the polyurethane has a coefficient of 1000 to 100,000, and the acid value is 5 to 12 mgKOH/g, which has a hardening reaction. The functional group and the carbonate-bonded ethyl urethane are preferably more preferably a number average molecular weight of from 3,000 to 50,000 and an acid value of from 10 to 50 mgKOH/g. In the present specification, the acid value of the polyurethane is a valence of the acid value measured by a potentiometric titration method of n s κ ο 〇 7 〇. The solvent to be used for the reaction for producing the ethyl urethane can be, for example, a solvent used in the synthesis of polyethyl urethane having a structural unit represented by the formula (4) to the formula (6), for example, The solvent described in paragraphs [0 1 9 1 ] to [0 1 9 7 ]. Next, a polyurethane having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and further containing an organic residue derived from a dimer diol will be described. In the present specification, 'dimer diol' means that the dimer acid and/or its lower alcohol ester are reduced in the presence of a catalyst, and the residual acid portion of the dimer acid is used as the carbon number of the alcohol 36 Alcohol is the main component. In the case where the main component is contained in an amount of 50% by mass or more, a diol having a carbon number of 22 to 44' and not a carbon number of 36 may be contained in addition to the diol having a carbon number of 36. The dimer diol' in the present specification is particularly preferably a hydrogenated dimer diol derived from a carbon-carbon double bond of a dimer acid. The commercially available product of the dimer diol is, for example, PRIPOL (registered trademark) 203 3 (manufactured by Croda Corporation) or Sovermol (registered trademark) 908 (manufactured by Cognis Co., Ltd.). PRIp〇L (registered trademark) 2〇33 is a mixture of compounds represented by the following formulas (48) and (49) as a main component. "Dimer acid" refers to an acid obtained by intermolecular 2-merization of an unsaturated fat-65-201113312 acid, and an unsaturated fatty acid having a carbon number of 1 to 22 is subjected to 2-polymerization to form a carbon number of 36 The dibasic acid obtained from the polymer is a main component. Commercially available products include PRIPOL (registered trademark) 1 006, the same 1009, the same 1015, the same 1025, etc. (made by Croda), EMPOL (registered trademark) 1062 (Co gn is company). R10

)(CH2)-〇H \(CH4_OH (4 8) (wherein R10 and R11 are both alkyl 'P and q are integers above 〇' and the carbon numbers and r and q contained in r1q and R11 The total is 3〇.) R12-CH—(CH2)r-〇H (49)

R13—CH—(CH2)s-〇H (wherein R12 and R13 are all alkyl groups, r and s are integers of 0 or more′, and the total number of carbons contained in R12 and R13 and the sum of •· and s are 34. Further, the "organic residue derived from a dimer diol" in the present invention means a structure in which hydrogen of at least one alcoholic hydroxyl group of the dimer diol is removed. In the present invention, "the organic residue J derived from a carbon number of 3 to 18 alcohols means a structure in which at least one alcoholic hydrogen group having a carbon number of 3 to 18 is removed. The functional group of the oxy group, and having the structural unit represented by the formula (1), and further containing the organic residue derived from the dimer diol, can be made, for example, by the following components (a) ), component (b), component (c), and component (1) are synthesized by reacting a necessary raw material component (required component -66-201113312 (Z)). Component (a) diisocyanate, component C b ) has a (poly)carbonate polyol having an organic residue derived from a diol having a carbon number of 3η 8 , a diol having a carboxyl group as a component (c), and a dimer diol component (Z) of the component (1) being selected from the group consisting of b) 'Component (C) and the polyol component other than the polyol of the component (1) (a) The diisocyanate may be any one as long as it has two isochlorite groups in one molecule. For example, there is an aliphatic group. An alicyclic or aromatic diisocyanate is preferably an aliphatic or alicyclic group having an isocyanate group of 2 to 3 Å. Aromatic diisocyanates, specifically, for example, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3 -bis (isocyanate) Methyl)cyclohexane, 1, bis(isocyanatomethyl)cyclohexane, 2,4-benzylidene diisocyanate, 2,6-benzylidene diisocyanate, diphenylmethane _4,4,_Diisocyanate, 1,3 - benzoyl diisocyanate, ;, 4 benzoyl diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 2, 4 , 4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexane methylene diisocyanate, norbornane diisocyanate, etc. Component (b) has a carbon number of 3 to 18 The average molecular weight of the (poly)carbonate polyol coefficient of the organic residue derived from the diol is preferably from 400 to 10,000', more preferably from 450 to 5,000, most preferably from 500 to 3,000. When the number average molecular weight is less than 4 〇〇 It is difficult to obtain better softness, and when the average molecular weight exceeds 10,000, the heat resistance or solvent resistance is deteriorated. Therefore, the foregoing process The (poly)carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, specifically, for example, UH-CARB and UN-CARB manufactured by Ube Industries Co., Ltd. , UD-CARB, UC-CARB, DALACL Chemical Industry Co., Ltd., PLACEL, C D-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL, kuraray polyol C-590 manufactured by the company kuraray , C-1065N, C-1015N, C-2015N, etc. These polycarbonate polyols may be used alone or in combination of two or more. As described above, when a (poly)carbonate polyol is produced, the polyol component of the remaining raw material may be contained. However, in the present specification, the remaining polyol component is defined as not contained in the "(poly)carbonate polyol). "By. For example, when 1,9-nonanediol and diethyl carbonate are used as raw materials, in the presence of a catalyst, when a (poly)carbonate polyol is produced by a transesterification reaction, the raw material is 1,9-壬. When the diol remains in 5% by mass of the (poly)carbonate polyol of the product, the remaining 1,9-nonanediol is not contained in the "(poly)carbonate polyol", and is included in the later description. Within the composition (z). a diol having a carboxyl group as the component (c), for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N,N-bis(hydroxyethyl)glycine, N , N-bis(hydroxyethyl)glycine, and the like. Among these, from the viewpoint of solubility in a solvent, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferred. These polyols having a carboxyl group may be used singly or in combination of two or more. The "dimer diol" of the component (1) means that the dimer-68-201113312 acid and/or its lower alcohol ester is reduced in the presence of a catalyst as described above, and the carboxylic acid moiety of the dimer acid The diol having 3 to 6 carbon atoms of the alcohol is mainly composed. Here, the main component is a case where the content is 50% by mass or more, and the carbon number is 22 to 44 instead of the diol having a carbon number of 36, in addition to the carbon number of 36 diol. The dimer diol in the present specification is particularly preferably a hydrogenated dimer diol derived from a carbon-carbon double bond of a dimer acid. Commercial products of dimer diols, for example, PRIPOL 203 3 (made by Croda) or Sovermol 90 8 (

