TW201031708A - Resin composition for printed wiring board - Google Patents

Abstract

Disclosed is a resin composition for printed wiring boards that comprises (A) a polyimide resin that has hexafluoroisopropanol groups and a siloxane structure and (B) a heat curable resin. The resin composition has excellent solvent resistance and excellent heat resistance with little temperature variation in the modulus of elasticity.

Description

201031708 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to printing comprising (A) a polyimine resin having a hexafluoroisopropanol group and a decane structure, and (B) a thermosetting resin A resin composition for a circuit board. [Prior Art] Φ Polyimide resin excellent in heat resistance is widely used in the field of electronics and aerospace. A material having a heat-insulating property and a low elasticity has been developed in which a rhodium-oxygenane structure is introduced into the polyimide resin (Patent Document 1). However, solvent resistance may not be satisfactory. In order to improve the problem, a composition of a polyimine resin having a phenolic hydroxyl group and a polyoxyimide resin and an epoxy resin can be used as an adhesive for a printed circuit board or the like (Patent Document 2). However, as the temperature changes, the change in the elastic rate is not always satisfactory. Further, the use of a thermosetting resin may also cause problems such as deformation or cracking of the printed circuit board, and may not be satisfactory. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-12666 [Patent Document 2] JP-A-2004-5 1 794A No. 201031708 [Summary of the Invention] [Inventions to be solved] Problem to be Solved by the Invention It is an object of the present invention to provide a resin composition containing a polyamidene resin having a siloxane structure and a thermosetting resin, which is excellent in heat resistance and solvent resistance, and has higher reliability for printed circuit boards. Resin composition. [Means for Solving the Problem] In order to solve the above-mentioned problems, the inventors of the present invention have found that a polyimine resin having a fluorinated alkane structure having a hexafluoroisopropanol group and a thermosetting resin are found. The resin composition has a small change in the modulus of elasticity as a function of temperature, and is excellent in heat resistance and solvent resistance, and is excellent in characteristics as an insulating material for a printed circuit board, and has completed the present invention. In other words, the present invention contains the following contents. (1) A resin composition for a printed circuit board comprising (A) a polyimide resin having a hexafluoroisopropanol group and a decane structure, and (B) a thermosetting resin (2) The resin composition for a printed circuit board according to the above (1), which further comprises (C) an inorganic ruthenium filler. (3) The resin composition for a printed circuit board according to the above (1) or (2), wherein the thermosetting resin is an epoxy resin. (4) The resin composition for a printed circuit board according to any one of the above items (1) to (3), wherein the polyimine resin has the following formulas (1) and (2); -6- 201031708

(wherein 'R1 is a 4-valent organic group, R2 is a divalent diamine residue having a hexafluoroisopropanol group' and R3 means a divalent alkoxydiamine residue' 1) The number of repetitions in one of the repeating units indicated by 袠 is an integer of 1 or more and 1 〇〇 or less, and the number of repetitions in one of the repeating units represented by the formula (2) is an integer of 1 or more and 100 or less) The repeating unit represented. (5) A resin composition for a printed circuit board according to any one of the above items (1) to (4), wherein the hexafluoroisopropanol group and the decane oxide structure are six The functional group equivalent of the fluoroisopropanol group (hereinafter referred to as HFA group equivalent) is 1000 to I〇〇〇〇g/mol. (6) A resin composition for a printed circuit board according to any one of the above (1) to (5), wherein (A) a fluorene-imide resin having a hexafluoroisopropanol group and a decane structure The oxyalkylene content is 50 to 80% by weight. (7) A solder resist ink comprising the resin composition for a printed circuit board according to any one of the above items (1) to (6). (8) A type of adhesive film is formed by forming a resin composition layer for a printed circuit board according to any one of the above items (1) to (6). (9) A metal foil-attached adhesive film formed on a metal foil to form a resin composition layer for a printed circuit board according to any one of the above items (1) to (6), 201031708 (10) The resin composition for a printed circuit board according to any one of the above items (1) to (6) is impregnated with a sheet-like fibrous base material. (11) A metal foil-containing prepreg obtained by laminating a metal foil to the prepreg of the above item (10). (12) A protective layer film formed by forming a resin composition layer for a printed circuit board according to any one of the above items (1) to (6). (13) A printed circuit board comprising the resin composition for a printed circuit board according to any one of the items (1) to (6) above. The printed circuit board of the above item (13), wherein the insulating layer comprises a solder resist layer, an interlayer insulating layer, and a protective layer. (1 5 ) A printed circuit board which is formed by the solder resist ink of the above item (7). (16) A printed circuit board in which a solder resist layer is formed by the adhesive film of the above item (8). (17) A printed circuit board in which an interlayer insulating layer is formed by the adhesive film of the above item (8). Reference numeral (18) is a printed circuit board which is formed by forming an interlayer insulating layer and/or a conductor layer by an adhesive film of the metal foil of the above item (9). (1) A printed circuit board comprising an interlayer insulating layer formed by the prepreg of the above (1). (20) A printed circuit board in which an interlayer insulating layer and/or a conductor layer are formed by the prepreg of the metal foil of the above (1 1). (2 1 ) A printed circuit board comprising a protective layer formed of the protective layer film of the above item (1 2). -8 - 201031708 [Effect of the Invention] The fat group is made of a resin which contains a polyimine resin and a thermosetting resin of the present invention, and has low elasticity, and has excellent heat resistance and solvent resistance, and the resin is used. The composition is excellent in solvent resistance, and has a small change in the modulus of elasticity and a resin composition for a printed circuit board which is excellent in heat resistance. [Embodiment] [Mode for Carrying Out the Invention] The present invention relates to (A) a resin composition for a printing board having a hexafluoroisopropanol group and an alkane structure, and (B) a thermosetting resin. Hereinafter, the present invention will be described in terms of preferred embodiments. The base (preferably, the (A) polyimine resin of the present invention has hexafluoroisopropanol hereinafter referred to as HFA group) and a decane structure. The polyimine resin # is a repeating unit represented by the following formulas (1) and (2). 〔化2〕

In the formula, R1 represents a tetravalent organic group, R2 represents a divalent amine residue having a valence group, and R3 represents a divalent oxane diamine. The repeating number 分子 in one of the repeating units represented by the formula (1) is an integer of 1 or more and 100 or less (1SMS100). Preferably, the HFA residue of the formula (2) represents a repeating number N of one of the repeating units of -9 - 201031708, preferably an integer of 1 or more and 100 or less (1SNS100). R1 represents a tetravalent organic group, for example, having the following structure

-10- 201031708 ch2, CH (CH3), c ( ch3 ) 2, c ( cf3 ) 2, or C ( CCh ) 2 In the formula, the hydrogen atom on the aromatic ring can be halogen atom, carbon number i~8 The alkyl group is substituted. The divalent residue having a divalent group having an HFA group is represented by R2, for example, the following structure. 〔化4〕

Where 'A is synonymous with the above. The J system represents an integer of 1 to 4.艮 is not an integer from 1 to 6. The p and Q systems respectively represent an integer of 〇~2, M (P + Q) S4. • The hydrogen atom on the 'aromatic ring' in the formula may be substituted by a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like. The divalent naphthenic diamine residue represented by R ^ is, for example, the one having the following structure. 〔化5〕

201031708 (wherein R4 and R5 are each independently represent an alkyl group, a phenyl group or an oxyalkylene group of the carbon number', and the R6 to R10 series independently represent the alkoxy group of the carbon number u, and the alkoxy group having a carbon number of 1 to 5. The base or the phenoxy group, 3, b, and c are each independently represented by an integer of 1 or more, b + cgl, a + b + c260. In the formula, the hydrogen atom on the aromatic ring may be a halogen atom or a carbon. The polyalkyleneimine resin of the present invention can be produced by reacting a tetrabasic acid dianhydride represented by the formula (3) with a diamine compound represented by the formulas (4) and (5). <6> <1YO <YO ο H2N-R2——NH2 (4) H2N-R3-NH2 (5) (In the formula, Hi, R2 and RM are synonymous with the above.) The quaternion represented by the formula (3) The tetravalent organic group represented by R1 of the acid dianhydride is the same as described above. Specific examples of the tetravalent organic group represented by R1 are diphenyltetrabenzoic acid, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ',4,4'_biphenyltetracarboxylic dianhydride, 2,3',44,_biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'_diphenylfluorene tetraresidic acid, wild, 4,4,-(hexafluoroisopropylidene)·bis-(phthalic anhydride), 201031708 4,4' -oxyphthalic acid dianhydride, 4,4,_(4,4, isopropylidenediphenoxy)-bis-(ben-carboxylic acid monoanhydride), 1,3-dihydro-13 dioxo ·5-isobenzopyrene-(1-methylethylidene)-di-4,1_phenylene ester, ethylene glycol double-dehydrated trimellitate, 3,4,9,10-茈Dicarboxylic acid di-n-butyl, 9,9-bis(3,4-dicarboxy-based) behenic anhydride, 1,3_monohydro-indole 3·dioxo-5-isobenzofurancarboxylic acid-I,4 - phenyl phenyl ester, I, 2, 3, 4-cyclopentane tetracarboxylic acid di-hepatic, U, 3, 4 cyclobutane tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid Xuan, 4_(2,5-dioxotetrahydrofuran-3.yl)_1,2,3,4-tetrahydronaphthalene dicarboxylic anhydride, Hong (2 5 · monooxotetrahydrofuranyl)-3 -methyl-3 -Huan Jican 2 Dicarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furnyl)-naphthalene [ 1,2-C]pyran -1,3-one-one, etc. These tetradecanoic dianhydrides can be used in combination of two or more. The diamine compound having an HFA group represented by the formula (4) is, for example, represented by the following formula. [7]

(4-b) In the formula, the A series is not synonymous with the above. The J system represents an integer of 丨~彳. The K series is not an integer. The P and Q systems independently represent an integer from 0 to 2, 1 ^ ( P + Q ) $4. In the formula, the hydrogen atom on the aromatic ring may be substituted by a halogen atom, an alkyl group having a carbon number of 1 to 8 -13 to 201031708, or the like. In the formula (4-b), the amine groups on the naphthalene ring may be bonded to the same benzene ring, respectively, or may be bonded to different benzene rings. Similarly, when the HFA group is a complex number, it may be bonded to the same benzene ring, or may be bonded to a different benzene ring.

The diamine compound represented by the formula (4-a) can be produced by a known method described in the specification of International Publication No. WO 06/043 50 1 . The diamine compound represented by the formula (4-c) can be produced by a known method described in the specification of International Publication No. 2006/041 1 15 . The diamine compound represented by the formula (4-b) can be made into a corresponding naphthalene diamine compound and six according to a known method described in the specification of International Publication No. 2006/043 50 1 and International Publication No. 2006/041 115. The reaction of fluoroacetone or hexafluoroacetone·3 hydrate is carried out by introducing an HF thiol group onto a naphthalene ring. These HFA group-containing diamine compounds can be used in combination of two or more types. The diamine oxime represented by the formula (5) is, for example, represented by the following formula.

(5 a) wherein R4 and R5 each independently represent an alkylene group of a carbon number, a phenylene group or an oxygen-extension group, and the R6 to R10 groups independently represent an alkyl group having a carbon number of 1 to 5 and an alkyl number of carbon atoms. The oxy group or the phenoxy group, &amp;, b, and c each independently represent 〇 or an integer of 1 or more ' b + cgl, a + b + cg6 〇. In the formula, aryl -14 - 201031708 The hydrogen atom on the aromatic ring can be halogen atoms, carbon number! The base structure of the present invention is preferably a structure of the following formula (5b). (chemical 9), etc.

