TW201130888A - Polyimide resin, method for producing same, adhesive resin composition, coverlay film and circuit substrate - Google Patents

Abstract

Provided is a polyimide resin obtained by reacting the keto group of a polyimide siloxane having constitute units represented by the following formula (1) and (2), with an amino compound having at least two primary amino groups as functional group. [wherein, Ar represents a four-valent aryl group derived from aromatic tetra carboxylic acid anhydride, R1 represents a two-valent diaminosiloxane residue derived from diaminosiloxan, R2 represents a two-valent aromatic diamine residue derived from aromatic diamine, Ar and/or R2 containing a keto group, m and n represent the exist mole ratio of each constitute unit, m is in the range of 0.75 to 1.0, n is in the range of 0 to 0.25].

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin which can be used as an adhesive in a circuit board such as a flexible printed circuit board, a method for producing the same, and a use thereof. [Prior Art] In recent years, with the progress of miniaturization, weight reduction, and space saving of electronic equipment, a flexible printed circuit board (FPC) which is thin, lightweight, and flexible, and has excellent durability even if it is repeatedly bent. : The need for Flexible Printed Cinmits) has increased. Since the FPC system can be formed in a three-dimensional and high-density space, the use of the movable portion of an electronic device such as an HDD, a DVD, or a mobile phone, or a component such as a cable or a connector, continues to expand. In the FPC, a cover film can be used for the purpose of protecting the wiring portion. The cover film is formed by laminating a film for covering a synthetic resin such as a polyimide film with a binder layer. In the production of FPC, a film for covering is applied to a circuit board via an adhesive layer by a method such as hot stamping. The adhesive layer requires high adhesion to both the wiring pattern of the copper wiring and the film for covering. In the case of such an adhesive for a cover film, it has been proposed that it can be processed at a relatively low temperature by thermocompression bonding, and has excellent properties such as heat resistance, and is suitable for the combination of a polyimide resin having an oxynitride unit and an epoxy resin. In the resin, an adhesive resin composition for a printed circuit board which is obtained by mixing one or more kinds of plasticizers selected from the group consisting of a phosphate ester, a phthalate ester, a polyester, and a fatty acid ester (for example, Patent Document 1). 322574 4 201130888 In addition, in order to improve the low-temperature adhesion, low hygroscopicity, adhesion to heat, and PCt resistance of the polyimide film which is used in the film, it has been proposed to make bis(3,4-di) A method for producing a polyimine resin which reacts with other acid anhydrides and/or other diamines after reacting with a specific structure of oxime-monoamine (for example, Patent Document 2). Moreover, the purpose of safely and safely manufacturing a high molecular weight polyimine resin having a polyoxonium structure in the main chain has also been proposed to make the polyoxonium diamine and the polyoxyl acid two needles specific to the molar. a method for producing a polyimine resin having a molecular weight adjusted by mixing and dehydrating and condensing in a specific range, and reacting until the molecular weight is not increased, and reacting the aromatic diamine with a specific molar ratio in the reaction liquid (for example, Patent Literature) 3). [PATENT DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] In the processing of FPC, it is almost necessary to include a soldering step. Therefore, an adhesive used for a cover film is required to have a high heat resistance. In this regard, the polyimide resin having excellent heat resistance is suitable as the material of the adhesive for the cover film. However, if the heat resistance of the joint is further improved, the function as an adhesive for the cover film can be further enhanced. In the electronic equipment for vehicles using the FPC, it is placed in a high-temperature environment of about 150 °C by 322574 5 201130888. Therefore, the use of the FPC cover film and wiring is reduced during long-term use, and the wiring protection function is reduced. Dramatically reduce the problem. In the case where the use of the FPC is expanded, it is not limited to the electronic device for vehicles, and the FPC is used in a severe temperature environment in the same manner, and will increase in the future. In this way, it is strongly sought to reduce the adhesion force of the cover film in the FPC used in a high-temperature environment. Therefore, an object of the present invention is to provide a polyimide resin having excellent solder heat resistance, further repeated exposure to a high temperature, and an adhesive layer which does not lower the adhesion between the wiring layer and the cover film. . [Means for Solving the Problem] The inventors of the present invention have found that the ruthenium iodide-containing polyimine resin reacts with the amine compound having a first-order amine group in order to solve the above problems. The solder heat resistance of the polyimide resin is remarkably improved, and the reduction in the adhesion force is greatly improved even in the use of a high-temperature environment, and the present invention has been completed. That is, the polyimine resin of the present invention is a ketone group having a polyfluorene imine oxime having a constituent unit represented by the following general formulae (1) and (2), and having at least two The amine group of the amine group of the first-order amine group reacts to form a C=N bond, and has a structure in which the above-mentioned polyamidoxime oxime is crosslinked by the above-described amine compound. 6 322574 201130888 ΟΛΥΟ ΟΛΥΟ Ν v-1_> ο ο '