Cognis company). Except for component (a), component (b), component (c), and component (1), it is not included in component (a), component (b), component (c), and component (1). Any diol component (ingredient (z)). The component (z) is, for example, iota, 2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol' 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydrazine , 9-decanediol, 2-methyl-1,8-octanediol, 1,10-nonanediol' 1,2-tetradecanediol, 2,4-diethyl-l,5- Pentandiol, 2-butyl-2-ethylpropanediol, iota, 3-cyclohexyl dimethanol, iota, 3-benzenedimethanol, 1,4-benzenedimethanol, and the like. When a (poly)carbonate polyol is produced, the polyol component of the remaining raw material may be contained. However, the remaining polyol component is not contained in the component (b) but contains the component (ζ). The polyurethane having a functional group which can react with an epoxy group and having a structural unit represented by the formula (1), which is a component of the thermosetting composition of the present invention, has a function capable of reacting with an epoxy group. And a method for producing the polyurethane, such as a structural unit represented by the formula (-69 - 201113312 η, and further containing an organic residue derived from a dimer diol) It can be produced by the following method. In the presence or absence of a known carboxylic acid such as dibutyltin dilaurate in the presence or absence of an esterification catalyst, a solvent is used to make the component (a), the component (b), and the component. (c) and component (1) are synthesized by reacting a necessary raw material component (component (z) if necessary). When the reaction is carried out without a catalyst, the wiring board of the present invention (II) will be finally improved. The order of the raw materials to be used is not particularly limited, and the components (b), (c), (1) and, if necessary, components (z) are usually added first. ), after dissolving in the solvent, at 20 to 140 ° C, preferably The component (a) is added dropwise at 60 to 120 ° C, and then reacted at 50 to 160 ° C, preferably at 60 ° C to 150 ° C. The raw material is introduced into the molar ratio system. The component (a), the component (b), the component (c), and the component (1) are adjusted to have a molecular weight and an acid value of the ethyl urethane obtained by reacting the essential raw material component. By using a monohydroxy compound, The molecular weight of the polyurethane can be adjusted. In other words, when the desired number average molecular weight is reached (or near the intended number average molecular weight), the terminal isocyanate group is blocked to suppress the increase in the number average molecular weight. When a monohydroxy compound is added, even if the number of isocyanate groups of the component (a) is less than or equal to or more than the total of the components (b), (c), (1) and (z) There is no problem with the number of hydroxyl groups. -70- 201113312 In addition, when the monohydroxy compound is used excessively, the unreacted monohydroxy compound remains as a result, but at this time, the excess monohydroxy compound is directly used as a part of the solvent. Alternatively, it may be removed by distillation, etc. The monohydroxy compound is introduced into the ethyl urethane obtained by reacting the component (a), the component (b), the component (c), and the component (1) as essential raw materials. In the middle of suppressing the increase in the molecular weight of the polyurethane (ie, stopping the reaction), in order to introduce the monohydroxy compound into the polyurethane, the monohydroxy compound can be at 230 to 150 ° C. Preferably, it is dropped into the solution at 70 to 140 ° C, and then maintained at the same temperature to complete the reaction. Further, the component (1) is used in an amount relative to the component (b) and the component ( The total amount of the component (1) and the component (z) is 5 to 50% by mass, more preferably 10 to 45% by mass, most preferably 15 to 40% by mass. When it is less than 5% by mass, 'there is no effect at all, so it is not good. Further, when the amount is more than 50% by mass, the adhesion to the polyimide substrate of the protective film to be described later may be lowered, which is not preferable. As described above, the number average molecular weight of the polyurethane obtained by reacting the component (a), the component (b), the component (c), and the component (1) as essential components is preferably 1 Torr. 〇〇~1 00000, more preferably 3000~50000' Tejia is 5000~30000. When the number average molecular weight is less than 1, the elongation, flexibility, and strength of the cured film may be impaired when it is ,, and when it is more than 1 〇〇, when it is 0 〇 0, the solubility in the solvent is lowered 'and even dissolved The viscosity is also high, and is limited in use - 71 - 201113312 The acid value of the polyurethane is preferably 5 to 120 mgKOH/g, more preferably 10 to 50 mgKOH/g. When the acid value is less than 5 mg K0H/g, the reactivity with the epoxy group-containing compound having a tricyclodecane structure is lowered, and the heat resistance of the protective film of the wiring board obtained by curing the protective film thermosetting composition is lowered. On the other hand, when it exceeds 120 mgKOH/g, the protective film may become too hard and brittle. The average molecular weight of the polyurethane has a coefficient of 1000 to 100,000 ' and an acid value of 5 to 120 mgKOH/g, and has a functional group for hardening reaction and The carbonate-bonded ethyl urethane is preferably more preferably a number average molecular weight '3000 to 50,000, and an acid value of 10 to 50 mgKOH/g. The solvent to be used for the reaction for producing the ethyl urethane can be, for example, a solvent used in the synthesis of polyethyl urethane having a structural unit represented by the formula (4) to the formula (6), for example, The solvent described in paragraphs [0191] to [0197]. The solvent which is an essential component of the thermosetting composition of the present invention (I) is a compound of the above-mentioned polyurethane having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1). The solvent is directly used as a solvent for the thermosetting composition of the invention (I), and is more economical. Further, in order to adjust the viscosity, a solvent may be further added. The concentration of the solvent in the thermosetting composition of the invention (I) is preferably from 10 to 90% by mass, more preferably from 20 to 70% by mass. The thermosetting composition of the invention (I) may further contain a curing accelerator, and is preferably. The hardening accelerator is not particularly limited as long as it is a compound which can promote the reaction of an epoxy group and a carboxyl group, and examples thereof include melamine, acetamidine-72-201113312 decylamine, benzoguanamine, and 2,4-diamino-6. -Methyl propylene oxiranylethyl- s-trisyl, 2,4-methylpropanoid oxiranyloxyethyl-s-trisyl, 2,4.diamino-6-vinyl-s-three Triazine-based compound such as azine, 2,4-diamino-6-vinyl-S-triazine, trimeric isocyanate adduct, imidazole, 2-methylimidazole, 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyano Ethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl -2-methylimidazole, 1-(cyanoethylaminoethyl)-2-methylimidazole, N-[2-(2-methyl-1-imidazolyl)ethyl]urea, 1-cyanoethyl Base-2-undecylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazole guntrienolate, 1-cyanoethyl 2-ethyl-4-methylimidazolium iron trimellitate, 1 -Cyanoethyl-2-undecylimidazole key trimellitate, 2,4-diamino _6_[ 2' -methylimidazolyl-(丨')]-ethyl-s-three exposure , 2,4-amino--6-[ 2'- eleven-indolyl-mercapto-(1')]-ethyl-s-triterpene, 2,4-diamino-6-[ 2 '-Ethyl-4'-methylimidyl-(1')]-ethyl-s-trisyl, 1-t-cavity-2-methyl-3-pyridyl iron chloride, Ν,Ν'-bis(2-methyl-1-amidinoethyl) urea, hydrazine, Ν'-bis(2-methyl-1-imidazolylethyl) adipate diamine, 2_ Phenyl 4-methyl-5-hydroxymethylimidazole, 2-phenyl-4_5-dihydroxymethylimidazole, 2-methylimidazole·trimeric isocyanate adduct, 2-phenylimidazole. Polyisocyanate adduct, 2,4-diamino-6-[ 2'-methylimidazo-(1')]-ethyl-s-triazine. Trimeric isocyanate addition , 2_Methyl-4_methylpyridinium, 2-ethyl-4-methyl-5-methylpyridyl imidazole, 2-phenyl-4-methylcarbamimidazole, 1-phenyl 2-Benzyl imidazole, 〗 〖2-dimethylimidazole, 〗 〖-(2-Bisyl-73-201113312-based) imidazole 'vinylimidazole, 1-methylimidazole, hydrazine-allylimidin 2-ethylimidazolium, 2-butylimidate '2-butyl-5-carbamic acid, 2,3-dihydro-1H-pyrrolo[l,2-a]benzimidazole, Benzyl-2-phenylimidazolium bromide ' 1-dodecyl-2-methyl-3-benzylimidazolium chloride, etc., a quinone compound, 1,5-diazabicyclo (4.3. 〇) Derivation of ruthenium compounds such as ruthenium _5 and its salts, 1,8-diazabicyclo (5.4.0) undecene-7 and its salts, such as diazabicycloalkenes and cyclic oxime compounds a tertiary amino group-containing compound such as triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol, etc., triphenylphosphine , diphenyl (P. tolyl) phosphine, cis (alkylphenyl) phosphine, ginseng (alkoxyphenyl) phosphine, ginseng (alkyl. alkoxyphenyl) phosphine, ginseng (dialkyl benzene) Phosphine, ginseng (trialkylphenyl)phosphine, cis (tetraalkylphenyl)phosphine, cis (dialkoxyphenyl)phosphine, cis (trialkoxyphenyl)phosphine, ginseng Organic scaly compounds such as oxyphenyl)phosphine, trialkylphosphine, dialkyl arylphosphine, alkyldiarylphosphine, dicyanodiazepine, etc. . These hardening accelerators may be used singly or in combination of two or more types. Among these hardening accelerators, when it is considered to have both a hardening promoting action and electrical insulating properties, it is preferably a melamine, an imidazole compound, a cyclic ruthenium compound, a cyclic ruthenium compound derivative, a phosphine compound, and an amine compound, and more preferably It is melamine, 1,5-diazabicyclo(no)nonene-5 and its salt, 1,8-diazabicyclo(5.4.0)-{--carbene-7 and its salts. The amount of the hardening accelerator to be added is not particularly limited as long as it can achieve a hardening promoting effect. However, from the viewpoint of the hardenability of the thermosetting composition of the invention (I) and the electrical insulating property or water resistance of the film obtained by curing the thermosetting composition of the invention (I), The thermosetting composition of the invention (I) having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and having a tricyclodecane structure The total amount of the epoxy group-containing compound is 1 〇 0 parts by mass, preferably in the range of 5 parts by mass to 5 parts by mass, more preferably 〇·ΐ to 3.0 parts by mass. When the amount is less than 0.05 parts by mass, hardening is difficult in a short time, and when it exceeds 5 parts by mass, the electrical insulating properties or water resistance of the cured product obtained by curing the composition may be deteriorated. In the thermosetting composition of the invention (I), inorganic fine particles and/or organic fine particles may be added in order to adjust the fluidity, and it is preferably added. In the present specification, the term "inorganic fine particles and/or organic fine particles" is defined not only as inorganic fine particles but also as organic fine particles, and is also defined as an organic compound which is physically coated with an organic compound in a powdery inorganic compound or chemically surface-treated with an organic compound. The inorganic composite is a microparticle. The inorganic fine particles and/or the organic fine particles to be used in the thermosetting composition of the present invention (I) are an epoxy group-containing epoxy group having a tricyclodecane structure dispersed in an essential component of the invention (I). In the composition of the compound, the polyurethane having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and a solvent, the slurry is not particularly limited. Examples of the inorganic fine particles include cerium oxide (Si 02 ), aluminum oxide (Al 2 〇 3 ), titanium oxide (Ti 〇 2 ), oxidized giant (Ta 205 ), zirconia (ZrO 2 ), tantalum nitride (Si 3 N 4 ), and barium titanate. (BaO. Ti02), barium carbonate (BaC03), lead titanate (PbO · Ti02), lead titanate (PZT) -75- 201113312, lead zirconate titanate (PLZT), gallium oxide (Ga203), spinel Stone (Mg0, Al203), Moldite (3Al203.2Si〇2), Cordierite (2MgO • 2Al203, 5Si02), Talc (3Mg0.4Si02.H20), Aluminum Titanate (Ti02-Al203), Containing Trioxide Oxidation error (Y2〇3_Zr〇2), barium strontium silicate (BaO. 8Si02), boron nitride (BN), calcium carbonate (CaC03), calcium sulfate (CaS04), zinc oxide (ZnO), magnesium titanate ( MgO·Ti02), barium sulfate (BaS04), organic bentonite, carbon (C), etc., may be used alone or in combination of two or more. The organic fine particles are preferably fine particles of a heat resistant resin having a guanamine bond, an oxime bond, an ester bond or an ether bond. These resins are preferably a polyimide resin or a precursor thereof, a polyamide amidoximine resin or a precursor thereof, or a polyamide resin from the viewpoint of heat resistance and mechanical properties. The average particle diameter of these inorganic fine particles and/or organic fine particles is preferably 0.01 to 1 〇em, more preferably 0·1 to 5//m. In addition, the amount of the inorganic fine particles and/or the organic fine particles is from 1 to 150 parts by mass based on 100 parts by mass of the total of the carboxyl group-containing polyurethane, the solvent and the curing agent contained in the curable resin composition. It is preferably 1 to 120 parts by mass, more preferably 1 to 60 parts by mass. The thermosetting composition for a protective film of a wiring board of the invention (I) can be used as a thermosetting property of a protective film for a wiring board for patterning Chip On Film (hereinafter referred to as COF) by a screen printing method. The "COF" described in the present specification refers to an assembly method in which a bare wafer is mounted on a flexible wiring board and connected. -76-201113312 When the thermosetting composition of the present invention (I) is used as a thermosetting composition for a protective film of a wiring board for patterning C Ο F by a screen printing method, in order to make printing The foam disappears or is inhibited, and an antifoaming agent can be used, and it is preferably used. When the thermosetting composition of the present invention (I) is printed as described above, the antifoaming agent has a function of eliminating or suppressing the generated bubbles, that is, it is not particularly limited. Specific examples of the antifoaming agent used in the thermosetting composition of the invention (I) include, for example, BYK-07 7 (manufactured by BYK-Chemie Japan Co., Ltd.), SN defoamer 470 (manufactured by Sannopco Co., Ltd.), and TSA75 0S (Momentive Performance). Polycarbonate defoamer such as sand oil SH-203 (manufactured by Dow Corning Co., Ltd.), Dappo SN-348 (manufactured by Sannopco Co., Ltd.), Dappo SN-354 (manufactured by Sannopeo Co., Ltd.), D appo SN - 3 6 8 (S a η η opco company),