• Rf (5b) where Re and Rf independently represent alkoxy groups, phenyl groups, or phenoxy groups of 1 to 5 carbon atoms, „! is 6〇 or more, and each repeating unit is '6. Or Rf may be different. The diamino sulfoxane represented by the formula (5a), for example, bis-dipropyl)-1,1,2,2-tetramethyldioxane, 1,3_bis (3- Amine)-1,1,2,2-tetramethyldioxane, bis(4-aminophenoxy)^ decane, 1,3-bis(4-aminophenoxy)tetramethyl Anthracite,] tetramethyl-1,3-bis(4-aminophenyl)dioxane, ιυ, ki-I,3-bis(2-aminoethyl)dioxane, 1,1,3,3_Tetraphenylbis(2-aminoethyl) oxalate, 1,1,3,3-tetraphenyl-ι,3-bispropylpropyl)dioxane, 1,1,3,3-tetramethyl-;!,3_bis(2•amine) dioxin, I,1,3,3-tetramethyl-1,3-bis(3-amino group Propyl oxane, 1,1,3,3-tetramethyl-1,3-bis(4-aminobutyl)difluorene 1,3-dimethyldimethoxy-1,3-bis ( 4_Aminobutyl)di,1,1,3,3,5,5-hexamethyl-1,5-bis(4-aminophenyl)tris-1,1,5,5-tetraphenyl Base-3,3-dimethyl-1,5-bis (3-amine Propyl) group, an integer of carbon (3-aminobutyldimethyl 1,1,3,3-tetraphenoxy-1,3-(3-aminoethyl)dioxane, oxime Aloxane, trioxane-15- 201031708 alkane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-I,5·bis(4-aminobutyl) trioxane Alkane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(5-aminopentyl)trioxane, 1,1,5,5-tetra Methyl-3,3-dimethoxy-1,5-bis(2-aminoethyl)trioxane, 1,1,5,5-tetramethyl-3,3-dimethoxy - 1,5-bis(4-aminobutyl)trioxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-U5-bis(5-aminopentyl) Trioxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-aminopropyl)trioxane, 1,1,3,3,5, 5-hexaethyl-1,5-bis(3-aminopropyl)trioxane' 1,1,3,3,5,5-hexapropyl-1,5-chun bis (3-amine The propyl group may be used alone or in combination of two or more. The diamine compound other than the diamine compound represented by the formulas (4) and (5) may be used. The type or combination of two or more types is used in combination. For example, it is represented by the following formula (6): [Chemical 1 〇] H2N - R11 - NH2 (6) n (wherein R11 represents a divalent diamine residue having an HFA group and a divalent alkoxyalkyl diamine A divalent organic group other than the residue. The diamine compound is not particularly limited, and examples thereof include 1,4 -diaminobenzene, I,3,diaminobenzene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4 a diamine compound containing 1 benzene ring, 4,4'-diamino group, etc., such as diamino 2,5-dimethylbenzene or 1,4-diamino-2,5-dihalobenzene Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4, diaminobenzophenone, 3,3'-diaminobiphenyl Ketone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenyl-16- 201031708 milled, 3,3'-diaminodiphenyl maple, 3,4'- Diaminodiphenylphosphonium, 4,4'-diaminodiphenylmethane, 3,3'-aminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4' -diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 2,2-bis(4-aminophenyl) ) propane, 2,2-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl) Hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 1,1'-bis(4-aminophenyl)cyclohexane 〇, 〇-dimethoxyaniline, 〇-tolidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-Diaminobiphenyl, 4,4'-diaminophenylaniline, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3' ,5,5'-tetramethyl-4,4'-diaminodiphenyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3 , 3',5,5'-tetraethyl-4,4'-diaminobiphenyl, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4'-methylene-bis(2,6-diisopropylaniline), 4, 4'-Methylene-bis(2-ethyl-6-methylaniline), 3,3'-diethyl #yl-4,4'-diaminobiphenyl, 3,3'-dimethoxy -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diethyl-4,4'-diamino Diphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3, 3'-Diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 1,5- Diamine compound containing two benzene rings such as diaminonaphthalene or 2,3-diaminonaphthalene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-amino group) Phenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy) Benzene, 1,4-bis(3-aminophenyl)benzene, α,α'-bis-17- 201031708 (4-aminophenyl)-1,4-diisopropylbenzene, α,α a diamine compound containing 3 benzene rings, such as bis(4-aminophenyl)-1,3-diisopropylbenzene, 2,2-bis[4-(4-aminophenoxy)benzene Propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl], 2,2- Bis[4-(3-aminophenoxy)phenyl], 4,4'-(4-aminophenoxy)biphenyl, 4,4'-(3-aminophenoxy) Benzene, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(3-aminophenyl)anthracene, 9,9-bis(4-amino-3-methylphenyl) Ruthenium, 9,9-bis(4-amino-3-fluorophenyl) a diamine compound containing 4 or more benzene rings, such as ruthenium, 5,10-bis(4-aminophenyl)anthracene, 1,3-diaminoguanidine or 1,6-diaminoguanidine, 4, a diamine compound having an alicyclic structure such as 4'-methylene bis(cyclohexylamine) or 4,4'-methylene bis(2-methylcyclohexylamine), 1,4-diaminobutane, 1 , 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1 a diamine compound having a linear hydrocarbon structure such as 10-diaminodecane, 1,1 diaminoundecane or 1,12-diaminododecane, trade name Versamine 5 51 ( cognis Japan Diamine compound having a dimer diamine structure, such as manufactured by Jeffamine D-230, D-400, D-2000, D-4000, XT J-5 00, XTJ-501 'XTJ-502 &gt; HK -511 'XTJ-504' XTJ-542 &gt; XTJ-533, XTJ-536 (manufactured by huntsman Co., Ltd.), etc., a diamine compound having a polyoxyalkylene diamine structure. The diamine sulfoxane of the formula (5) preferably has a NH2 equivalent of from 400 to 6000 g/mol, more preferably from 40 Å to 2500 g/mol, and more preferably from 2010 to 31 MPa, more preferably from 400 to 1000 g/m. 〇l range. When the NH2 equivalent is larger than this range, the molecular weight of the oxime structure is large, so the hydrophobicity of the resin is too strong, and the compatibility with the thermosetting resin is poor, and the resin itself may have a polarity of the quinone and the oxime portion. The difference is too large and it is difficult to stabilize the resin synthesis. On the other hand, when the NH2 equivalent is less than this range, the molecular weight of the decane structure becomes small, and it is difficult to obtain sufficient flexibility. On the other hand, those having a phenyl group are preferred because they have good compatibility with a thermosetting resin. Ο When the tetrabasic acid dianhydride represented by the formula (3) and the diamine compound represented by the formula (4) and (5) (the diamine compound represented by the formula (6), the formula (4) to the formula (6) are represented by The reaction ratio of the total of the diamine compounds is not particularly limited, and may be any one of them. It is preferred to increase the functional group equivalent of all the diamine compounds used for the reaction from the viewpoint of improving the molecular weight of the obtained resin and improving the mechanical properties. The sum of the numbers is preferably equal to the number of functional group equivalents of the tetrabasic acid dianhydride. Specifically, the functional group equivalent number of the acid anhydride group of the tetrabasic acid dianhydride used is X, and the functional group equivalent number of all the amine groups of the amine compound used is γ, which is preferably 〇S|(XY)丨The reaction is carried out under the conditions of /XS 0.3, more preferably under the conditions of 〇S|(XY) I/XS0.1. The functional group equivalent number X (mol) of the acid anhydride group can be determined by the formula of X = B 1 / A1 when the functional group equivalent of the acid anhydride group is A1 (g/mol) and the input amount is B1 (g). In other words, the functional group equivalent is a molecular weight of a compound having one functional group, and the number of functional group equivalents is the number of functional groups indicating the weight (input amount) of the compound. Similarly, the functional group equivalent A2 (g/mol) of the amine group containing the HFA group-containing diamine compound represented by the formula (4), the input amount is B2 (g), and the diamine represented by the formula -19-201031708 (5) The functional group equivalent A3 (g/mol) of the amino group of the oxocyclone, the input amount is B3, the functional group equivalent of the amine group of the diamine compound represented by the formula (6) is A4 (g/mol), and the input amount is B4. (g) can be obtained by the formula of Y = (B2 / A2) + (B3 / A3) + (B4 / A4). The diamine compound represented by the formula (6) is an optional component, and when it is not contained, (B4/A4) = 0 in the above formula. Further, the ratio of the input of the diamine compound of the formulae (4) to (5) reflects the content of the oxirane structure and the content of the HFA group in the obtained resin, and therefore, by arbitrarily setting these two enthalpy The range of the ratio of the ratio of the diamine compounds of the formulae (4) to (5) is naturally determined. First, the amount of the oxymethane structure contained in the obtained resin is preferably from 40 to 90% by weight, more preferably from 50 to 80% by weight. When the proportion of the decane structure is more than 90% by weight, the viscosity of the resulting resin is increased and it is difficult to use. Conversely, when it is less than 40% by weight, the resin lacks flexibility. The content of the oxirane structure Z (% by weight) is when the weight of the yttrium imidized water is B5, which can be Z (% by weight) = {Β3/( ^