χ JJ (2) η ΝγΑΓγΝ — R2. ο ο [wherein, each Ar represents a tetravalent aromatic group derived from an aromatic tetracarboxylic anhydride, and R1 represents a divalent value derived from a diamine siloxane. a diamine-based oxime-burning residue, R2 represents that (4) a divalent aromatic diamine residue derived from a scented diamine contains a ketone group in Ar and/or R2, and m and n represent the presence of each constituent unit. The adhesive resin composition of the present invention contains the following components (A and (8); (A) has the following formula (in the range of 'm is 〇.75 to 1 ,, to 〇25). 1) and (2) a constituent unit having a weight average molecular weight of 1 〇, 〇〇〇 to 200,000; and (B) an amine having at least 2 primary amine groups as a functional group The base compound contains the above-mentioned (B) component in a range of from 〇〇〇4 mol to 15 mol with respect to the ketone group 1 mole in the above component (A). 322574 7 201130888 ΟΛγο ΑΓ ΟΛΥΟ Ν V—____> 〇〇AXN—R2· Τ Τ ο ο ·· (2) [wherein, each Ar represents an aromatic tetracarboxylic anhydride a tetravalent aromatic group derived from a living group, I represents a divalent diamine oxime residue derived from a diamine siloxane, and R 2 represents a divalent aromatic diamine residue derived from an aromatic diamine. The ketone group is contained in Ar and/or R2, and m and η represent the molar ratio of each constituent unit, m is in the range of 0.75 to 1.0, and η is in the range of 0 to 0.25. The cover film of the present invention is obtained by curing the adhesive composition of the present invention. The cover film of the present invention is a cover film for laminating the adhesive layer and the cover film layer, wherein the adhesive layer is made of the above adhesive resin. The circuit board 5 of the present invention includes a substrate, a wiring layer formed on the substrate, and the cover film covering the wiring layer. In this case, at 150 ° C for 1,000 hours in the air. The peeling strength of the wiring layer and the cover film after the long-term heat resistance test is preferably 〇.2 kN/m or more. The method for producing the polyimine resin of the present invention comprises: preparing 8 322574 201130888 containing a ketone group Step of the polyimine solution of polyamidooxane a step of adding an amine compound having at least two first-order amine groups as a functional group to the polyimine solution; and subjecting the ketone group of the aforementioned polyamidoxime to the amine of the amine compound In the step of condensing the ketone group, it is preferred to add an amine compound to the ketone group 1 molar in such a manner that the total of the first-stage amine groups is in the range of 0.004 mol to 1.5 mol. Further, there is a step of reacting an acid anhydride component containing an aromatic tetracarboxylic dianhydride with a diamine component containing a diamine sulfoxane and an aromatic diamine to form the polyimine oxime, and the aroma of the raw material At least one of the tetracarboxylic dianhydride and the diamine component contains a ketone group. A method of manufacturing a circuit board according to the present invention, comprising: a substrate, a wiring layer formed on the substrate, and a circuit substrate on which a cover film covering the wiring layer is formed, wherein: a step of coating and drying the coating resin composition on the coating film layer to form a coating film of the adhesive layer in a state of a solution; and arranging the coating film so that the adhesive layer is adjacent to the wiring layer, and performing hot pressing Next, the ketone group of the component (A) and the amine group of the first component of the component (B) are subjected to a condensation reaction to form a C=N bond simultaneously with the thermocompression bonding. In the above aspects of the invention, the aforementioned amine compound is preferably a diterpene compound. [Effect of the Invention] 322574 201130888 The polyimine resin of the present invention is contained in the arsenic and/or R2 of the polyimine oxime having the constituent units represented by the general formulae (1) and (2). a ketone group having a crosslinked structure obtained by reacting with an amine compound having at least two primary amine groups as a functional group, so that the welding property is excellent, and at the same time, it is repeatedly placed in a high temperature environment to form a metal wiring layer. The adhesive layer which does not reduce the adhesive force is > Therefore, the use of the polyimide resin of the present invention improves the peeling strength of the cover film of the formed adhesive layer, and the reliability of the circuit substrate using the cover film can be improved. [Embodiment] [Formation for Carrying Out the Invention] [Polyimide Resin] The polyanilin resin of the present invention is obtained by having a constituent unit represented by the general formulae (1) and (2) The Ar and/or κ of the amine alkoxy group contains a lysine and reacts with an amine compound having at least two primary amino groups as a functional group to form a bond (> a structure in which an oxyalkylene is crosslinked by an amine compound. The group Ar in the above formulas (1) and (2) represents a tetravalent aromatic group derived from an aromatic tetra-salt anhydride, and is represented by a diamine-based oxyfluoride. a divalent diamine fluorinated alkane residue, the group representing a divalent aromatic diamine residue derived from an aromatic diamine. The constituent unit represented by the formula (丨) in the resin is present in an amount of 75 In the range of % to 100% by mole, preferably in the range of 80% by mole to 1% by mole. [Polyimine oxime] having the above formula (丨), (2 ) shown in the composition of the unit of the brew 10 322574 201130888 imine oxime, the base Ar and / or base by the total person + t 丞 heart contains a ketone group, this ketone is related to the amine In the structural unit t represented by the general formulae (1) and (2), the aromatic (10) acid which is used to form the group of the formula (1) can be, for example, 3,3',4 which is not represented by the following formula (1). , 4,-benzophenone tetracarboxylic dianhydride (btda).