Acrylic acid-based defoamer such as Disparlon 2 3 0HF (manufactured by Nakamoto Chemical Co., Ltd.), acetylene glycol such as Surfynol DF-1 10D (made by Nisshin Chemical Industry Co., Ltd.), Surfynol DF-37 (made by Nissin Chemical Industry Co., Ltd.) A defoaming agent, a fluorine-containing polyfluorinated defoaming agent such as FA-630, or the like. In the thermosetting composition of the invention (I), a surfactant such as a flat agent may be added if necessary, such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, carbon black, naphthalene. A well-known coloring agent such as black. Further, when it is necessary to suppress the deterioration of the acid value of the resin and the discoloration during heating, an antioxidant such as a phenol-based antioxidant, a phosphite-based antioxidant or a thioether-based antioxidant may be added, and it is preferably added. -77- 201113312

-78- 201113312

(5 3)

(5 4)

(5 5)

CH, CH, COOCH, CH, OCH: (5 6) -79- 201113312

(5 8)

(5 9)

OH

(6 0) The phosphite-based antioxidant is, for example, a compound of the following formula (6 1 ) to formula (7 1 ). -80- 201113312

OP one 3

OP 3

(6 1) (6 2) (6 3) (6 4) (6 5) -81 - 201113312

(6 7)

(6 8) CH, CH,

-82- 201113312

(7 0)

V~V /°'R \ /〇-P, (7 1) ,V=/ O-R

R-O /~v CH R-〇 ch R : alkyl group of c12 to c1s The thioether-based antioxidant is, for example, a compound of the following formula (72) to formula (77).

R : the base of c12~cis

H27C^0C0CH2CH^S-CH2CH2C00-CuH27 ( 7 4 ) -83- 201113312 H29Ci7OCOCH2CH2-s-CH2CH2CO〇-C14H29 (7 5) H^C^OCOCHjCHj-S-CHjCH^OO-C,^ (7 6) H37C1- 50C0CH2CHfS-CH2CH2C00-CieH37 (7 7) Add a flame retardant or a slip agent if necessary. The thermosetting composition of the invention (I) can be obtained by uniformly kneading and mixing one or all of the compounding components in a roll mill, a bead mill or the like. When mixing one part of the ingredients, the remaining ingredients can be remixed in actual use. When the thermosetting composition of the present invention (I) is used as a thermosetting composition for a protective film for forming a patterned wiring board for a COF using a screen printing method, the present invention is used for the thermosetting property of the present invention. The composition has good printability, and preferably has a certain range of thixotropy index. The "thixotropy index" described in the present specification is defined as the use of a conical plate type viscometer (manufactured by Brookfield Co., Ltd.; DV-11 + Pro spindle) Model; CPE-52) The ratio of the viscosity at a rotation speed of 1 rpm at 25 ° C to the viscosity at 10 ° C at 10 ° C. The thermosetting composition of the present invention (I) was used. In the case of using a thermosetting composition for a protective film for a wiring board for patterning COF by a screen printing method, the thermosetting composition of the invention (I) is excellent in printability, and the composition is at 25 °. The thixotropy index of C is preferably in the range of 1.1 to 3.0, more preferably in the range of 1.1 to 2.5. When the composition of the thermosetting-84-201113312 of the present invention (I) is used as a solder resist ink composition, Thixotropy index of thermosetting composition at 25 ° C When it is less than 1.1, after the thermosetting composition is printed, the composition may flow, and the film thickness may not be constant, or the printing pattern may not be maintained. Further, the thermosetting composition is at 25 ° C. When the thixotropy index is more than 3.0, the defoaming property of the coating film of the composition may be deteriorated, and the protective film of the wiring board of the invention (II) will be described next. The present invention (Π) is the invention ( I. The protective film of the wiring board which is cured by the thermosetting composition of the wiring board of the present invention. The protective film of the wiring board of the invention (II) is generally the wiring board of the invention (I). After the protective film is partially or completely removed by a solvent in the thermosetting composition, the curing reaction is carried out by heating to obtain a cured product. For example, when the protective film of the wiring board of the invention (II) is obtained, the following is obtained. The protective film is obtained in the first step to the third step. First step: a step of printing the thermosetting composition of the invention (I) to obtain a coating film. Second step: the coating film obtained in the first step is at 20° C ~loot the atmosphere, allowing the solvent to evaporate, a step of coating a portion or a whole amount of solvent to be removed. Third step: the coating film obtained in the second step is thermally hardened in an atmosphere of loot~250t to obtain a thermally hardened coating film ( The step of hardening the coating film. The first step is a step of printing the thermosetting composition of the invention (I) to obtain a coating film, but the thermosetting composition of the invention (I) is printed at -85-201113312 The method is not particularly limited. For example, a coating film can be obtained by a screen printing method, a roll coating method, a spray method, a curtain coating method, or the like, but it is preferably a screen printing method. The coating film obtained in the first step is at 20 ° C ~ 1 0 0. The solvent is evaporated in an atmosphere of (: to obtain a coating film for removing a part or a whole amount of the solvent. The time for removing the solvent is preferably 4 hours or less, preferably 2 hours or less. Further, the third step is a second step The coating film obtained in the step is thermally hardened in an atmosphere of 100 ° C to 25 ° C to obtain a step of thermally hardening the coating film (ie, hard coating film). The heat hardening time is preferably from 20 minutes to 4 hours. The range is more preferably in the range of 30 minutes to 2 hours. Finally, a method of manufacturing the flexible wiring board of the invention (III) and the flexible wiring board coated with the protective film of the invention (IV) will be described. III) A part or all of the surface on which the wiring of the flexible wiring board formed by forming the wiring on the flexible substrate is covered by the protective film of the wiring board of the present invention (II) In the present invention, the thermosetting composition for the protective film of the wiring board of the invention (I) is printed on the wiring pattern portion of the flexible wiring board by the tin plating treatment. A printing film is formed on the pattern, and the printing film is 80 to 13 A method for producing a flexible wiring board which is coated with a protective film and which is characterized in that a protective film is formed by heat-hardening at 0 ° C. The thermosetting composition of the invention (I) is, for example, a wiring of a flexible wiring board for coating a COF. The whole or a part of the method can be used as a protective film for the coil of -86-201113312 for C 0 F. The specific steps of the manufacturing method of the invention (IV) will be described below. For example, the following steps A to c can be formed. Protective film for flexible wiring board 〇Step A: The step of obtaining a coating film by screen-printing the thermosetting composition of the present invention (S) on a wiring pattern portion of a flexible wiring board which has been subjected to tin plating treatment Step B: The coating film obtained in the step A is subjected to evaporation under a 2 〇~1 〇〇 atmosphere to obtain a coating film in which a part or a whole amount of the solvent is removed. Step C: Coating the step B The film is subjected to a step of obtaining a protective film of the thermosetting flexible wiring board by heat-hardening in an atmosphere of 80 to 130. The temperature at which the solvent of the step B is evaporated is taken into consideration of the evaporation rate of the solvent and can be quickly moved to the lower portion. Step 2 (step C) 0 to 1 0 0 ° C, preferably 60 to 10 ° C. More preferably 70 to 90 ° C. The time for evaporating the solvent of the step B is not particularly limited 'preferably 10 to 120 minutes, more Preferably, it is 20 to 100 minutes, and the operation of the above step B is performed as necessary, and the operation of step a is followed by the operation of step C, and the hardening reaction and the solvent removal can be simultaneously performed. The conditions are preferably from 9 to 13 ° C, preferably from 9 to 13 ° C, from the viewpoint of preventing diffusion of the plating layer and obtaining better warpage and flexibility as a protective film. The time of the thermal hardening performed in the step C is not particularly limited, and is preferably from 20 to 150 minutes, more preferably from 30 to 120 minutes. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples. <Measurement of Acid Value> The functional group having the reactive group reactive with the epoxy group of the essential component of the invention (I), and the polyurethane having the structural unit represented by the formula (1) has as a ring When the carboxyl group of the functional group of the oxy group is reacted, the acid value is measured by the following method. The solvent in the above-mentioned carboxyl group-containing polyurethane solution was distilled under reduced pressure to obtain a polyurethane having a carboxyl group. The acid value was determined by potentiometric titration according to JIS K0070 using a polyurethane having this carboxyl group. The apparatus used for the potentiometric titration method is as follows. Device name: Kyoto Electric Industrial Co., Ltd. Potentiometric difference automatic titrator AT-510 Electrode: Composite glass electrode made by Kyoto Electronics Industry Co., Ltd. 73ι 73 <Measurement of hydroxyl value> Based on Π S Κ 0 0 7 0 Neutralization titration The hydroxyl value was measured. -88-201113312 <Measurement of number average molecular weight of ethyl urethane> The measurement conditions of GPC in the polystyrene conversion measured by GPC are as follows. Device name: HPLC unit manufactured by Japan Spectrophotometer HSS-2000 Column: S h 〇 d e X column L F - 8 0 4 with 3 links (in-line) Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL/min