B1+B2 + B3 + B4-B5) } The formula of χ1〇〇 is obtained. B5 is the lower of the above X or γ as W, which can be obtained by the equation of B5 = 18xW. Further, when the diamine compound represented by the formula (6) is an arbitrary component, 'B4 = 0 in the above formula, when the component is not contained. The upper limit of the content of the structure of the saxophone is preferably from 8 〇% by weight, more preferably 7% by weight, more preferably 70% by weight, particularly preferably 65 重量% from the viewpoint of maintaining heat resistance at room temperature. %. The lower limit 含量 of the content of the structure of the chopping house is preferably from 50% by weight to more preferably from 54 to -20 to 201031708, more preferably 58% by weight from the viewpoint of exhibiting flexibility. Further, the upper limit 官能 of the functional group equivalent of the HFA group of the obtained polyimine resin (hereinafter referred to as HF A group equivalent) is too small from the amount of the HF A group in the resin, and the resin composition of the resin is used for hardening. The viewpoint of preventing incomplete hardening is preferably 1 0000 g/m ,l, more preferably 8 500 g/mol, still more preferably 6000 g/mol, still more preferably 5000 g/mol, and particularly preferably 4000 g/mol. The lower limit of the HFA group equivalent of the obtained polyimine resin is such that the crosslinking density increases when the resin composition is hardened due to the inclusion of a large amount of HFA groups, and the content of the siloxane structure is naturally reduced, in order to prevent hardening. The viewpoint of lowering the softness of the object is preferably 1 000 g/m〇l, more preferably 1 500 g/mol, still more preferably 2000 g/mol, still more preferably 2500 g/mol. The HFA group equivalent V (g/mol) of the polyimine resin is such that when the HFA group equivalent of the HFA group-containing diamine compound is Η, V(g/mol) = (B1+B2 + B3 + B4-B5) ) The formula of +(B2/H) is obtained. The diamine compound represented by the formula (6) is an optional component, and when it is not contained, φ B4 = 0 in the above formula. The terminal of the polyimine resin differs depending on the reaction ratio of the tetrabasic dianhydride to the diamine compound, and may be an amine group, an acid anhydride group or an acid anhydride group to form a ring-opened dicarboxy group. The reaction operation is not particularly limited. For example, heating and dehydrating imidization in a polymerization solution is preferred because it is easy to handle. Specifically, first, a solvent which is azeotroped with water, such as toluene or xylene, is added to a solvent in which a diamine compound having an HFA group and a siloxane diamine are dissolved in an inert gas atmosphere. Next, a tetrabasic acid dianhydride is added, and the reaction is carried out at 80 ° C or lower, preferably -21 - 201031708 0 to 50 ° C for 24 hours to obtain a polyaminic acid solution. The obtained polyaminic acid solution is heated at 1 Torr to 20 (TC, preferably 150 to 200 ° C, at which time the detached water is removed azeotropically with toluene, and the closed-loop can be obtained as a solution of the brewing amine. In the case where it is confirmed that the theoretical amount of water is distilled off and no water is found to flow out, the reaction is completed. Further, unlike this method, the acetic acid/pyridine mixed solution can be used to carry out the dehydration ring closure of polyglycine at a low temperature. The reaction solvent to be used in the reaction is not particularly limited as long as it does not react with the raw material and the obtained resin, and examples thereof include tetrahydrofuran, 1,4- dioxin, cyclopentanone, cyclohexanone, and γ-butyl. Internal vinegar, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, ethylene carbonate, propylene carbonate, ethyl cellulose Acetate, butyl cellulose acetate, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl isobutyl ketone, hydrazine-methyl pyrrolidone, hydrazine, hydrazine-dimethyl acetamide , hydrazine, hydrazine-dimethylformamide, dimethyl hydrazine, etc., preferably cyclohexanone, γ-butyrolactone. These solvents may be used alone. It is used in combination or in combination of two or more. It is particularly preferably a solvent such as cyclohexanone or γ-butyrolactone and an aromatic hydrocarbon solvent such as petroleum naphtha. The obtained polyimine resin solution is put into water or methanol. In a weak solvent such as a solvent, the polymer is precipitated and dried, and then re-dissolved in a solvent for use in combination. The upper limit of the number average molecular weight (Μη) of the polyimine resin of the present invention is from the resin. The viewpoint that the viscosity of the composition is increased to prevent the decrease in usability is preferably 50,000, more preferably 40,000, more preferably 30,000, still more preferably 25,000, and particularly preferably 20,000. In addition, the number average of the polyimide resin The lower limit 量 of the amount of the molecule 201031708 is preferably 9000, more preferably 10,000, more preferably 15,000, from the viewpoint of exhibiting flexibility of the resin composition. The weight average molecular weight (Mw) of the polyimine resin in the present invention The upper limit 値 is preferably 50,000, more preferably 40,000, more preferably 30,000, from the viewpoint of increasing the viscosity of the resin composition and preventing the decrease in usability. Further, the lower limit of the number average molecular weight of the polyimide resin is from Representing resin The viewpoint of the flexibility of the composition is preferably 9000, more preferably 10,000, still more preferably 15,000, particularly preferably 〇20000. The number average molecular weight and the weight average molecular weight are by gel permeation chromatography (GPC) method (polystyrene)値 measured by the GPC method, the number average molecular weight and the weight average molecular weight, specifically, the LC-9A/RID-6A manufactured by Shimadzu Corporation, and the column used by Showa Denko Co., Ltd. Shodex K-800P/K-804L/K-804L, mobile phase using a solution of 0.4% by weight of lithium bromide dissolved in N-methylpyrrolidone, and measured at a column temperature of 40 ° C, using a calibration curve of standard polystyrene Calculated. ® The resin composition of the present invention contains (B) a thermosetting resin. By mixing the thermosetting resin with the yttrium imine resin having the oxyalkylene structure obtained as described above, it is possible to obtain a thermosetting resin having a small heat-shrinkable shrinkage and having high flexibility and exhibiting high heat resistance and adhesion. Things. Examples of the thermosetting resin include an epoxy resin, a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound, a benzoxazine compound, an amine quinone compound, and a cyanate compound. In this case, a thermosetting resin having a functional group reactive with the HFA group contained in the resin (A) skeleton is selected, and among them, an epoxy resin having two or more glycidyl groups is more preferable. Also -23- 201031708 Add epoxy resin hardener, hardening accelerator, etc. The epoxy resin used in the embodiment of the present invention is not particularly limited as long as it contains two or more glycidyl groups. For example, there are phenols such as bisphenol A, bisphenol F, bisphenol S, resorcinol phenol novolac, cresol novolac, and the like, and glycidyl ethers such as butanediol, polyethylene glycol, and polypropylene glycol. An active hydrogen bonded to a nitrogen atom such as a glycidyl ether such as glycidyl ether, phthalic acid, isophthalic acid or tetrahydrophthalic acid, or a nitrogen atom such as aniline or trimeric isocyanate is substituted with a glycidyl group. Glycidyl type (also including methyl glycidol type) epoxy resin, vinyl cyclohexene diepoxide obtained by epoxidation of intramolecular olefin bonds, 3,4-epoxycyclohexylmethyl-3 , 4-epoxycyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc. An alicyclic epoxy resin, a glycidyl ether of a p-xylene-modified phenol resin, a glycidyl ether of a meta-xylene-p-xylene-modified phenol resin, a glycidyl ether of a terpene-modified phenol resin, and a dicyclopentadiene denaturation Glycidyl ether of phenol resin, glycidyl ether of cyclopentadiene-modified phenol resin, glycidyl ether of polycyclic aromatic ring-modified phenol resin, containing naphthalene The glycidyl ether of a cyclic phenol resin, a biphenyl type epoxy resin, or the like may be used singly or in combination of two or more. The monoepoxy compound may suitably be used in combination with an epoxy compound having at least two epoxy groups in the above one molecule, and the monoepoxy compound is, for example, a styrene oxide, a cyclohexene oxide, a propylene oxide, or a methyl group. Glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octene oxide, dodecene oxide, and the like. The epoxy resin to be used is not limited to one type, and two or more types may be used in combination. -24- 201031708 The epoxy resin hardener used in the embodiment of the present invention is not particularly limited as long as it is used to cure the epoxy resin, and examples thereof include a phenol compound, a carboxylic acid compound, an acid anhydride compound, and an amine system. A compound, a benzoxazine-based resin, an amine quinone-based resin, a cyanate-based compound, or the like. Among these hardeners, a phenolic compound is particularly preferred. The phenolic compound is preferably one having two or more phenol groups. For example, there are bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolac resin, cresol Φ phenolic resin, p-xylene modified phenol resin, meta-xylene, p-xylene modified phenol resin, decene denaturation Phenolic resin, dicyclopentadiene-modified phenol resin, cyclopentadiene-modified phenol resin, polycyclic aromatic ring-modified phenol resin, phenol resin containing naphthalene ring, biphenyl type epoxy resin, phenol resin containing triazine structure, etc. It can be used alone or in combination of two or more types. The carboxylic acid compound preferably has two or more carboxyl groups. For example, terephthalic acid 'isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, trimellitic acid, methyl nadic acid, dodecyl succinic acid ® , hexachlorobicyclo An organic acid such as heptene dicarboxylic acid, maleic acid or adipic acid may be used singly or in combination of two or more. The acid anhydride compound is preferably one having one or more acid anhydride groups. For example, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, hexachlorobicycloheptene dicarboxylic anhydride, Maleic anhydride or the like may be used alone or in combination of two or more. The amine compound can be used as a curing agent for addition reaction with an epoxy resin or anionic polymerization of an epoxy resin itself. For example, there are tertiary amines such as benzyldimethylamine-25-201031708, 2-(dimethylaminomethyl)phenol, 2,4,6-(dimethylaminomethyl)phenol, or 2 -methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methyl An imidazole such as imidazole, and an imidazolidine compound having both an imidazole moiety and a stanol moiety, ΙΜ-10 00 (daily ore metal (share)) or IS-1 000 (daily ore metal (share)), and 4,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3' -diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenyl milling, 3,3'-diaminodiphenyl milling, 3, 4'-diaminodiphenyl milling, 4,4'-diaminodiphenylmethane, 3,3'-aminodiphenylmethane, 3,4'-diaminodiphenylmethane, etc. An aromatic amine compound, an aliphatic amine compound such as m-xylenediamine, diethylenetriamine or tetraethylenepentamine, a melamine resin, or a 2-vinyl-4,6-diamino-s- Triazine The triazine compounds, urea and the like blind. The benzoxazine-based compound preferably has two or more benzoxazine moieties, and examples thereof include a B-a type benzoxazine and a B-b type benzoxazine (manufactured by Shikoku Chemical Industries Co., Ltd.). The amine quinone imine compound is a compound obtained by reacting a maleimide compound with an amine compound. Particularly preferred are those having two or more secondary amine groups, such as techmite E2020 (manufactured by Printech). The cyanate ester-based compound preferably has two or more cyanate groups, and examples thereof include Primaset BADCY, Primaset BA230S, Primaset LECY, and the like manufactured by lonza Japan Co., Ltd. The epoxy resin hardening accelerator used in the embodiment of the present invention is not limited to -26 - 201031708. For example, there are a phosphorus compound such as triphenylphosphine, triphenyltriphenylborate, tetraphenylphosphinium tetraphenylborate or benzyldimethylamine, 2-(dimethylaminomethyl) a tertiary amine such as phenol or 2,4,6-(dimethylaminomethyl)phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole An imidazole such as 2-phenylimidazole, 1-benzyl-2-methylimidazole or 1-cyanoethyl-2-methylimidazole, or guanylurea. The amount of the thermosetting resin in the resin composition is different depending on the specific type of hydrazine, and is generally different from that of (A) poly(imine) resin (B). The thermosetting resin is from 1 to 200 parts by mass, more preferably from 5 to 100 parts by mass. When the amount of the thermosetting resin is too small, the hardening is insufficient, and the chemical resistance and heat resistance may be inferior. When the amount is too large, the flexibility may be insufficient. Further, in the case of the epoxy resin, the stoichiometric ratio of the epoxy resin hardener to the sum of the HFA-based polyfluorene-containing polyimine resin in the skeleton is not particularly limited, but is preferably set to 0.7 to 1.3. The range is preferably 0.8 to 1.2. By setting it in this range, the unreacted partial pressure of the functional groups can be lowered, and the chemical resistance and electrical properties can be improved. In the polyamidene resin and the thermosetting resin which do not contain an HFA group and a siloxane, even if a siloxane resin is added separately, the compatibility may be inferior, and the HF A group and a siloxane structure are used. In the case of the quinone imine resin, the compatibility with the thermosetting resin tends to be better. It is preferred to add (C) an inorganic chelating agent to the resin composition of the present invention. By adding an inorganic chelating agent, it is possible to adjust the viscosity characteristics before curing, adjust the elastic modulus after hardening, and improve the strength to reduce the thermal expansion rate. The inorganic cerium filling material is, for example, cerium oxide, aluminum oxide, mica, mica (mica -27-201031708), ceric acid salt, barium sulfate, magnesium hydroxide, titanium oxide, etc., preferably cerium oxide or aluminum oxide, particularly preferably Yttrium oxide. The inorganic chelating agent preferably has an average particle diameter of 3 μηη or less, an average particle diameter of 1.5 μm or less, and an average particle diameter of preferably ι μιη or less from the viewpoint of insulation reliability. The average particle diameter can be measured by a laser diffraction/scattering particle size distribution measuring device LA-500 (manufactured by KK). The content of the inorganic filler in the resin composition is preferably from 5 to 60% by weight, more preferably from 5 to 30% by weight, based on 100% by weight of the nonvolatile component of the resin composition. When the content of the inorganic filler is less than 5% by weight, the effects of adjusting the viscosity, adjusting the modulus of elasticity, improving the strength, and lowering the thermal expansion ratio tend not to be sufficiently exhibited, and the content of the inorganic filler is more than 60% by weight. /. At the time, the softness of the cured product of the resin composition tends to be brittle. In the resin composition of the present invention, an organic hydrazine may be added as necessary. The organic chelating agent is, for example, acrylic rubber particles, polyoxyn oxide particles or the like. The organic chelating agent preferably has an average particle diameter of 3 μm or less, more preferably an average particle diameter of 1.5 μm or less, and more preferably an average particle diameter of Ιμηη or less. In the resin composition of the present invention, various resin additives, resin components other than the components (Α) and (Β), and the like can be added to the extent that the effects of the present invention can be exhibited. Examples of the resin additive include a tackifier such as Orben (manufactured by Shiraishi Kogyo Co., Ltd.) and Bentone (manufactured by Rheox Co., Ltd.), a polysulfonate system, a fluorine-based or acrylic-based antifoaming agent, a flattening agent, an imidazole-based compound, and a thiazole system. a surface treatment agent such as a triazole-based adhesion imparting agent or a decane coupling agent, a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, a phosphorus-containing compound, a bromine-containing compound, or the like. A flame retardant such as aluminum hydroxide or magnesium hydroxide, or phosphorus-28-201031708 is an antioxidant such as an antioxidant or a phenolic antioxidant. The resin composition of the present invention can be used for a solder resist ink, an adhesive film, a metal foil-attached adhesive film, a protective layer film, a prepreg, and a metal foil-containing prepreg. (Resistance Ink) The resin composition of the present invention is dissolved or dispersed in various organic solvents to form a paste, and a solder resist ink required for forming an insulating protective film for a printed circuit board can be produced. The organic solvent to be used herein is not particularly limited, and a solvent having a boiling point of 150 ° C or higher is preferably used, and a solvent having a boiling point of 180 ° C or higher is more preferably used. When a solvent having a boiling point of less than 150 °C is used, the solder resist ink is dried on the screen during the ink coating operation, and stencil mesh may be clogged. The solvent having a boiling point of 150 ° C or higher is, for example, N,N'-dimethylformamide, N,N'-diethylformamide, hydrazine, Ν'-dimethylacetamide, N-methyl. a solvent containing a nitrogen-containing compound such as 2-pyrrolidone or tetramethylurea, a solvent containing a sulfur-containing compound such as dimethyl arsenic, a solvent of a cyclic ester compound of γ-butyrolactone, a cyclohexanone, and a methyl group. An ketone-based solvent such as cyclohexanone or isophorone, an ether-based solvent such as diglyme or triglyme, an ester solvent such as carbitol acetate or propylene glycol monoethyl ether acetate. Such as polar solvents. These solvents may be used in combination of two or more kinds. If necessary, a nonpolar solvent such as an aromatic hydrocarbon may be appropriately mixed, and for example, a petroleum brain having a boiling point of 1 60 ° C or higher may be used. When the organic solvent is used arbitrarily in the resin composition of the present invention to form a paste, (A) a polyfluorene-containing resin having a siloxane structure and (B) a thermosetting resin, a solvent, a hardener, and a hardening accelerator are contained.塡 Filling material, -29- 201031708 Adding ingredients such as additives, using a planetary mixer, a 3-roller, a bead mill, etc., mixing, dissolving or dispersing to prepare. When the solid resin is mixed, a solution in which the solid resin is dissolved in an organic solvent is prepared in advance, and then the above kneading operation is carried out. (Adhesive film) The resin composition of the present invention may be used in the form of an adhesive film of a resin composition layer (layer A) and a support film (layer B) which are preferred forms for manufacturing a circuit board. Adhesive films are familiar to those skilled in the art and can be made according to known methods. For example, in the same manner as the above-described method for producing a solder resist ink, first, a (A) polyfluorene-containing resin having a siloxane structure and (B) a thermosetting resin, a solvent, a curing agent, a curing accelerator, a chelating material, and addition are added. Ingredients such as materials. Further, these components are kneaded, dissolved or dispersed using a planetary mixer, a three-roller, a bead mill or the like to prepare a resin composition varnish. Then, the resin varnish is applied onto the support film, and finally, the organic solvent is dried by heating or blowing hot air to form a resin composition layer, whereby an adhesive film can be produced. The support film is a support when the adhesive film is produced, and is finally peeled off or removed when the circuit board is manufactured or printed. The support film is, for example, a polyolefin such as polyethylene or polyvinyl chloride, a polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), a polyester such as polyethylene naphthalate, or a polycarbonate. The thickness of the resin composition layer (layer A) such as a metal foil such as release paper or copper foil varies depending on the use of the adhesive film. When the multilayer soft 30-201031708 circuit board is manufactured by the Build-Up Process, the thickness of the conductor layer forming the circuit is 5 to 70 μm, and therefore, the thickness of the layer corresponding to the interlayer insulating layer is preferably The range of 1〇~1〇〇μηι. Further, the thickness of the support film is not particularly limited, but is preferably from 10 to 150 μm, more preferably from 25 to 50 μm. The solvent for varnish preparation is not particularly limited. For example, a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, ethyl acetate vinegar vinegar vinegar '2-ethoxyethanol acetate, propylene glycol monomethyl ether acetate, carbitol acetic acid Acetate such as Φ such as ester, carbitol such as 2-ethoxyethanol or butyl carbitol, cyclic ester compound such as γ-butyrolactone, aromatics such as toluene, xylene, and petroleum brain A hydrocarbon, dimethylformamide, dimethylacetamide, hydrazine-methylpyrrolidone or the like. Among them, from the viewpoint of improving the drying property of the solvent at the time of film production, those having a boiling point of 160 ° C or less are preferable, and those having a boiling point of 100 ° C or less are more preferable. Further, these solvents may be used in combination of two or more types. The drying conditions are not particularly limited, and in order to maintain the adhesion ability, it is important that the thermosetting resin composition is not hardened during drying. Further, when a large amount of the organic solvent remains in the adhesive film, the expansion occurs after curing. Therefore, the ratio of the organic solvent in the resin composition layer is preferably 5% by weight or less, more preferably 3% by weight or less. . The specific drying conditions vary depending on the curability of the thermosetting resin composition or the amount or boiling point of the solvent in the varnish. For example, when the varnish contains 30 to 60% by weight of a solvent, it is preferably dried at 80 to 120 ° C. 3~15 minutes. Those skilled in the art can appropriately set the preferred drying conditions by simple experimentation. (Adhesive film with metal foil) -31 - 201031708 The resin composition of the present invention may contain an adhesive film of a resin composition layer (layer A) and a metal foil (layer C) which are preferable forms for manufacturing a circuit board. Form to use. Adhesive films with metal foils are familiar to those skilled in the art and can be made according to known methods. For example, the above adhesive film may be laminated with a metal foil. The support of the support film of the adhesive film described above is made of a metal foil, and another support can be laminated on the resin composition layer (layer A) on which the metal foil is formed. The type of the metal foil used for the adhesive film with a metal foil of the present invention is not particularly limited, and copper, nickel, aluminum, stainless steel, bismuth-copper alloy, phosphor bronze or the like can be used. However, as a metal foil for forming a printed circuit, It is preferably a copper foil. As the copper foil, a rolled copper foil or an electrolytic copper foil may be used, or an extremely thin copper foil with a carrier may be used. (Protective layer film) The resin composition of the present invention can be formed by forming an adhesive film containing a resin composition layer (layer A) and a heat-resistant film (layer D) which are preferable forms for manufacturing a circuit board. A protective layer film necessary for an insulating protective film of a printed circuit board. The protective layer film is familiar to those skilled in the art, for example, by preparing a varnish in which the resin composition of the present invention is dissolved in an organic solvent, and applying the resin varnish to a heat-resistant film by heating or blowing hot air or the like. The organic solvent is dried to form a resin composition layer. The heat-resistant film is a support for producing a protective film, but unlike the above-mentioned adhesive film, it is finally laminated on the outermost circuit of the circuit board when manufacturing a printed circuit board. The heat-resistant film is, for example, polyester such as PET or polyethylene naphthalate, polyimine, polyether phthalocyanine-32 - 201031708 amine, polyamidoximine, polyetheretherketone, polyether maple, liquid crystal Polymers, etc. The thickness of the resin composition layer (A) varies depending on the thickness of the conductor layer forming the circuit. When the thickness of the conductor layer is 5 to 70 μm, the thickness of the layer corresponding to the interlayer insulating layer is preferably 1 〇 to 1 〇〇. The range of μιη. Further, the thickness of the heat-resistant film is not particularly limited, and is preferably from 1 〇 to ΙΟΟ μηη, more preferably from 15 to 50 μm. The solvent for preparing the varnish is not particularly limited, and examples thereof include a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, ethyl acetate, butyl acetate, 2-ethoxyethanol acetate, and propylene glycol. Ethyl acetates such as methyl ether acetate and carbitol acetate; cyclic ester compounds such as carbitol and γ-butyrolactone such as 2-ethoxyethanol and butyl carbitol An aromatic hydrocarbon such as toluene, xylene or petroleum brain, dimethylformamide, dimethylacetamide or hydrazine-methylpyrrolidone. Among them, from the viewpoint of improving the drying property of the solvent at the time of film production, those having a boiling point of 160 t or less are preferable, and those having a boiling point of 100 ° C or less are more preferable. Further, these solvents may be used in combination of two or more types. 〇 Φ The drying conditions are not particularly limited, and in order to maintain the adhesion, it is important that the thermosetting resin composition is not hardened during drying. Further, when a large amount of the organic solvent remains in the adhesive film, the expansion occurs after curing. Therefore, the ratio of the organic solvent in the resin composition layer is preferably 5% by weight or less, more preferably 3% by weight or less. . The specific drying conditions vary depending on the hardenability of the thermosetting resin composition or the amount or boiling point of the solvent in the varnish. For example, when the varnish contains 30 to 60% by weight of a solvent, it is preferably dried at 80 to 120 ° C. 3~15 minutes. Those skilled in the art can appropriately set the preferred drying conditions by simple experimentation. -33- 201031708 (Prepreg) The prepreg of the present invention can be impregnated with a thermosetting resin composition of the present invention in a sheet-like reinforcing substrate containing fibers by a hot melt method or a solvent method to heat a half. Hardened to make. In other words, the prepreg in which the thermosetting resin composition of the present invention is impregnated with the flaky reinforcing substrate containing fibers can be formed. Further, as will be described later, an adhesive film containing a thermosetting resin composition is prepared by laminating both surfaces of a sheet-like reinforcing material. For the fiber-containing sheet-like reinforcing substrate, for example, a glass cloth or an aromatic polyamide fiber can be used, and it is often used as a fiber user for a prepreg. In the hot melt method, the thermosetting resin composition of the present invention is not required to be dissolved in an organic solvent, but the resin is applied onto a coated paper having a good release property, and then laminated on a sheet-like reinforcing substrate, or borrowed. A method of producing a prepreg by directly coating or the like by a die coater. Further, in the solvent method, the sheet-like reinforcing substrate is immersed in a resin varnish in which the thermosetting resin composition of the present invention is dissolved in an organic solvent, and the resin varnish is impregnated into the sheet @-shaped reinforcing substrate, in the same manner as the adhesive film. Then dry the method. (Prepreg with metal foil) A prepreg system with a metal foil is laminated on a metal foil to a prepreg impregnated with the resin composition of the present invention. The manufacturing method is not particularly limited. For example, a sheet-like reinforcing substrate impregnated with a resin varnish may be bonded to a metal foil and then dried. Further, a prepreg prepared in advance is laminated between the release film and the metal foil, and a prepreg with a metal foil can also be produced. Here, the type of the metal foil used for the metal foil prepreg of the present invention is not particularly limited, and copper, nickel, aluminum, stainless steel 'yttrium-copper alloy, phosphor bronze, or the like can be used. In general, a metal foil is often used as a copper foil, and a copper foil may be any one of a rolled copper foil, an electrolytic copper foil, and an extremely thin copper foil with a carrier. Adhesive film, adhesive film with metal foil, protective layer film, prepreg, prepreg with metal foil, and the surface of the resin composition layer on which the support is not adhered can be further laminated with a protective film according to the support . The thickness of the protective film is not particularly limited, but is preferably 1 to 40 μm, more preferably 10 to 30 μm. By laminating the protective film, it is possible to prevent dirt or the like from adhering to the surface of the resin composition layer or to prevent injury. Further, these can be wound into a drum shape for storage. Solder resist inks, protective film, and adhesive films can be used to form the outermost insulating protective film. Adhesive films, metal foil-attached adhesive films, prepregs, and metal foil prepregs can be used to make multilayer substrates other than the outermost layer. Reference (manufacture of a printed circuit board in which an insulating protective film is formed on the outermost layer) &lt;Insulation protective film by solder resist ink&gt;