Detector: RI-2 03 1 PluS manufactured by JASCO Corporation. Temperature: 4 0.0 °C Sample amount · Sample loop 100 μ 1 Sample concentration: Prepared to about 0.1% by mass < Polyurethane solution Measurement of Viscosity> The viscosity of a carboxyl group-containing polyurethane solution was measured by the following method. Using a carboxyl group-containing polyurethane solution of about 0.8 g, using a conical plate type viscometer (Brookfield type; DV-11 + Pro spindle model; CPE-52) at a temperature of 25.01 and a number of revolutions of 5 rpm. The viscosity after the passage from the start of the measurement to 7 minutes was measured. <Measurement of Thixotropy Index> The thixotropic index of the thermosetting composition was measured by the following method. Using a thermosetting composition of about 0.6 g, the thixotropy index is a conical plate type viscometer (Brookfield type; DV-11 + Pro spindle -89 - 201113312 model; CPE - 5 2 ) at a temperature of 2 5 · 0 The viscosity after the passage from the start of the measurement to 7 minutes was measured under the conditions of ° C and a number of revolutions of 〇 rpm. Thereafter, the viscosity after the passage from the start of the measurement to 7 minutes was measured under the conditions of a temperature of 2 5.0 ° C and a number of revolutions of 1 rpm. The thixotropy index is calculated as follows. Method for obtaining the thixotropic index: Thixotropy index = [viscosity of lrpm] - [viscosity of l rpm] (Reference Synthesis Example 1) The production of the 2-functional hydroxy-terminal quinone imine (A) is provided with a nitrogen introduction tube, A water separator (Dean-stark Receiver) and a glass-made separable flask with a capacity of 500 mL in a cooling tube were charged with 2,3,3',4'-biphenyltetracarboxylic dianhydride 58.88 (0.201 «〇1), 17.0 g (0.10 mol) of phorone diamine, 15.0 g (0.20 mol) of 3-aminopropanol and 200 mL of dimethylacetamide were stirred at 100 ° C for 1 hour under a nitrogen atmosphere. Next, 50 mL of toluene was added, and the mixture was heated at 180 °C for 4 hours, and the water produced by the hydrazine imidization reaction was removed by azeotropy with toluene. The reaction solution was poured into 2 L of water, and the resulting precipitate was obtained by filtration, washed with water and dried under reduced pressure to yield 78.8 g of powder. The result of 1 H-NMR of the compound was confirmed to be a bifunctional hydroxy-terminal quinone imine (hereinafter referred to as bifunctional hydroxy-terminal quinone imine (A )) in which m (average enthalpy) of formula (3) is 1. . (Reference Synthesis Example 2) Production of a bifunctional hydroxy-terminal quinone imine (B) can be separated by a glass having a nitrogen introduction tube, a water-oil separator (Dean-stark Receiver -90 - 201113312), and a cooling tube capacity of 500 mL. In the flask, 2,3,3',4'-biphenyltetracarboxylic dianhydride 58.8§(0.20〇1〇1), isophoronediamine 25.55g (〇.l5mol), 3-aminopropyl The alcohol was 7.51 (〇.lmol) and dimethylacetamide (200 ml), and the mixture was stirred at 1 ° C for 1 hour under a nitrogen atmosphere. Next, toluene (50 m L) was added, and the mixture was heated at 180 ° C for 4 hours, and the water produced by the hydrazine imidization reaction was removed by azeotropy with toluene. The reaction solution was poured into 2 L of water, and the resulting precipitate was obtained by filtration, washed with water and dried under reduced pressure to give 72.0 g of powder. As a result of 1H-NMR of this compound, it was confirmed that the compound was a bifunctional hydroxy-terminal quinone imine (hereinafter referred to as a bifunctional hydroxy-terminal quinone imine (B)) having m (average enthalpy) of the formula (3). <Synthesis of Polyurethane Polyethylenimine> (Implementation Synthesis Example 1) Synthesis of Polyamidoacetate Polyimine (1) In a glass flask having a nitrogen introduction tube capacity of 300 mL , a mixture of kuraray polyol C*20丨5 ((poly)carbonic acid diol and raw material diol (ie, 1,6-hexanediol and 3-methyl-1,5-pentanediol), raw materials The molar ratio of diol to the molar ratio: 1,6-hexanediol: 3-methyl-1,5-pentanediol = 85 • 15, the base price of 56, lmgKOH/g, 1,6-hexanediol Residual concentration 1.5% by mass, residual concentration of 3-methyl-1,5-pentanediol 〇5 mass%) 5 0 00g (25mm〇l), 2,2-dimethylolpropionic acid 3.35g (25mmol , 4 4 , monophenylmethane methane diisocyanate 15.64 g (62.5 mmo1) ' y - butyrolactone 69.76 g, stirred under nitrogen atmosphere at 60 ° C for 3-5 hours. Next, & force 卩# test 2 prepared bifunctional hydroxy-terminal quinone imine (A) -91 - 201113312 20.92g (25mmol), r-butyrolactone 20.92g, stirred at 80 ° C for 10 hours . Thus, the number average molecular weight determined by GPC of a solution of polyurethane polyethylenimine (hereinafter referred to as polyethyl urethane polyethylenimine (1)) was 6,800. Adding 7-butyrolactone: diethylene glycol diethyl ether = 2 7.7 : 72.3 (mass ratio) of a mixed solvent of 23.75 g of the solution of the polyurethane polyethylenimine (1), adjusted to a solid concentration 44% by mass. This solution has a viscosity of 40 Pa_s. Further, the ethyl urethane poly(imide) (1) has an acid value of 15.6 mg-KOH/g. (Synthesis Example 2) Synthesis of Polyurethane Polyethylenimine (2) PLACCELCD-220 in which 1,6-hexane-based polycarbonate diol was charged into a glass container of 5 L having a nitrogen introduction tube ((poly)carbonate diol and a mixture of raw material diol (ie, 1,6-hexanediol), hydroxyl value 5 6.1 mg KOH / g, residual concentration of 1,6-hexanediol 3.0% by mass) lOO. Og (0.50 mol) and 4,4'-diphenylmethane diisocyanate 250.27 g (1.00 mol) and r-butyrolactone 833.15 g, and then the temperature was raised to 140 ° C, and the reaction was carried out for 5 hours. Further, 3,3 ',4,4 '-diphenylphosphonium tetracarboxylic dianhydride 358.29 g (1.00 mol) and 4,4'-diphenylmethane diisocyanate 125.14 g (0.50 mol) were added to the reaction mixture. 584.97g of r-butyrolactone was reacted with 16 (TC) for 5 hours. The obtained polyurethane polyethylenimine (hereinafter referred to as polyurethane urethane (2) It is diluted with a mixed solvent of 7-butyrolactone: diethylene glycol diethyl ether = 6 7 : 3 3 (mass ratio) to obtain a polyaminocarbamic acid-92- having a viscosity of 40 P a.s and a solid concentration of 40% by mass. 201113312 A solution of ethyl ester polyimine (2). The number average molecular weight of the polyurethane polyimine (2) obtained by GPC is 14000°. Polyurethane polyethylenimine ( 2) The infrared absorption (IR) spectrum was measured to confirm the absorption of the carboxylic anhydride. The solution of the polyethyl urethane poly(imide) (2) was synthesized and used for the following evaluation within the day. Synthesis of Branched Polyurethane Containing Carboxyl Group and Carbonate Bonds (Example 3 of Implementation) Synthesis of Polyurethane (1) equipped with a stirring device, a thermometer, and condensation In the reaction vessel, a mixture of C-IOMN (a (poly)carbonate diol made by Kuraray Co., Ltd. and a raw material diol (ie, 1,9-nonanediol and 2-methyl-1,8-octanediol) was charged. , raw material diol input molar ratio; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15: 85, hydroxyl value lH.SmgKOH / g, 1,9-nonanediol Residual concentration: 2.1% by mass, residual concentration of 2-methyl-1,8-octanediol: 9.3% by mass) 220.4 g (0.221 m〇l), 2,2-dimethylolbutanoic acid (Japan Chemical Industry Co., Ltd.) 42) g (〇.285 mol), trimethylolpropane 2.7 g (20-1 mmol), butyrolactone 510.0 g and diethylene glycol diethyl ether 90.0 g 'and then heated to 1 ° C to dissolve all the raw materials. The temperature of the reaction mixture was lowered to 90 C, and 133.7 g of methylene bis(4-cyclohexyl isocyanate) was dropped by a dropping funnel over 30 minutes. The reaction was carried out under ucTc. After 9 hours, it was confirmed that the isocyanate almost disappeared, and ethanol 丨·3 g ( 28.2 mm 〇l) was dropped, and then reacted at 8 (TC for 3 hours to obtain a polyaminocarboxylic acid having a carboxyl group and a carbonate bond containing -93-201113312. Ethyl ester (hereinafter referred to as a solution of ethyl urethane (η). The viscosity of the solution containing the obtained polyurethane (1) is 10 1 P a · s. The solution containing ethyl urethane (1) The number average molecular weight of the polyurethane (1) contained was 14,000, and the acid value of the ethyl urethane (1) was 40.0 mg-KOH/g. The solid content concentration in the solution containing the ethyl urethane (1) was 40.0% by mass. <Synthesis of a polyurethane having a carboxyl group and a carbonate bond and having a structural unit derived from a dimer diol> (Example of Synthesis Example 4) Synthesis of Polyurethane (2) In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, C-2015N (manufactured by Kuraray Co., Ltd. (poly)carbonic acid diol and raw material diol (ie, 1,9-nonanediol and 2-methyl-) Mixture of 1,8-octanediol), molar ratio of raw material diol to the molar ratio; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15:85, hydroxyl value 56.5 mgKOH /g, 1,9-decanediol residual concentration 1.0% by mass, 2-methyl-1,8-octanediol residual concentration 3.6% by mass) 107.9g (0_05 4m〇l), 2,2-two Hydroxymethylbutyric acid (manufactured by Nippon Kasei Co., Ltd.) 32.3 g (0.218 mol), PRIPOL2033 (dimer diol 98.2% by mass, monool 0.6% by mass, trimer triol 1.2% by mass, hydroxyl group price; 205 mg KOH/ g) 1 07.9g (0. 1 94mol ), tricyclo[5·2.1.02'6] decane dimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) -94- 201113312 14.8g (0_075mol), r-butyrolactone 2 9 7.〇g and diethylene glycol II Charm MS.Og' is heated to 10 (TC dissolves all the raw materials. The temperature of the reaction solution is lowered to 90 ° C, and 142.1 g of methylene bis(cyclohexyl isocyanurate) is added by a dropping funnel. 542m〇l) was dropped in 30 minutes. After ι2〇χ: reaction for 9 hours, it was confirmed that the isocyanate vinegar almost disappeared, and then 3.6 g (0.049 mol) of isobutanol (manufactured by Kyowa Fermentation Chemical Co., Ltd.) was dropped. The reaction was carried out at 12 〇t for 4 hours to obtain a polyurethane hydroxyacetate (hereinafter referred to as polyurethane) having a carboxyl group and a carbonate bond and having a structural unit derived from the dimer oxime. a solution of 2)). The viscosity of the solution containing the obtained polyurethane (2) is 78 Pa_s. The polyurethane containing the ethyl urethane (2) solution (2) The number average molecular weight is 13, and the acid value of the ethyl urethane (2) is 40.0 mg-KOH/g. The solid content concentration in the solution containing the ethyl urethane (2) is 45.0% by mass. (Example 5 of the implementation of the synthesis) The synthesis of the polyurethane (3) was carried out in a reaction vessel equipped with a stirring device, a thermometer and a condenser. C-2015N (mixture of (poly)carbonate diol made by Kuraray Co., Ltd. with raw material diol (ie, 1,9-nonanediol and 2-methyl-1,8-octanediol), raw material diol Injecting molar ratio; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15:85, hydroxyl group 56.5 mgfCOH/g, residual concentration of 1,9-nonanediol 1.0% by mass The residual concentration of 2-methyl-1,8-octanediol was 3.6 mass%. -95-201113312 46.7g (0.024mol), 2,2-dihydroxymethylbutyric acid (manufactured by Nippon Kasei Co., Ltd.) 32.1g (0.217 mol), PRIPOL2033 (dimer diol 98.2% by mass, monool 0.6% by mass, trimer triol 1.2% by mass, hydroxyl value; 205 mg KOH/g) ll6.7 g (0.210 mol), UM-90 ( 1/1) (mixture of (poly)carbonate diol made by Ube Industries Co., Ltd. with raw material diol (ie, 1,6-hexanediol and cyclohexanedimethanol), raw material diol input Mo Erbi ; 1,6-hexanediol: cyclohexane dimethanol = 1 / 1, hydroxyl value 122.7 mg KOH / g, residual concentration of 1,6-hexanediol 3.9% by mass, residual concentration of cyclohexane dimethanol · 4.7 Mass%) 70.0g (0.077mol), -butyrolactone 297.0g and diethylene glycol diethylene I98.0g, 1〇〇 ° C was heated to dissolve all material. The temperature of the reaction mixture was lowered to 90 ° C, and 136.0 g (0.51 8 mol) of methylene bis(4-cyclohexyl isocyanate) was dropped over 30 minutes by a dropping funnel. After reacting at 120 ° C for 9 hours, it was confirmed that the isocyanate was almost disappeared, and then 3.6 g (0.049 mol) of isobutanol (manufactured by Kyowa Chemical Co., Ltd.) was dropped, and further reacted at 120 ° C for 4 hours to obtain a carboxyl group and A carbonate bond, and a solution of a polyurethane having a structural unit derived from a dimer diol (hereinafter referred to as a polyurethane (3)). The viscosity of the solution containing the obtained polyurethane (3) is 84 Pa·s » the number average molecular weight of the polyurethane (3) contained in the solution containing the ethyl urethane (3) The acid value of the polyurethane (3) of 12,000 is 30.0 mg-KOH/g. The solid content concentration in the solution containing the ethyl urethane (3) was 45.0% by mass. -96-201113312 (Reference Synthesis Example 3) In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, C-1015N (a (poly)carbonate diol and a raw material diol (ie, 1,9-made by Kuraray Co., Ltd.) were charged. a mixture of decanediol and 2-methyl-1,8-octanediol), a molar ratio of the starting diol; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15: 85, hydroxyl group 112.3 mgKOH/g, residual concentration of 1,9-nonanediol 2.1% by mass, residual concentration of 2-methyl-1,8-octanediol 9.3% by mass) 3 8.6 g and Sovermol ( Registered trademark) 908 (dimer diol, manufactured by Cognis Co., Ltd.) 30.7 g, 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) 12.2 g and r-butyrolactone 120.2 g, heated to l〇 〇°C dissolves all raw materials. Methylene bis(4-cyclohexyl isocyanate) 4 3 . 5 g was added dropwise by a dropping funnel over 5 minutes. After the completion of the dropwise addition, the mixture was reacted at 110 ° C for 7 hours, and it was confirmed that the isocyanate was almost eliminated. Then, isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped at 2 · 0 g, and then reacted at 120 ° C for 2 hours. A solution containing ethyl urethane (hereinafter referred to as polyethyl urethane (4)) was obtained. The number average molecular weight of the polyurethane (4) contained in the solution containing the ethyl urethane (4) is 12, and the acid value of the 〇〇〇'polyurethane (4) is 39.8 mg-KOH/g. The solid content concentration in the solution containing the ethyl carbamate (4) was 50.3 mass%. (Refer to Synthesis Example 4) -97- 201113312 Feeding Alcohol) Ethyl Ester Ester 〇g (Methyl ester degree is used to invest C-1015N in a reaction vessel equipped with a stirring device, thermometer and condenser (Kuraray Co., Ltd.) a mixture of a (poly)carbonate diol and a raw diol (ie, I,9-nonanediol and 2-methyl-1,8-octanediol), a raw material diol, a molar ratio; 1,9 -decanediol: 2-methyl-i, 8_octyl = 15: 85, diameter base price H2.3 mg IC〇H/g, residual concentration of 1,9-nonanediol 2.1% by mass, 2-methyl group Residual concentration of -1,8-octanediol 9.3% by mass 1 78 .lg, dioctyltin dilaurate (Nitto Chemical Co., Ltd. product name Neostann U-810) 0.23g, 7-butyrol vinegar I91.3g And didiol diethyl ether 3 3.· 8 g 'When all the raw materials were dissolved by heating to 80 ° C. 47.0 g of methylene bis(4-cyclohexyl isocyanate) was dropped by a liquid funnel in 5 minutes. After the reaction, the mixture was reacted at 80 ° C for 4 hours to confirm that the isocyanic acid almost disappeared. Then, isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped, and then reacted with 8 (TC for 1 hour to obtain a polyamine. Ethyl carbamate a solution called ethyl polyurethane (5)). The polyamino acid ethyl ester (5) contained in the solution containing ethyl urethane (5) has a number average molecular weight of 19,000, and a polyamine group. The acid value of the ethyl formate (5) is Omg-KOH/g. The solid content in the solution containing the ethyl carbamate (5) is 50.1% by mass. (Integration Example 1) Containing polyaminocarboxylic acid In the solution of the ethyl ester polyimine (1), for the 100 parts by mass of the polyurethane polyethylenimine (1), 1,8-diazabicyclo ring (5.4.0) added as a hardening accelerator 1% by mass of undecene _7 (hereinafter referred to as DBU (98-201113312) (manufactured by Sannopco Co., Ltd.), and then uniformly stirred and mixed. Further added cerium oxide powder (trade name manufactured by Japan Aero Sil Co., Ltd.; aerosilR972) 7 After the mass part, talc (trade name: SG 2 0 0 0, manufactured by Nippon Talc Co., Ltd.), 5 parts by mass, first, coarse kneading, followed by a three-roll mill (manufactured by Inoue Co., Ltd.: S-43/4xll) After repeating the mixing for 3 times, the kneading was carried out to obtain a polyimine (1) containing uniformly mixed polyurethane. A product (hereinafter referred to as a main component composition A 1 ). An epoxy resin having a structure of the following formula (2) is added to a container equipped with a stirrer, a thermometer, and a condenser (trade name, manufactured by DIC Corporation; 7200 Η epoxy equivalent 278 g/eq) 300 g, 7-butyrolactone 180 g, and diethylene glycol diethyl ether 12 2 g, and stirring was started. Stirring was continued while the temperature in the vessel was raised to 70 using an oil bath. (: After the internal temperature is raised to 70 °c, 'continue to stir for 30 minutes. Then, after confirming that HP-72 00H is completely dissolved, 'cool down to room temperature to obtain a solution containing HP-7 200H at a concentration of 50% by mass (hereinafter referred to as For the hardener solution B 1 ).

(In the formula, '1 series means an integer of 〇 or 丨.) Mixing 100 parts by mass of the main component composition a 1 and 9, 6 parts by mass of the hardener 彳谷液 B 1 and the antifoaming agent (Μ 〇 Mentive P erf 〇rmance Materials company trade name: TSA 7 5 0 S ) 0 · 5 parts by mass, using -99 - 201113312 Wipe the knife and mix thoroughly. Then, a mixed solvent of r-butyrolactone: diethylene glycol diethyl ether = 85:15 (mass ratio) which is required to have a thixotropic index of 1.3 is added, and the viscosity is adjusted to obtain a thermosetting composition (hereinafter, It is called thermosetting composition G 1 ). (Implementation Example 2) Aer〇sil3 80 was added to 100 parts by mass of polyurethane polyethylenimine (2) in a solution containing polyurethane polyethylenimine (2) ( 1 part by mass of DBU (manufactured by San-apro Co., Ltd.) of 7.9 parts by mass and hardening catalyst, and first coarse kneading, followed by a three-roll mill (formed by Inoue Co., Ltd.: S-43/) 4x11) After the kneading was repeated three times, the kneading was carried out to obtain a composition containing polyethylenimine (2) (hereinafter referred to as a main component A 2 ). 20 parts by mass of the hardener solution B1 and an antifoaming agent (trade name: TSA 7 5 0 S, manufactured by Momentive Performance Materials Co., Ltd.) were added in an amount of 0.5 parts by mass to 1 part by mass of the main component A2. Lactone: diethylene glycol diethyl ether = 85: 15 (mass ratio) diluted to obtain a viscosity of 35Pa's, a thixotropic index of 2.2, a non-volatile content of 40% by mass of polyurethane polyethylenimine (2) A thermosetting composition (hereinafter referred to as a thermosetting composition G2). (Example 3) The solution containing the above-mentioned polyurethane (1) was mixed with 11: 1.1 mass-100-201113312 parts, oxidized sand powder (trade name of Japan Aerosil Co., Ltd.; aer〇silR9 74) 5.0 0.36 parts by mass of melamine (manufactured by Seiko Chemical Industry Co., Ltd.) as a hardening accelerator, and repeated three times of kneading using a three-roll mill (manufactured by Inoue Co., Ltd.: S-43/4X 1 1) In the kneading, a composition containing ethyl polyurethane (1) (hereinafter referred to as a main component composition A3) was obtained. To 100 parts by mass of the main component composition A3, 22.7 parts by mass of the hardener solution B1 and 0.60 parts by mass of an antifoaming agent (trade name: TSA750S, manufactured by Momentive Performance Materials Co., Ltd.) were mixed, and the mixture was thoroughly stirred and mixed using a spatula. Then, a mixed solvent of r-butyrolactone: diethylene glycol diethyl ether = 85:15 (mass ratio) which is required to have a thixotropic index of 1.3 is added, and the viscosity is adjusted to obtain a thermosetting composition (hereinafter, It is called thermosetting composition G 3 ). (Example 4) A solution containing 1.1 1 part by mass of the solution containing the above-mentioned polyurethane (2) and 5.0 parts by mass of oxidized sand powder (trade name: aerosil R9 74, manufactured by Nippon Aerosil Co., Ltd.) as a hardening accelerator 0. 36 parts by mass of melamine (manufactured by Seiko Chemical Industry Co., Ltd.), and the kneading was repeated three times using a three-roll mill (former type: S-43/4x 1 1 of the company). A composition of ethyl urethane (2) (hereinafter referred to as a main component composition A 4 ). 25.5 parts by mass of the hardener solution B1 and the antifoaming agent are mixed with respect to 100 parts by mass of the main component composition A4 (MomenHve performance -101 - 201113312