The solder resist ink of the present invention is particularly suitable for the manufacture of flexible circuit substrates. Specifically, by applying the solder resist ink of the present invention to a predetermined portion of the flexible printed circuit board, by drying the coated surface, it is possible to obtain a soft print in which the entire surface or a part of the surface is protected by the solder resist of the present invention. Circuit board. The drying condition is suitably set by a person skilled in the art depending on the kind of the solder resist to be used, but at least the condition that the solvent constituting the solder resist ink is sufficiently dried and the resin composition is sufficiently thermally hardened. It is preferably dried at 100 to 200 ° C for 35 to 201031708 for 1 to 120 minutes. The thickness of the surface protective film to be formed is not particularly limited, and is preferably 5 to ΙΟΟμιη. The type of the flexible printed circuit board that protects the surface by the resin composition of the present invention is not particularly limited. For example, when various soft printed circuit boards such as a flexible printed circuit board for TAB, a flexible printed circuit board for COF, a multilayer flexible printed circuit board, and a conductive paste printed flexible printed circuit board are used, the resin composition of the present invention can be used. The resin composition of the present invention is particularly suitable for use as a protective coating film for a flexible printed circuit board for TAB or a flexible printed circuit board for COF.瘳 &lt;Preparation of Insulating Protective Film by Protective Layer Film&gt; The protective layer film of the present invention is particularly suitable for the production of a flexible circuit substrate. Specifically, first, the protective layer film of the present invention is bonded to a predetermined portion of the flexible printed circuit board by lamination using a vacuum laminator or by press lamination of a metal plate. Next, the resin composition layer (A) is cured to obtain a flexible printed circuit board having a full surface or a part of the surface protected by the protective layer film of the present invention. At this time, the pressure-bonding conditions are due to the type of the protective film used, and those skilled in the art can appropriately set them. The lamination is preferably carried out under reduced pressure at a temperature of 100 to 200 ° C, a pressure of 1 to 40 kgf/cm 2 and an air pressure of 20 mmHg or less. In addition, the lamination may be in the form of a batch or a continuous cylinder. The curing conditions are due to the type of the resin composition layer (A) to be used, and those skilled in the art can appropriately set them, but at least the resin composition must be sufficiently thermally hardened, preferably 100 to 200 ° C. ~1 20 minutes. -36-201031708 &lt;Production of Insulating Protective Film by Adhesive Film&gt; The adhesive film of the present invention is suitable as an insulating protective film for the outermost layer of a circuit board, similarly to the above-mentioned solder resist ink or protective layer film. Specifically, first, the adhesive film of the present invention is bonded to a predetermined portion of the flexible printed circuit board by lamination using a vacuum laminator or by press lamination of a metal plate. Next, after the support film (B) is peeled off, the resin composition layer (A) is cured to obtain a soft printed circuit board having a full surface or a part of the surface protected by the adhesive film of the present invention. The pressure-bonding condition at this time is due to the type of the protective layer film used, and those skilled in the art can appropriately set the pressure at a temperature of 100 to 200 ° C, a pressure of 1 to 40 kgf/cm 2 , and an air pressure of 20 mmHg or less. It is preferred to carry out the lamination below. In addition, the lamination may be in the form of a batch or a continuous drum. The curing conditions are due to the type of the resin composition layer (A) to be used, and those skilled in the art can appropriately set them, but at least the resin composition must be sufficiently thermally hardened, preferably 100 to 200 ° C. ~120 minutes. ❿ (Production of Multilayer Substrate) &lt;Case of Using Adhesive Film&gt; The adhesive film of the present invention is particularly suitable for the production of a multilayer flexible circuit substrate. Specifically, first, the adhesive film of the present invention is bonded to one side or both sides of a pre-made two-sided flexible printed circuit board by lamination using a vacuum laminator or press lamination with a metal plate. Next, the support film layer (B) was peeled off using a vacuum laminator, and the exposed resin composition layer (A) was bonded to another two-sided flexible circuit board -37-201031708 prepared in advance. Then, the resin composition layer (A) is cured. Finally, by forming a perforation, conduction between the layers is obtained, whereby a multilayer flexible printed circuit board can be obtained. At this time, the pressure-bonding condition is appropriately set by the person skilled in the art due to the type of the adhesive film to be used. The lamination is preferably carried out under reduced pressure at a temperature of 100 to 200 ° C, a pressure of l to 40 kgf / cm 2 , and an air pressure of 20 mmHg or less. In addition, the lamination may be in the form of a batch or a continuous drum. The curing conditions are due to the type of the resin composition layer (A) used, and those skilled in the art can appropriately set them, but at least the resin composition is sufficiently thermally hardened, preferably hardened at ~200 °C. 120 minutes. Further, a highly multilayered circuit substrate can be obtained by repeating the same operation. The circuit board to be used can simultaneously combine a single-sided circuit board or a double-sided circuit board, or a Rigid Flex circuit board in which a rigid (Rigid) circuit board such as a glass epoxy board and a flexible circuit board are combined. &lt;Case of using a metal foil-attached adhesive film&gt; The metal foil-attached adhesive film of the present invention is particularly suitable for producing a multilayer flexible circuit substrate. Specifically, first, the adhesive film of the copper foil of the present invention is bonded to a preformed two-sided flexible printed circuit board by lamination by a vacuum laminator or by press lamination of a metal plate. Face or two sides. Next, the resin composition layer (A) is cured, and finally, a pattern circuit is formed on the outermost copper foil to form perforations, and conduction between the layers is obtained, whereby a multilayer flexible printed circuit board can be obtained. At this time, the pressure-bonding condition is due to the type of the adhesive film used, and those skilled in the art can appropriately set the pressure at a temperature of 100 to 200 ° C, a pressure of 1 to 40 kgf / cm 2 , an air pressure of 20 mmHg and 201031708 or less. It is preferred to carry out the lamination below. In addition, the lamination may be in the form of a batch or a continuous drum. The curing conditions are due to the type of the resin composition layer (A) to be used, and those skilled in the art can appropriately set them, but at least the resin composition must be sufficiently thermally hardened, preferably at 100 to 200 ° C. ~120 minutes. Further, a highly multilayered circuit substrate can be obtained by repeating the same operation. Further, the means for forming the interlayer insulating layer necessary for manufacturing the multilayer circuit substrate is a means for simultaneously forming an insulating protective film of a circuit formed on the outermost layer of the multilayer substrate by using a bonding film with a metal foil and the above-mentioned adhesive film. Any of the foregoing solder resist inks, or a protective layer film or an adhesive film may be used. &lt;Case of Using Prepreg&gt; Next, a method of manufacturing the multilayer printed circuit board of the present invention using the prepreg of the present invention will be described. The prepreg of the present invention is laminated on one side of a pre-made two-sided flexible circuit board or The two-sided method includes, for example, a method in which a prepreg or a plurality of sheets of the prepreg are overlapped, and a release film is placed thereon, and a metal plate is placed and laminated by a laminating press under pressure and heating. At this time, the prepreg is laminated and hardened to the circuit substrate at the same time, the pressure is preferably 1 to 40 kgf/cm 2 , the temperature is preferably 100 to 200 ° C, and lamination is performed in the range of 1 to 120 minutes. Hardening is preferred. Further, the prepreg can be laminated on the circuit substrate by a vacuum laminator and then heat-hardened. In this manner, after forming an insulating layer as a cured product of the prepreg on the circuit substrate, if necessary, a via hole or a via hole or a through hole is formed on the insulating layer to roughen the surface of the insulating layer. Thereafter, a conductor layer is formed by electroplating, -39 - 201031708 to manufacture a multilayer printed circuit board. &lt;Case of using metal foil-containing prepreg&gt; The method of manufacturing the multilayer printed circuit board of the present invention using the metal foil-attached prepreg of the present invention and the above-described multilayer flexible circuit board using the prepreg The same way. The metal foil can be directly used as a conductor layer by using a prepreg with a metal foil. The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples. (Synthesis of Polyimine Resin) [Synthesis Example 1] 4,4,-(hexafluoroisophthalic acid) was added to a 500 mL separable flask equipped with a moisture metering device, a nitrogen introduction tube, and a stirrer connected to a reflux condenser. Propyl)-bis-(phthalic anhydride) (hereinafter referred to as 6FDA) 25 parts by mass, γ-butyrolactone 69.9 parts by mass, toluene 7 parts by mass, diamine-based decane oxime-22-9409 (Shin-Etsu Chemical Industrial (stock) system 55.7 parts by mass (amine equivalent 665 ), 2,6-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)- 1,5-naphthalene The amine (hereinafter referred to as HFA-NAP) was 6.7 mass, and the reaction was carried out by stirring at 45 ° C for 2 hours under a nitrogen stream. Subsequently, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene under a nitrogen flow while maintaining the temperature at about 160 °C. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water was not observed, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, it was cooled and finished, and a varnish containing a weight of HF A-based polyimine resin (A1) 55 and 201031708% was produced. The content of the siloxane structure in the resin at this time was 65.2% by weight, and the HFA group equivalent was 3313 g/mol. The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. For the coating film, when the infrared absorption spectrum was measured by the reflection method, no absorption based on the polyaminic acid showing an unreacted functional group was observed, and the absorption based on the quinone imine group was confirmed in ITSOcnr1 and 1 720 CHT1 at φ 3300. ～3500(:1^1) The absorption of the hydroxyl group derived from the HFA group was confirmed. Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was 5 g. The GPC measurement was carried out using this preparation solution, and Mn=11064 and Mw=18769 were measured. [Synthesis Example 2] A 500 mL separable flask equipped with a moisture metering device, a nitrogen introduction tube, and a stirrer connected to a reflux condenser was used. 32 parts by mass of 6FDA, 28.6 parts by mass of γ β butyrolactone, 28.6 parts by mass of ipzole 1 50, 7 parts by mass of toluene, and 50.1 parts by mass of diamino sulfoxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) were added ( 6.5 parts by mass of an amine equivalent of 430) and HFA-NAP, and the mixture was stirred at 45 ° C for 2 hours under a nitrogen stream to carry out a reaction. Then, the reaction solution was heated, and the water was condensed while maintaining a temperature of about 1 60 ° C under a nitrogen stream. Azeotrope with toluene When it is confirmed that the water quantitatively accumulates the amount of water and the water is not discharged, the temperature is raised again, and the mixture is stirred at 20 (TC for 1 hour), and then cooled and finished to prepare a polyimine resin (A2) having an HFA group. 55 wt% varnish. Ipzole is an aromatic system -41 - 201031708 high-boiling solvent. The rhodium content of the resin is 58.4 wt% and the HFA base equivalent is 3316 g/ The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes to dry. For this coating film, by reflection When the infrared absorption spectrum was measured by the method, the absorption based on the polyaminic acid showing the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1 780 CHT1 and 1 720 CHT1, and it was confirmed to be derived from the HFA group at 3300 to 3500 cnT1. The absorption of the hydroxyl group was measured, and 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was 5 g. The GPC measurement was carried out using the preparation solution, and Mn was measured. = 23 086, Mw = 3 5970. [Synthesis Example 3] 3,3',4,4'-benzophenone IV was placed in a 500 mL separable flask equipped with a moisture metering device, a nitrogen introduction tube, and a stirrer connected to a reflux condenser. 23 parts by mass of carboxylic acid dianhydride (hereinafter referred to as BTDA), 30 parts by mass of γ-butyrolactone, 3 parts by mass of ipzolel 50, 7 parts by mass of toluene, and diamine-based decane KF-8010 (Shin-Etsu Chemical Industry ( 4 parts by mass (amine equivalent 430), the reaction was carried out by stirring at 45 ° C for 1 hour under a nitrogen stream, followed by the addition of 3,3'-bis(1-hydroxytrifluoromethyl-2,2,2 -Trifluoroethyl)-4,4'-methyldiphenylamine (hereinafter referred to as HFA-MDA) 6.1 parts by mass was added, and the mixture was stirred at 45 ° C for 2 hours to carry out a reaction. Subsequently, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 °C under a nitrogen stream. When it is confirmed that the water quantitatively accumulates the amount of water accumulated and the water is not flowing out -42- 201031708, the temperature is raised again and stirred at 200 °C for 1 hour. Then, cooling and finishing were carried out to prepare a varnish containing 55 wt% of the polyimine resin (A3) having an HFA group. The content of the decane structure in the resin at this time was 64.9 wt%, and the HFA group equivalent was 327 1 g/mol. The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. With respect to this coating film, when the infrared absorption spectrum was measured by the reflection method, φ was not found to be absorbed based on the polyaminic acid showing an unreacted functional group, and the absorption based on the quinone imine group was confirmed at 1 780 CHT1 and 1 720 CHT1. 3300 to 3500 (^1^1) The absorption of the hydroxyl group derived from the HFA group was confirmed. Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the whole was prepared. 5g. Using this preparation solution, the GPC measurement was carried out, and it was found that Mn = l 8914 and Mw = 3 8256. [Synthesis Example 4] # 500 mL of a moisture quantitative receiver, a nitrogen introduction tube, and a stirrer connected to a reflux condenser To the separation flask, 20 parts by mass of BTDA, 70.9 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and 61.5 parts by mass of diamine-based decane X-22-940 9 (manufactured by Shin-Etsu Chemical Co., Ltd.) were added (amine equivalent 665). 7.4 parts by mass of HFA-NAP, and the reaction was carried out by stirring at 45 ° C for 2 hours under a nitrogen stream. Then, the reaction solution was heated, and the condensation water was mixed with toluene under a nitrogen flow while maintaining a temperature of about 1 60 ° C. Boiling off. Confirm moisture quantification When the amount of water accumulated and the amount of water not accumulated, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour, and then cooled and finished to prepare -43-201031708. Polyurethane resin (A4) having an HFA group 55 weight % varnish. The content of the decane structure in the resin at this time is 70.9 wt%, and the HFA base equivalent is 2881 g/mol. The obtained polyimine resin varnish is applied on a copper plate from 75 ° C to 120 ° °C was heated at 12 minutes and then dried by heating at 180 ° C for 90 minutes. For the coating film, when the infrared absorption spectrum was measured by the reflection method, no polyamine based on the unreacted functional group was found. Absorption, the absorption of the quinone imine group was confirmed at 1 780 CHT1 and 1 720 CHT1, and the absorption of the hydroxyl group derived from the HFA group was confirmed at 3 3 00 to 3 5 0001^1. Further, the obtained polyimide resin varnish 36 mg was weighed. The mixture was mixed with Ν-methylpyrrolidone in which 0.5% by weight of lithium bromide was dissolved, and the total amount was 5 g. The GPC measurement was carried out using the preparation solution, and Mn = 13135 and Mw = 3 5245 were measured. [Synthesis Example 5] Moisture metering device and nitrogen introduction of reflux cooler In a 500 mL separable flask of a tube or a stirrer, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride (hereinafter referred to as DSDA) was added in an amount of 19 parts by mass, γ-butyrolactone 22.7 parts by mass, and ipzolel. 50 22.7 parts by mass, 7 parts by mass of toluene, 30.9 parts by mass of diamine sulfoxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent 430), and the mixture was stirred at 45 ° C for 1 hour under a nitrogen stream to carry out a reaction. Then, 7.5 parts by mass of HFA-NAP was added, and the reaction was carried out by stirring at 45 ° C for 2 hours. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 1 60 ° C under a nitrogen stream. When it is confirmed that the water quantitatively accumulates the amount of water accumulated and the water does not flow out, the temperature is raised again and stirred at -44-201031708 2 00 °C for 1 hour. Then, cooling and finishing were carried out to prepare a varnish containing 55 wt% of the polyimine resin (A5) having an HFA group. At this time, the content of the decane structure in the resin is 55.7 wt%, and the HFA base equivalent is 18 1 Og/mol. The obtained polyimine resin varnish is applied on a copper plate from 75 ° C to 120 t to 12 The temperature was raised in minutes and dried by heating at 180 °: 90 minutes. For the coating film, when the infrared absorption spectrum was measured by the reflection method, it was found that the absorption based on the polyamic acid showing the unreacted functional group was found to be based on the quinone imine group at 1 780 (:1^1 and 1). The absorption of the hydroxyl group derived from the HFA group was confirmed at 3 3 00-3 500 (:1^1). Further, 36 mg of the obtained polyimide resin varnish and 0.4% by weight of N-methyl group dissolved in lithium bromide were weighed. The pyrrolidone was mixed and prepared to be 5 g in total. The GPC measurement was carried out using this preparation solution, and Mn = 2733 7 and Mw = 507 1 3 were measured, and the nitrogen in the tube was measured, but the device was subjected to a cold flow. 6 Preparation Example: Adding 6FDA 25 parts by mass, 68.1 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine-based decane -22-9409 in a 500 mL separable flask with a stirrer (Shin-Etsu Chemical Industry) (Stock): 58.4 parts by mass (amine equivalent: 665) and 1,5-diaminonaphthalene (hereinafter referred to as NDA) 1.8 parts by mass, and the reaction was carried out by stirring at 4 VC for 2 hours under a nitrogen stream. Next, the reaction solution was heated. Condensed water is mixed with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. The water was removed by boiling. When the water amount and the amount of water that did not accumulate in the water content meter were detected, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the cooling was carried out -45-201031708 'End' production containing no phenolic group and HF A The polyamicimide resin (B1) is 55 wt% varnish. At this time, the content of the structure of the sand oxide in the resin is 70.2% by weight. The obtained polyimine resin varnish is coated on the copper plate 'by 75° The temperature was raised at 120 to 120 ° C for 12 minutes, and then dried by heating at 18 ° C for 90 minutes. For the coating film 'infrared absorption spectrum by reflection method', no aggregation based on the unreacted functional group was observed. The absorption of proline was confirmed to be based on the absorption of quinone imine at 1 780 cm·1 and 1 720 CHT1. In addition, 36 mg of the obtained polyimide resin varnish and 0.4% by weight of N-methyl was dissolved in lithium bromide. The ketone was mixed and adjusted to a total of 5 g. GPC measurement was carried out using this preparation solution, and Mn = 15974 and Mw = 30002 were measured. [Synthesis Example 7] A moisture metering device, a nitrogen introduction tube, and a stirring provided with a reflux condenser were provided. Put into a 500mL separable flask 6FDA 36 parts by mass, γ Q butyrolactone 19.6 parts by mass, ipzolel 50 29.3 parts by mass, 7 parts by mass of toluene, diamine sulfoxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 1.5 parts by mass (amine equivalent 430 The reaction was carried out by stirring at 45 ° C for 1 hour under a nitrogen stream, followed by addition of 3.2 parts by mass of NDA, 16.4 parts by mass of γ-butyrolactone, and 6.7 parts by mass of ipZ〇lel 50, and the mixture was stirred at 45 ° C for 2 hours to carry out a reaction. Next, the reaction solution is heated, and maintained at about 160 ° C.