The product name of Materials Co., Ltd.; TSA750S) 0.60 parts by mass, mixed thoroughly with a spatula. Then, a mixed solvent of r-butyrolactone: diethylene glycol diethyl ether = 60:40 (mass ratio) which is required to have a thixotropic index of 1.3 is added to adjust the viscosity to obtain a thermosetting composition (hereinafter, It is called thermosetting composition G 4 ). (Example 5) The mixture of 111.1 parts by mass of the solution containing the above-mentioned polyurethane (3) and cerium oxide powder (trade name: aer〇silR974, manufactured by Nippon Aerosil Co., Ltd.) 5.0 parts by mass, and melamine as a hardening accelerator (manufactured by Nissan Chemical Industry Co., Ltd.) 0 · 36 parts by mass, and the kneading was repeated three times using a three-roll mill (formed by Inoue Co., Ltd., S- 4 3 /4 X 1 1) A composition containing ethyl urethane (3) (hereinafter referred to as a main component composition A 5 ). 19.1 parts by mass of the hardener solution B1 and an antifoaming agent (trade name of Momentive Performance Materials Co., Ltd.; TSA 7 5 0 S ) 0 _ 60 parts by mass, using a spatula, with respect to 100 parts by mass of the main component composition A5 Mix well with stirring. Then, a mixed solvent of 7-butyrolactone: diethylene glycol diethyl ether = 60:40 (mass ratio) which is required to have a thixotropic index of 1.3 is added, and the viscosity is adjusted to obtain a thermosetting composition (hereinafter, It is called thermosetting composition G 5 ). (Implementation Example 6) Mixing 3 0.3 mass - 102 - 201113312 parts of hardener solution B 1 and antifoaming agent (1 〇mentive P erf 〇rmance Materials) with respect to 1 part by mass of the main component A 3 Product name; TSA 7 5 0 S ) 0 _ 60 parts by mass, stir well with a spatula. Then, a mixed solvent having a thixotropic index of r-butyrolactone: diethylene glycol diethyl ether = 85:15 (mass ratio) is added to adjust the viscosity to obtain a thermosetting composition (hereinafter, It is called thermosetting composition G 6 ). (Example 7) The hardener solution B1 and the antifoaming agent (trade name of Momentive Performance Materials Co., Ltd.; TSA 7 5 0 S) were mixed with 3 parts by mass of the main component composition A4. · 60 parts by mass, mix thoroughly with a spatula. Then, a mixed solvent having a thixotropic index of 1.3 -butyrolactone: diethylene glycol diethyl ether = 60:40 (mass ratio) is added, and the viscosity is adjusted to obtain a thermosetting composition (hereinafter, It is called thermosetting composition G 7 ). (Example 8) The hardener solution B1 and the antifoaming agent (trade name of Momentive Performance Materials; TSA750S) 0.60 parts by mass were mixed with 100 parts by mass of the main component composition A 5 , Stir well with a spatula. Then, a mixed solvent of r-butyrolactone: diethylene glycol diethyl ether = 60:40 (mass ratio) which is required to have a thixotropic index of 1.3 is added, and the viscosity is adjusted to obtain a thermosetting composition (hereinafter, It is called thermosetting composition G8). -103- 201113312 (Comparative Example 1) CELLOXID202 1 P (made by Daicel Chemical Industry Co., Ltd., (3', 4'-epoxycyclohexane) methyl group) with respect to 100 parts by mass of the main component A1 -3,4-epoxycyclohexanecarboxylate, epoxy equivalent 126g/eq) 4.2 parts by mass and defoaming! J ( Momentive

Performance Materials, Inc., manufactured by Performance Materials, Inc.: TSA750S) 0.5 parts by mass is uniformly mixed in the composition containing the aforementioned polyurethane urethane (1) to obtain a polyethylene urethane containing polyurethane (1) The thermosetting composition (hereinafter referred to as thermosetting composition Η 1 ). (Comparative Example 2) Υ Η - 4 3 4 (trade name of amine-type epoxy resin manufactured by Dongdu Chemical Co., Ltd., epoxy equivalent 120 g/eq) was added to 100 parts by mass of the main component composition A 2 . 10 parts by mass and 0.5 parts by mass of TSA750S (trade name of defoamer manufactured by Momentive Performance Materials), diluted with 7-butyrolactone to obtain a viscosity of 3 5 P a . s, a thixotropic index of 2.4, a nonvolatile content of 40 mass % of a thermosetting composition (hereinafter referred to as thermosetting composition H2) containing polyethyl urethane polyethylenimine (2). (Comparative Example 3) A container equipped with a stirrer and a condenser was charged with jER 828EL (Nippon Epoxy Resin Co., Ltd. bisphenol A epoxy resin epoxy equivalent 190 g/eq) 300 parts by mass, diethylene glycol monoethyl ether 300 parts by mass of acetate -104-201113312, began to mix. Stirring was continued for 1 hour. Then, after confirming that jER8 2 8 EL was completely dissolved, a solution containing jER8 2 8 EL having a concentration of 50% by mass was obtained. This solution was used as the hardener solution B 2 . 1 part by mass of the solution containing the above-mentioned polyurethane (4), 1 part by mass of 'yttrium oxide powder (trade name, manufactured by Nippon Aerosil Co., Ltd.; aer〇SilR974), 5.0 parts by mass, melamine as a hardening accelerator (曰0. 36 parts by mass of the Chemical Industry Co., Ltd., and the kneading was repeated three times using a three-roll mill (formed by Inoue Co., Ltd.: S-43/4 X 1 1), and the mixture was mixed to obtain a polyamine. A composition of ethyl urethane (4) (hereinafter referred to as a main component composition A 6 ). 14.2 parts by mass of the hardener solution B 1 and the antifoaming agent (trade name of 〇 〇 mentive erf 〇rmance Materials Co., Ltd.; TSA 7 5 0 S ) 0.60 parts by mass based on 100 parts by mass of the main component composition A6. Use a spatula to mix thoroughly. Then, a mixed solvent in which the thixotropic index is required to be a required amount of butyrolactone: diethylene glycol monoethyl ether acetate = 1: 1 (mass ratio) is added, and the viscosity is adjusted to obtain a thermosetting composition ( Hereinafter referred to as a thermosetting composition Η 3 ). (Comparative Example 4) 8.9 parts by mass of a solution containing the aforementioned polyurethane (5) and 5.0 parts by mass of cerium oxide powder (trade name: aerosil R9 74, manufactured by Nippon Aerosil Co., Ltd.) as a hardening accelerator Melamine (manufactured by 曰 化学 化学 化学 〇 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 重复 重复 重复 重复 重复 重复 重复After kneading, a composition containing ethyl polyurethane (5) (hereinafter referred to as a main component composition A7) was obtained. 22.7 parts by mass of the hardener solution B1 and an antifoaming agent (trade name of Momentive Performance Materials Co., Ltd.; TSA 7 5 0 S) 0.60 parts by mass were mixed with 80.9 parts by mass of the main component composition A7, and thoroughly stirred using a spatula. mixing. Then, a mixed solvent of r-butyrolactone: diethylene glycol diethyl ether = 85:15 (mass ratio) which is required to have a thixotropic index of 1.3 is added, and the viscosity is adjusted to obtain a thermosetting composition (hereinafter, It is called thermosetting composition H4). (Examples 1 to 8 and Comparative Examples 1 to 3) As shown in Table 1, each of the thermosetting composition G 1 to the thermosetting composition G 8 and the thermosetting composition Η 1 to the thermosetting composition were used. H4, by the method described later, the adhesion of the polyimide and the copper to which the tin plating treatment was applied, the evaluation of the warpage property, and the evaluation of the long-term electrical insulation reliability were evaluated. The results are shown in Table 1. Evaluation of adhesion of polyimine and copper to tin-plating treatment The thermosetting composition G1 was applied to a flexible copper-clad laminate by screen printing (trade name of Sumitomo Metal Mining Co., Ltd.) ; S'PERFLEX copper thickness; 8 μm, polytheneimide thickness; 38/zm) applied to a tin-plated substrate and a polyimide film (Kapton (registered trademark) 3 00H, manufactured by DuPont Toray Co., Ltd.) to thermally harden The thickness of the composition is 1 5 /zm (thickness after drying), placed in a hot air circulating dryer at 80 °C 30-106-201113312 minutes 'after' placed at 120 °C hot air circulation drying The machine was hardened in 120 minutes. On the hardened coating film, 100 grid patterns were cut at intervals of 1 mm, and a tape cut to a length of about 75 mm was adhered to the lattice portion, and the peeling tape (article specified by Jis Z 1522) was brought close to 60. The angle is pulled away by 0.5~1 _ 0 seconds. The tape for peeling was manufactured by Nitto Denko Corporation and evaluated according to the following criteria. 〇: There are more than 80 square lattices remaining, △: the number of square lattices remains 50 or more, and the number of squares is less than 80, and the number of square squares is only less than 50. The results are shown in Table 1. Further, the same evaluation was carried out using the thermosetting composition G 2 to the thermosetting composition G 8 and the thermosetting composition Η 1 to the thermosetting composition H4. These results are collectively shown in Table 1. Evaluation of warpage The thermosetting composition G1 was applied to the substrate by screen printing, placed in a hot air circulating dryer of 8 (TC) for 30 minutes, and then placed in a hot air circulating drying at 12 °C. The film was hardened for 60 minutes in the machine, and a 38-thick polyimide film (Kapton (registered trademark) 150EN, manufactured by DuPont Toray Co., Ltd.) was used for the substrate.

The coating of the thermosetting composition was cut into a 50 mm φ with a circular cutter using a coating film which was hardened by a dryer. A person who is cut into a circle has a convex or concave warped deformation near the center. The test piece was allowed to stand for 12 hours or more under the conditions of temperature 23±0.5°C -107-201113312 and humidity 60±5 % RH, and the lower part was placed in a convex state, and the maximum warpage was from the plane. The center of the circle is symmetrical, and the length average is used to measure the height average of the warpage from the plane. When the symbol is the direction of the warpage and the lower side is in a state of being convex, the polyimide film is evaluated as "+ j" when the cured film is on the upper side and "-" when the cured film is on the lower side. The results are shown in Table 1. Further, the same results were evaluated using the thermosetting composition G2 to the thermosetting composition G8 and the thermosetting composition Η 1 to the thermosetting composition Η 4 . The results are shown in Table 1. Evaluation of Flexibility The thermosetting composition G 1 was applied to a flexible copper-clad laminate by screen printing (trade name of Sumitomo Metal Mining Co., Ltd.; S'PERFLEX copper thickness; 8/zm, Jujua The amine is thick; on the copper of 38μπ〇, it has a width of 7 5mm and a length of 1 l〇mm. The thickness of the coating film after hardening becomes 15 //m, and then it is kept at room temperature for 10 minutes, and is placed at a hot air of 120 °C. The circulating dryer was hardened for 60 minutes, and the PET film on the inner side of the produced test piece was peeled off, and cut into a short booklet having a width of 1 Omni by a dicing blade, and then bent at a width of about 180 degrees to make the coating film surface outer. The compressor was compressed at 0.5 ± 0.2 MPa for 3 seconds using a compressor. The bent portion was observed under a microscope using a 30-fold microscope to confirm the presence or absence of cracks. The results are shown in Table 1. -108- 201113312 The composition G2 to the thermosetting composition G8 and the thermosetting composition H1 to the thermosetting composition H4 were evaluated in the same manner. The results are shown in Table 1. Evaluation of long-term electrical insulation reliability (1) The hardenable composition G 1 is applied to the etching by screen printing Substrate of copper-plated laminate (trade name of Sumitomo Metal Mining Co., Ltd.; S'PERFLEX copper thickness; 8 μm, polytheneimide thickness: 38 # m), which is a micro-patterned substrate (JP-ET01) Wiring width / copper wiring width = 1 / 5 / m / 1 5 / m ) Apply tinned tinned flexible wiring board so that the thickness of the polyimide surface becomes 15 "m thickness (after drying) 'It was placed in a hot air circulating dryer at 80 ° C for 30 minutes, and then hardened by a hot air circulating dryer at 120 ° C for 120 minutes. Using this test piece, a bias voltage of 60 V was applied. Temperature and humidity constant test under the conditions of temperature 120 ° C and humidity 95% RH using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV Co., Ltd.) 1 hour, 1 hour later, 2 0 0 after the start of the above temperature and humidity constant test The resistance after the hour, after 300 hours, and after 400 hours is shown in Table 1. Further, the thermosetting composition G2 to the thermosetting composition G8, the thermosetting composition Η 1 to the thermosetting composition were used. The same evaluation was performed for η 4. These results are also shown in Table 1. Evaluation of long-term electrical insulation reliability (2) -109- 2 01113312 The thermosetting composition G is made of a screen-printed copper laminate (Sumitomo Metal Mining Co., Ltd., PERFLEX copper thickness; 8/zm, polytheneimide thickness: JPCA-ET01) The shape of the copper-free wiring compartment is =1 5 // m /1 5 // m ) The tin-plated place is applied to the sky so that the thickness of the polyimide surface becomes 15Mm|), and the hot air circulation dryer is placed at 8CTC. In the hot air circulating dryer of 30 120 °C for 120 minutes, the test piece was hardly used, and a bias voltage of 60 V was applied to make the temperature and humidity constant test of the condition of TESTER MODEL MIG-8600 (IMV company, humidity 85 % RH) The resistance 値 after 1000 hours after 1000 hours after the start of the test and after the start of the test, as shown in Table 1, the thermosetting composition G 2 ~ the thermosetting thermosetting composition Η 1~ The results of the thermosetting composition H4 are also shown in Table 1. The method is applied to the name of the etched product; 38 // m) The thickness of the manufactured wiring board (the width of the copper wiring width / the inside of the flexible wiring board (minutes after drying, and then placed. MIGRATION) for temperature 8 5 °C. From the above temperature and humidity, after 500 hours, as shown. Sex composition G 8, the same evaluation. -110- 201113312 Comparative Example 4 Thermosetting composition H4 〇ci 1 〇〇ΐχίο1. 5X109 i Short circuit 1 Short circuit short circuit ΐχ ίο1. 5X109 Short circuit short circuit Comparative example 3 Thermosetting composition H3 〇1 Ο 〇m 3X10! 4X108 4X108 4Χ108 1 3Χ108 IX 101° 9X105 5xl09 ιχίο1. Comparative example 2 Thermosetting composition H2 -2.0 0 〇m 2X10® 3X10! 1 2X108 1 3Χ108 1 3X10* 1 2X1010 lxio1» 1 ! 8X109 4ΧΙ09 Comparative Example 1 Thermosetting composition H1 〇1 Ο 〇m 7X108 8X108 7X108 7Χ108 7 x10s 2x 10!0 lxio10 8X109 4Χ109 Example 8 m 〇〇® chain 〇1 0 〇2xl09 3X109 4X109 _____ _ 4Χ109 3Χ109 1X101. 3X1010 5X1010 9ΧΙ010 Example 7 Thermosetting composition G7 〇1 〇〇诨1X109 2X109 3Χ 109 3 ΧΙΟ9 2 Χ109 lxio10 3xl0'° 5X1010 1X10" Example 6 1 Thermosetting 丨 composition G6 〇1 〇〇lxio9 1_ 2X109 3Χ108 3ΧΙ09 2Χ109 IX 1010 3X1010 4X 1010 δχ 1010 Example 5 Thermosetting composition G5 U-5 1 0 〇m IX 109 2X109 3 ΧΙΟ9 3Χ109 2Χ109 j ixio10 3X1010 4X 1010 7Χ1010 Example 4 Thermosetting composition G4 ΙΛ 1 0 〇« 1X109 2X109 2X10S 2Χ109 X 1X1010 Γ 3X1010 4X 1010 8Χ1010 Example 3 Thermosetting composition G3 t 〇〇m 1X109 2X109 2Χ109 1_____ 2Χ109 X lxio10 2X10'. 3X1010 6Χ Ι010 Example 2 Thermosetting composition G2 Ο c^a ο 〇m 9X10* 1X109 ΐχ ιο9 9Χ 108 9X 10s 2X 1010 3X1010 4X1010 7X10 丨0 Example 1 Thermosetting composition G1 Ο 〇〇m 9X108 2X109 2Χ109 2 ΧΙΟ5 1XI09 1X101. 3X1010 4X101. 8Χ1010 Unit e E aa The evaluation of the warpage of the thermosetting composition and the adhesion of the polyimine. η mm m» 握 斯 Li Sao (4) The presence or absence of the crack starts 100 hours after the start of 100 hours. After 1 hour, 1 hour, 300 hours, I, 400 hours, 1 hour, 10 hours, 1 hour, 1 hour, 1000 hours, 1 hour, 2000 hours, adhesion evaluation, flexibility evaluation, «1 -111 - 201113312 As a result of Table 1, by using the thermosetting composition of the invention (I), it is possible to provide a state in which a low-resistance ruthenium can be maintained at a high level, a novel composition exhibiting long-term electrical insulating properties, and a hardening of the composition. The resulting cured product. Industrial Applicability The thermosetting composition for a protective film of a wiring board of the present invention is suitable for use in the production of a flexible wiring board. -112-