The condensed water was azeotropically removed together with toluene under a nitrogen stream. When confirming the water content and the amount of water accumulated by the accumulator and the outflow of water, the temperature is raised again, and the mixture is stirred at 200 ° C -46 - 201031708 for 1 hour. Then, the mixture was cooled and finished to prepare a varnish containing 55 wt% of a polyamidimide resin (B2) having no phenol group and HFA group. At this time, the content of the decane structure in the resin was 58.6 wt%. The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. With respect to this coating film, when the infrared absorption spectrum was measured by the reflection method, 'the absorption based on the polyamic acid showing the unreacted functional group was not found' was confirmed based on the quinone imine group at 〇1 780 cm -1 and 1 720 cm·1. Absorption. Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was 5 g. GPC measurement was carried out using this preparation solution. Mn = 33046 and Mw = 67573 were measured. [Synthesis Example 8] In a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a β stirrer connected to a reflux condenser, 23 parts by mass of BTDA, 29.5 parts by mass of γ-butyrolactone, 29.5 parts by mass of ipZ〇lel 50, 7 parts by mass of toluene, and 49.1 parts by mass of diamino sulfoxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent) 430), the reaction was carried out by stirring at 45 ° C for 1 hour under a nitrogen stream. Then, 4,4'-diamino-3,3'-dimethyldiphenylmethane (hereinafter referred to as C-100) was added in an amount of 2.6 parts by mass. The reaction was carried out by stirring at 45 ° C for 2 hours. Subsequently, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 °C under a nitrogen stream. When it is confirmed that the water quantified by the water quantitative accumulator accumulates and the water is not seen to flow out, the temperature is raised again, and the mixture is stirred at -47 to 201031708 200 ° C for 1 hour. Then, cooling and finishing were carried out to prepare a varnish containing 50% by weight of a polyimine resin (B3) having no phenol group and HFA group. At this time, the content of the decane structure in the resin was 68.0% by weight. The obtained polyimine resin varnish was applied to a copper plate 'by 75'. (:~120° (: heating at 12 minutes, and then drying at 180 ° C for 90 minutes to dry. For the coating film, when the infrared absorption spectrum was measured by a reflection method], no unreacted functional groups were found. The absorption of poly-proline was confirmed to be based on the absorption of quinone imine groups at 1 780 cm·1 and 1 720 CHT1. In addition, 36 mg of the obtained polyimide resin varnish and 0.4-% by weight of N-A dissolved in lithium bromide were weighed. The mixture of the pyrrolidone was adjusted to a total of 5 g. The GPC measurement was carried out using the preparation solution. Mn = 3 8 052 and Mw = 11020 were measured. [Synthesis Example 9] A moisture metering device, a nitrogen introduction tube, and a nitrogen introduction tube connected to a reflux condenser were provided. In a 500 mL separable flask of a stirrer, 9 parts by mass of DSDA, 55.2 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine-based oxazane-2 2-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) were charged. 44.1 parts by mass (amine equivalent: 665), the reaction was carried out by stirring at 45 t for 1 hour under a nitrogen stream, followed by the addition of 1,3-bis(4-amino-3-hydroxyphenoxy)benzene (hereinafter referred to as AHPB) 6.3 parts by mass. The reaction was carried out by stirring at 45 ° C for 2 hours. Then, the reaction solution was heated. The condensed water was azeotropically removed together with toluene while maintaining a temperature of about 1 60 ° C. It was confirmed that the water quantitatively accumulates the amount of water accumulated and the water does not flow out, and the temperature is raised again, and the mixture is stirred at 200 ° C for 1 hour. Then, cold-48-201031708 was completed and finished, and a varnish containing 55 wt% of the polyamidamine tree (B4) having no phenolic group and HFA group was prepared. At this time, the content of the oxime structure in the resin was 65.3% by weight, OH equivalent was 1744 g/mol. The obtained polyamidene resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further heated at 180 ° C for 90 minutes. For the coating film, when the infrared absorption spectrum was measured by the reflection method, no absorption based on the polyamic acid showing an unreacted functional group was found, and it was confirmed based on yttrium imine at φ 1 780 CHT1 and 1 720 cm-1. The absorption of the base was confirmed to be derived from the absorption of the phenolic hydroxyl group at 3,300 to 3,500 CHT1. Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the whole was prepared. 5g. GPC measurement using this preparation solution Mn = 1 443 0 and Mw = 2863 0. [Synthesis Example 1 〇] In a separable flask equipped with a 5 mM mL of a moisture metering device, a nitrogen inlet tube, and a _ agitator connected to a reflux condenser 19 parts by mass of DSDA, 54.5 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, 44.1 parts by mass of diamine oxime oxime-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent 66 5 ), under nitrogen flow The reaction was carried out by stirring at 45 ° C for 1 hour, followed by the addition of 5.4 parts by mass of 3,3'-diamino-4,4'-dihydroxydiphenyl maple (hereinafter referred to as DABS), and stirring at 45 ° C for 2 hours. reaction. Then, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 °C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water does not flow out, the temperature is increased again, and the mixture is stirred at 200 ° C for 1 hour. Then, -49-201031708 was cooled and finished, and a varnish containing 55 wt% of a polyamidimide resin (B5) having no phenol group and HFA group was produced. At this time, the content of the decane structure in the resin was 66.2% by weight, and the OH equivalent was 1,722 g/mol. The obtained polyimine resin varnish was applied onto a copper plate. The temperature was raised from 75 ° C to 120 ° C for 12 minutes, and further heated at 180 ° C for 90 minutes to dry. For the coating film, when the infrared absorption spectrum was measured by the reflection method, the absorption based on the polyamic acid showing the unreacted functional group was not found to be based on the quinone imine group at 1 7 80 cm·1 and 1 720 cm·1. The absorption was confirmed to be derived from the absorption of the phenolic hydroxyl group at 3300 to 3500 (:111-1. In addition, the obtained polyamidene resin varnish 36 6 mg and the lithium bromide dissolved in 4% by weight of N-methylpyrrolidone were weighed. The mixture was mixed and adjusted to a total of 5 g. The GPC measurement was carried out using the preparation solution, and Mn = l 663 1 and Mw = 30691 were measured. [Synthesis Example 1 1] A moisture metering device and a nitrogen introduction tube which are connected to a reflux condenser are provided. 20 parts by mass of BTDA, 76.5 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine-based oxazepine-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) 72.9 were placed in a 50 mL separable flask of a stirrer. The mass fraction (amine equivalent: 655) was stirred at 45 ° C for 1 hour under a nitrogen stream to carry out a reaction. Then, 2.7 parts by mass of HFA-NAP was added, and the mixture was stirred at 45 ° C for 2 hours to carry out the reaction. Then, the reaction solution was heated to maintain At a temperature of about 160 ° C 'under a nitrogen stream, the condensation water and The toluene was removed azeotropically. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water is not discharged, the temperature is further increased by stirring at 200 ° C for 14 hours. Then, cooling and finishing are completed to produce a polyfluorene having an HFA group. Amine resin (A6) 55 wt% varnish. At this time, the content of the decane structure in the resin was 78.0% by weight, and the HFA group equivalent was 8392 g/mol. The obtained polyimine resin varnish was coated on a copper plate. The temperature was raised from 75 ° C to 120 ° C for 12 minutes, and then dried by heating at 180 ° C for 90 minutes. For the coating film, when the infrared absorption spectrum was measured by a reflection method, no unreacted functional groups were observed. The absorption of the poly-proline was confirmed to be based on the absorption of the quinone group at 1 780 CHT1 and 1 720 CHT1, and the absorption of the phenolic hydroxyl group was confirmed at 〇3 300 to 3500 cm·1. 3 6 mg of the resin varnish was mixed with 0.4% by weight of methyl bromide dissolved in methylpyrrolidone to prepare a total of 5 g. The GPC measurement was carried out using the preparation solution, and Mn=1 9275 and Mw = 24,410 were measured. [Synthesis Example 1 2] Link reflow 20 parts by mass of BTDA, 58.5 parts by mass of γβ butyrolactone, 7 parts by mass of toluene, and diamine-based decane Χ-22 were placed in a 500 mL separable flask of a moisture metering device, a nitrogen introduction tube, and a stirrer of a cooler. -9409 (manufactured by Shin-Etsu Chemical Co., Ltd.), 37.3 parts by mass (amine equivalent: 655), and stirred at 45 ° C for 1 hour under a nitrogen stream to carry out a reaction, followed by addition of 16 to 4 parts by mass of HFA-NAP, and stirring at 45 ° C for 2 hours. . Then, the reaction solution was heated, and the condensation water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulating the amount of water accumulated and the amount of water not flowing out, the temperature was raised again, and the mixture was stirred at 200 ° C for 11 hours. Then, cooling and finishing were carried out to prepare a varnish containing 55 wt% of a polyimine resin (A7) having an HFA group. At this time, the content of the alkane-51 - 201031708 in the resin was 52.2% by weight, and the HFA group equivalent was 10 〇 69 g/mol. The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried by heating at 180 ° for 90 minutes. In the case where the infrared absorption spectrum of the coating film was measured by the reflection method, no absorption based on the polyaminic acid showing an unreacted functional group was observed, and absorption based on the quinone imine group was confirmed at 1 780 CHT1 and 1 720 CHT1. 3 00 to 3 500 (^1^1 was confirmed to be derived from the absorption of a phenolic hydroxyl group. Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and it was prepared. The whole was changed to 5 g. GPC measurement was carried out using this preparation solution, and Mn = 26629 and Mw = 3 7452 were measured. (Preparation of Resin Composition) Epoxy resin and oxime contained in the above Synthesis Examples 1 to 12 were synthesized. The polyalkylene imide resin of the alkane, if necessary, the hardener, the hardening accelerator, and the inorganic chelating material are mixed in the amounts shown in Tables 1 and 2 (expressed in parts by weight of the solid content), and centrifugal defoaming mixing is used. The product (product name "Defoaming Taro", manufactured by Thinky) was stirred and mixed to obtain the resin compositions of Examples 1 to 8 and Comparative Examples 1 to 7. Further, the epoxy resin was a phenolic epoxy resin. Resin EP157 (Japanese epoxy resin) East ZX1 059 C) or a mixture of bisphenol A type and bisphenol F type epoxy braking Kasei (shares) Ltd.). The hardener is a dicyclopentadiene-modified phenol resin DPP6115L (manufactured by Nippon Oil Co., Ltd.), the hardening accelerator is made of imidazole-based P200 (made by Nippon Epoxy Co., Ltd.), and the inorganic ruthenium is made of spherical. Cerium oxide SC4050SX (manufactured by admatechs). It is necessary to use -52- 201031708 when mixing solvents. (Preparation of cured film) Next, the obtained resin composition was applied onto a PET film subjected to a release treatment, heated at 75 to 120 ° C for 12 minutes, and then heated at 180 ° C for 90 minutes to obtain 40 μιη thick hardened film. 〇 (Solvent resistance test) The hardened film was placed on a scale, and a cotton rod containing acetone was used on the surface to make the scale display the log load, and the round friction was observed to observe the surface state of the cured film. When the color change of the surface of the cured film was not observed, it was evaluated as 〇, and when color detachment occurred, it was evaluated as X. (Heat resistance test) The polyimine resin obtained in the synthesis example was prepared in the same manner as described above, and applied to the shiny side of the copper foil so that the thickness during drying was 40 to ΙΟΟμηη, and 75 to 12 ( After heating the TC for 12 minutes, it was heated at 180 ° C for 90 minutes to obtain a cured film. The copper foil forming the cured film was immersed in a ferric chloride solution, and after etching, it was dried at 100 ° C for 1 minute to prepare a copper foil. After the removal of the hardened film, the hardened film from which the copper foil was removed was subjected to a tensile test using a TENSILON universal testing machine (manufactured by A&amp;D) according to Japanese Industrial Standards (JIS K7127) to determine the modulus of elasticity before heat treatment. The hardened film of the copper foil obtained by the above method is respectively -53-201031708, (1) 220 ° C in air, 30 minutes, (2) 250 ° C in air, 30 minutes, (3) 270 in air. Heat treatment was carried out at ° C for 30 minutes, and the cured film of the copper foil after the heat treatment was immersed in a ferric chloride solution, and after etching, the film was dried at 1 ° C for 10 minutes to prepare a cured film obtained by removing the copper foil. Copper foil is removed from the leaking hard The film was subjected to a tensile test according to the Japanese Industrial Standard (jIS K7127) using a TENSILON universal testing machine (manufactured by A&amp;D) to determine the elastic modulus of the cured film after heat treatment under various conditions. "Elastation rate after heat treatment + before heat treatment The elastic modulus is taken as the rate of change of the elastic modulus. In addition, the difference between the elastic modulus after heat treatment at 70 ° C for 30 minutes in air and the elastic modulus before heat treatment is taken as the variation width of the elastic modulus. Table 1 and Table 2 The results of the heat resistance test and the solvent resistance test of the polyimine resin composition described in the table are shown in the table. -54- 201031708

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Epoxy resin ΕΡ 157 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Hardening promotion Agent 0.1200 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Hard 匕 DPP6115L 3.7 3.8 3.7 Polyimine resin containing HFA based Α 1 / Synthesis Example 1 66 Α 2 / Synthesis Example 2 63.2 Α 3 / Synthesis Example 3 67.6 Α 4 / Synthesis Example 4 60.5 Α5/Synthesis Example 5 37.4 Non-functional Β 1 / Synthesis Example 6 33 Β 2 / Synthesis Example 7 60.5 BV Synthesis Example 8 35.8 Containing Β 4 / Synthesis Example 9 36.3 Β 5 / Synthesis Example 10 35.8 Elasticity (MPa) (Change Rate) 80 9 52 54 460 98 103 28 312 248 220 before heat treatment. . , 30 points 105 (1.3) 10 (1.1) 62 (1.2) 78 (1-4) 427 (0.9) 89 (0.9) 104 (1,0) 33 (1.2) 420 (1_3) 385 (16) 250 ° C , 30 points 102 (1.3) 10 (1-1) 59 (1-1) 84 (1.6) 472 (1.0) 102 〇.〇) 105 (1.0) 41 (1.5) 454 (1.5) 430 (1.7) 270° C, 30 points 154 (1.9) 11 (1.2) 59 (1,1) 80 (1.5) 453 (1_〇) 102 (1.0) 119 (1.2) 46 (1.6) 485 (1.6) 525 (2.1) Variation width 74 2 7 26 7 4 16 18 173 277 Solvent-resistant acetone resistance 〇〇〇〇〇 〇〇 〇〇HFA base children (g/mol) 3313 3316 3271 2881 1810 \ \ \ \ \ 矽 烷 韵 (*»% 65.2 58.4 64.9 70.9 55.7 70.2 58.6 68.0 65.3 66.2 -55- 201031708 [Table 2]