Claims (1)

201113312 VII. Patent Application Range 1. A thermosetting composition for a protective film for a wiring board is characterized by an epoxy group-containing compound having a tricyclodecane structure and a functional group reactive with an epoxy group. And having the structural unit of the formula (1) and the solvent as an essential component' (1) (wherein R1 represents an alkylene group having a carbon number of 3 to 18', and η means an integer of 1 or more). 2. The thermosetting composition for a protective film of a wiring board according to claim 1, wherein the epoxy group-containing compound having a three-ring brothel structure has a tricyclo[5.2.1.0''6] decane structure or Tricyclo[3.3.1.13'7]decane structure and epoxy group-containing compound having an aromatic ring structure. 3. The thermosetting composition for a protective film of a wiring board according to the second aspect of the invention, wherein the epoxy group-containing compound having a tricyclodecane structure is a compound represented by the formula (2), (In the formula, 1 represents an integer of 0 or more). 4. The thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 3, which has a functional group -113-201113312 which can react with an epoxy group, and has a formula (i) The structural unit of the polyurethane is a polyurethane having a functional group reactive with an epoxy group and having a structural unit represented by the formula (1) and having a quinone bond. The thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 4, wherein the functional group reactive with the epoxy group is a carboxyl group. The thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 4, wherein the functional group reactive with the epoxy group is an acid anhydride group. 7. The thermosetting composition for a protective film of a wiring board according to the fourth or fifth aspect of the invention, which has a functional group reactive with an epoxy group and having a structural unit represented by the formula (1), and further having The polyimine bond of the quinone imine bond is a polyurethane polyethylenimine obtained by reacting the following components (a) to (d), component (a) diisocyanate, Component (b) (poly)carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, component (c) a diol having a carboxyl group, and component (d) represented by formula (3) 2-functional hydroxy-terminal quinone imine, 0 HO—R2—N Ο Ο N-R3-〇H (3) -114- 201113312 (wherein R2 and R3 each independently represent a divalent aliphatic or aromatic hydrocarbon group' Y 1 represents a tetravalent organic group derived from a tetracarboxylic acid or an anhydride group thereof, and the X1 system It represents a divalent organic group derived from a diamine or a diisocyanate, and 111 is an integer of 0 to 20). 8. The thermosetting composition for a protective film of a wiring board according to the fourth or sixth aspect of the invention, which has a functional group reactive with an epoxy group and has a structural unit represented by the formula (1), and further has The polyamidiamine of the quinone imine bond is a polyethylenimine having at least one structural unit selected from the group consisting of the formulas (4) to (6). In the formula, the plurality of R4 groups are each independently an alkylene group having a carbon number of 3 to 18'. The plurality of R5 groups are each independently an alkylene group having a carbon number of 3 to 18, and each of the a and b groups is independently an integer of 1 to 20, A plurality of X2 systems are each independently a divalent organic group. (5) In the formula, a plurality of R6 systems are each independently a carbon number of 3 to 18, and a plurality of R7 systems are each independently an alkylene group having a carbon number of 3 to 18, and the c & d systems are each independently 1~ An integer of 20, a plurality of X3 systems are each independently a divalent organic group, γ2 is a CH2, 302 or 0, -115- (6) 201113312 --X—ί3- where a plurality of R are independently independent, Y3 is discarded, and a plurality of R8 systems are each independently an alkylene group having a carbon number of 3 to 18, and the 9 series are each independently an alkylene group having a carbon number of 3 to 18. , e and f are each an integer from 1 to 20, and the plurality of X4 systems are each independently a divalent organic: a group of any one of the following formulas (7) to (33). -116- (11) 201113312 (14) (15) (16) -117- (17) 201113312 (18) (2 0) (2 1) 118- 201Π3312 (2 2) (2 3) (2 4) (2 5) (2 6) 119- 201113312 (2 7) (2 8) (2 9) (3 0) (3 1 ) (3 2) (3) The thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 3, which has a functional group reactive with an epoxy group, and has The polyurethane having the structural unit represented by the formula (1) is a polyurethane obtained by reacting the following components (a), (b), and (e) and a component (e). (a) a diisocyanate, a component (b) having a (poly)carbonate polyol having an organic residue derived from a diol having 3 to 18 carbon atoms, a component (c) having a carboxyl group, and a component (e) A thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 3, 5, 6 and 9 of the invention, wherein The epoxy group-reactive functional group and the polyurethane having the structural unit represented by the formula (1) are polyethyl urethanes further containing an organic residue derived from the dimer diol. The thermosetting composition for a protective film for a wiring board according to any one of claims 1 to 10, Wherein the solvent is at least one solvent having a boiling point of not more than 190 ° C and less than 200 ° C at atmospheric pressure and having a boiling point of from 200 ° C to 2 2 0 ° C at atmospheric pressure. A mixed solvent of at least one solvent. 1 2. A thermosetting composition for a protective film of a wiring board according to the first aspect of the invention, wherein at atmospheric pressure, it has a boiling point of 17 CTC or more and less than 2 〇〇 ° C. The solvent is at least one selected from the group A below, and has 200 at atmospheric pressure. The solvent having a boiling point of (220 ° C) is at least one selected from the group consisting of B - 121 - 201113312 below. Group A · ethylene glycol dimethyl ether (boiling point 162. 〇, bis 7 - alcohol diethyl ether (boiling point 189 〇 c), - _ ~ ~ ~ an ethyl methyl ether (boiling point 176 ° c), - inside - indole dimethyl ether ( , _ . 〇r,, (boiling point 17. 'mC), 3_methoxybutyl acetate vinegar K), ethylene glycol monobutyrate acetate vinegar (boiling 35192. 〇 - Β group B - alcohol butyl methyl ether (boiling point 212 艽), tripropylene glycol dimethyl ether (boiling point 2 丨 5 t ) 'di-ethyl-6-methyl ether (boiling point 2 16 T:), ethylene glycol dibutyl ether (boiling point 2 〇 Rc ), diethylene glycol di-monoethyl acetate acetate (boiling point 2l7t), 7-butyrolactone (boiling point 2〇4<t). 13 · Protective film of wiring board, characterized by the scope of patent application 1 A protective film for a wiring board obtained by curing a thermosetting composition of a protective film of a wiring board of any one of the two items. 1 4. A flexible wiring board covered with a protective film, characterized in that it is formed on a flexible substrate. A part or all of the surface of the flexible wiring board formed by the wiring is covered with a protective film of the wiring board of claim 13 of the patent application. A method for producing a flexible wiring board coated with a protective film, which is characterized in that a thermosetting composition for a protective film of a wiring board according to any one of claims 1 to 12 is printed to In the tinned wiring pattern portion of the flexible wiring board, a printed film is formed on the pattern. The printed film is cured by heating at 80 to 13 (TC is formed to form a protective film. -122-201113312 4. Designated representative image : (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None