EXAMPLES Example 7 Example 8 Comparative Example ό Comparative Example 7 Epoxy Resin ZX1059 2 3 3 2 2 Hardening Accelerator P200 0.1 0.2 0, 2 0.1 0.1 _ 塡 Filling Material SC4050SX 5 10 10 5 5 Polyimine Resin HFA-based A1/synthesis example 1 69 A6/synthesis example 11 68.8 A7/synthesis example 12 22 non-functional group B1/synthesis example 6 33 phenol group-containing B4/synthesis example 9 38.5 Elasticity (MPa) (rate of change) Before heat treatment 124 6 1315 】21 395 220°C, 30 minutes 138 (U) 6 (1.0) 1383 (U) 128 (1.1) 441 (1.1) 250. . , 30 points 158 Π.3) 11 Π-81 1364 (10) 181 (1.5) 608 Π.5) 270 ° C, 30 minutes 183 (1.5) 11 (1-8) 1332 〇.〇) 173 (1-4) 663 0.7) Variation width 59 5 17 52 268 Solvent resistance acetone resistance 〇〇〇X 〇HFA basis weight (g/mol) 3313 8392 1069 矽 烷 含量 6 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 6 5.2 5.2 5.2 5.2 6 6 6 5.2 6 6 6 6 6 6 5.2 5.2 6 6 6 6 Table 1 and Table 2 results. As shown in Comparative Examples 1 to 3 and 6, the composition of the polyimine resin containing a HFA group and a phenol group containing a decyloxy group was poor in solvent resistance. This is because the reactivity of the polyimide resin with epoxy resin is low. Further, when a composition of a polyoxyimine resin having a phenol group-containing oxime structure was prepared, as shown in Comparative Examples 4, 5 and 7 of Tables 1 and 2, after heat treatment at 250 ° C for 30 minutes The rate of change of the modulus of elasticity is large, and the variation width of the modulus of elasticity becomes large. Then, Examples 1 to 3, 5, 6, and 8 of the composition containing the HFA-based polyfluorene-containing polyoxyimine resin were subjected to heat treatment at 250 ° C for 30 minutes. The rate is small &gt; exhibits excellent heat resistance and is excellent in solvent resistance. In Examples 4 and 7, the rate of change of the modulus of elasticity after heat treatment at 25 (TC, 30 minutes) was large, but the modulus of elasticity before heat treatment was itself a very small number of 60 MPa or less, and it was found that the flexibility can be sufficiently maintained. In the case of 2, 3, 5, and 8, it is known that the content of the oxime of the polyaniline resin having a HFA group containing a decane structure is not too large, and the rate of change of the elasticity rate is small, and the flexibility is maintained. [Example 9] (Production of Adhesive Film A1) The resin composition of Example 2 was applied onto a PET film having a thickness of 38 μm after the release treatment by a die coater to have a thickness of 40 after drying. After coating, it is dried at 75 to 120 ° C for 12 minutes to form an adhesive film A1 which forms a resin composition layer. Next, a polypropylene film having a thickness of 15 μm is bonded to the surface of the resin composition layer, and is wound up at the same time. -57-201031708 [Example 1 〇] (Production of Adhesive Film Α 2) Using the resin composition of Example 5, an adhesive film A2 was produced in the same manner as in Example 9. [Example 1 1] (Attachment) Resin copper foil B1 (manufacturing) @ The resin composition of Example 2 was applied onto a copper foil having a thickness of 12 μm using a die coater to have a thickness of 40 μm after drying. After coating, it was dried at 75 to 120 ° C for 12 minutes to form a film. A resin-attached copper foil B1 of a resin composition layer. Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer, and wound into a roll shape at the same time. [Example 1 2] (copper foil with resin) Manufacture of Β2) Using the resin composition of Example 5, copper foil Β2 with resin was produced in the same manner as in Example 11. [Example 1 3] (Production of protective layer film) Using a die coater The resin composition of Example 2 was applied onto a polyimide film having a thickness of 25 μm to a thickness of 35 μm after drying. After coating, it was dried at 75 to 120 ° C for 12 minutes to form a resin composition layer. -58- 201031708, a protective film was produced. Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer, and wound into a roll shape at the same time. [Example 1 4] (Manufacture of solder resist ink) Modulation Resin of Example 2 In the case of the composition, the solid resin is dissolved in a high-boiling solvent, and the mixture is stirred and mixed by a centrifugal defoaming mixing machine (trade name "Defoaming Taro" or "Thinky"). [Example 1 5] (Evaluation of Manufacturing and Bending Durability of Flexible Circuit Board P1) First, the polypropylene film of the protective layer film produced in Example 13 was peeled off. Secondly, a copper layer was used ( a circuit surface of a soft circuit board obtained by a thickness of 12 μm η and a two-layer CCL (copper clad laminate β) composed of a polyimide film (thickness 20 μm) is opposed to a resin composition surface of the protective layer film by vacuum lamination The machine (manufactured by Nihon Seiki Co., Ltd.) was laminated at a temperature of 130 ° C, a pressure of 7 kgf / cm 2 , and a gas pressure of 5 mmHg or less. Subsequently, the film was heat-hardened in the order of (1) 120 ° C, 30 minutes, (2) 180 ° C, and 90 minutes to prepare a single-sided circuit board P1. When the surface of the protective layer film was made to the outside and the test was performed by bending to 180 degrees, whitening was not caused in the bent portion of the protective layer film, and good bending property was exhibited. [Example 1 6] -59- 201031708 (Evaluation of manufacturing and bending durability of flexible circuit board P2) The solder resist ink obtained in Example 14 was printed on a copper layer using a 2 〇〇mesh version of the screen. The circuit surface of a flexible circuit board obtained by a two-layer CCL composed of a polyimide film (thickness: 20 μm) was cured at 180 ° C for 90 minutes to form a single-sided circuit board Ρ 2 . After the production, the solder resist surface of the single-sided circuit board P 2 was subjected to a test of bending to 180° on the outer side, and no whitening or the like was observed in the bent portion of the protective layer film to exhibit good bending property. [Example 1 7] (Manufacture of multilayer flexible circuit board MP1 and measurement of peel strength)

First, the polypropylene film of the adhesive film A1 produced in Example 9 was peeled off. Then, the circuit surface of the flexible circuit board obtained by using the two layers of CCL composed of a copper layer (thickness 12 μm) and a polyimide film (thickness 20 μm) is opposed to the resin composition surface of the adhesive film by vacuum lamination The machine (manufactured by Nihon Seiki Co., Ltd.) was laminated at a temperature of 13 ° C, a pressure of 7 kgf / cm 2 , and a Q pressure of 5 mmHg or less. Then, the release-treated PET film of the adhesive film is peeled off, and the surface of the resin composition is opposed to the surface of the copper foil having a thickness of 18 μm, and then a vacuum laminator (manufacturing machine) Lamination was carried out under the conditions of a temperature of 13 ° C and a pressure of 7 kgf / cm 2 'air pressure of 5 mmHg or less. Further, heat treatment was carried out in the order of 120 ° C, 30 minutes, 180 ° C, and 90 minutes to produce a multilayer flexible circuit board MP1. The peeling strength of the conductor layer (corresponding to the S surface of the copper foil) on the circuit board MP1 and the adhesive film is 94.94 kgf/cm, and has strong adhesiveness. Peeling -60- 201031708 The strength measurement was evaluated in accordance with JIS C6481. [Example 1 8] (Production of multilayer flexible circuit board MP2 and measurement of peel strength) First, the polypropylene film of the adhesive film A2 obtained in Example 10 was peeled off. Then, an electric Φ road surface of a soft circuit board obtained by using a copper layer (thickness 12 μm) and a two-layer CCL composed of a polyimide film (thickness 20 μm) is opposed to the resin composition surface of the adhesive film by vacuum The laminator (manufactured by Nihon Seiki Co., Ltd.) was laminated at a temperature of 130 ° C, a pressure of 7 kgf / cm 2 , and a gas pressure of 5 mmHg or less. Then, the release-treated PET film of the adhesive film is peeled off, and the surface of the resin composition is opposed to the surface of the copper foil having a thickness of 18 μm, and is further produced by a vacuum laminator. The lamination was carried out under the conditions of a temperature of 130 ° C, a pressure of 7 kgf / cm 2 , and a gas pressure of 5 mmHg or less. Further, heat treatment was performed at 120 ° C for 30 minutes '18 (TC, 90 minutes) to produce a multilayer flexible circuit board β ΜΡ 2. The conductor layer on the circuit board ΜΡ 2 (corresponding to the S surface of the copper foil) and the peeling strength of the adhesive film l. 〇 5 kgf / cm, with strong adhesion. Peel strength measurement was evaluated in accordance with JIS C648 1. [Example 1 9] (Manufacture of multilayer flexible circuit board MP3) First, the resin obtained in Example 11 was used. The polypropylene film of the copper foil B1 is peeled off. Then, the circuit board and the resin of the soft circuit board -61 - 201031708 obtained by using a two-layer CCL composed of a copper layer (thickness 12 μm) and a polyimide film (thickness 20 μm) are used. The surface of the resin composition of the copper foil B1 was opposed to each other, and lamination was carried out under the conditions of a temperature of 130 ° C, a pressure of 7 kgf / cm 2 , and a gas pressure of 5 mmHg or less by a vacuum laminator (manufactured by Nihon Seiki Co., Ltd.). Heat treatment was carried out in the order of ° C, 30 minutes, 180 ° C, and 90 minutes to produce a multilayer flexible circuit board MP3. [Example 20] (Manufacture of multilayer flexible circuit board MP4) First, the resin obtained in Example 12 was used. Copper foil B2 The propylene film is peeled off. Then, the circuit surface of the flexible circuit board obtained by the two layers of CCL composed of the copper layer (thickness 12 μm) and the polyimide film (thickness 20 μm) and the resin composition of the resin-coated copper foil Β2 are used. In the opposite direction, lamination was carried out under the conditions of a temperature of 130 ° C, a pressure of 7 kgf / cm 2 , a gas pressure of 5 mmHg or less by a vacuum laminator (manufactured by Nihon Seiki Co., Ltd.), and then at 120 ° C, 30 minutes, and 180 ° C. The multilayer soft circuit board MP4 is manufactured by heat treatment in the order of 90 minutes. The present application is based on Japanese Patent Application No. 2008-288152, the entire contents of which are incorporated herein by reference.

Claims (1)

201031708 VII. Application for Patent Park: 1. A resin composition for a printed circuit board, characterized by (A) a polyimide resin having a hexafluoroisopropanol group and a decane structure and (B) a heat hardening Resin. 2- A resin composition for a printed circuit board according to the first aspect of the patent application, which further comprises (C) an inorganic ruthenium filler. 3. The resin 〇 composition for a printed circuit board according to claim 1 or 2, wherein the thermosetting resin is an epoxy resin. 4. The resin composition for a printed circuit board according to any one of claims 1 to 3, wherein the polyimine resin has the following formulas (1) and (2) 0 0 +ΝγΚΐγΜ_Κ34 0 〇 (2) (wherein R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, and R3 represents a divalent alkoxyalkylene diamine residue by formula (1) The repeating unit expressed by the number of repetitions in one of the repeating units Μ is an integer of 1 or more and 100 or less, and the repeating unit of the repeating unit represented by the formula (2) is an integer of 1 or more and 100 or less. . 5. The resin composition for a printed circuit board according to any one of claims 1 to 4, wherein the hexafluoroisophthalene of the polyfluorene imide resin having a hexafluoroisopropanol group and a decane structure The resin composition for a printed circuit board according to any one of the items 1 to 5, wherein (Α) has a hexafluoroiso group, the functional group equivalent of the propanol group is -63-201031708, which is a resin composition for a printed circuit board according to any one of claims 1 to 5. The polyamidene resin having a propanol group and a decane structure has a decane content of 50 to 80% by weight. A solder resist ink comprising a resin composition for a printed circuit board according to any one of claims 1 to 6. 8. An adhesive film which is characterized in that a resin composition layer for a printed circuit board according to any one of items 1 to 6 of the patent application is formed on a support. 9. A metal foil-attached adhesive film </ RTI> formed by forming a resin composition layer for a printed circuit board according to any one of claims 1 to 6 on a metal foil. A prepreg characterized in that the resin composition for a printed circuit board according to any one of the above-mentioned claims is immersed in a sheet-like fibrous base material. 11. A metal foil-containing prepreg' characterized in that a metal foil is laminated @ in the prepreg of claim 10 of the patent application. A protective layer film formed by forming a resin composition layer for a printed circuit board according to any one of claims 1 to 6 on a heat-resistant film. A printed circuit board comprising a resin composition for a printed circuit board according to any one of claims 1 to 6. 1 4. The printed circuit board of claim 13 wherein said insulating layer comprises a solder resist layer 'interlayer insulating layer and a protective layer. -64- 201031708 15. A printed circuit board characterized in that a solder resist layer is formed by the solder resist ink of claim 7 of the patent application. 16. A printed circuit board characterized by forming a solder resist layer by an adhesive film of claim 8 of the patent application. 17. A printed circuit board characterized by forming an interlayer insulating layer by an adhesive film of claim 8 of the patent application. 18. A printed circuit board characterized by forming an interlayer insulating layer and/or a conductor layer by an adhesive film attached to a metal foil of claim 9th. A printed circuit board characterized by forming an interlayer insulating layer by the prepreg of the first application of the patent application. 20. A printed circuit board characterized by forming an interlayer insulating layer and/or a conductor layer by a metal foil prepreg according to claim 11 of the patent application. 21. A printed circuit board characterized by forming a protective layer by a protective film of claim 12 of the patent application. -65- 201031708 IV. Designated representative 闽·· (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: None 201031708 V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none