Further, in the constituent units represented by the formulae (1) and (7), the aromatic tetrabasic acid which is a raw material for forming the group r may be used in addition to the above-described mercapto group, and the like, 3,3,4,4-diphenyl can be used. Base tetracarboxylic acid ## (BpDA), 3,3', 4,4'. diphenyl-based tetrakis(tetra) dianhydride (dsda), pyromellitic acid di-hepatic (PMDA), and the like. These may be used alone or in combination of two or more. Further, in the structural unit represented by the formula (1), as the group &, a diamine-based oxirane residue derived from the second-line Weilai of the formula (4) is exemplified. R? H2N -~~丨丨一丨丨一(4)(4) R6 R8 [R3 and R4 are respectively a divalent organic group which may also contain an oxygen atom, and a 5 to r8 knife is not a cigarette base having a carbon number of j to 6; The average number of repetitions is 1 to 20] q 322574 11 201130888 In particular, as the base, in order to impart solubility to the polyimine, R3 and R4 in the formula (4) are respectively a divalent hydrocarbon group, and R5 to r8 are respectively a carbon number of 1 The average number of repeats of the hydrocarbyl groups to 6 is from 5 to 15. The above diaminocarboxane residue has a base of a siloxane chain (Si-O-Si) which removes an amine group from a diamine siloxane, but by increasing the ratio of the oxime bond The inability to blend the plasticizer can also impart sufficient flexibility to the adhesive layer to inhibit the distortion of the cover film. Further, since the plasticizer contains a plurality of polar groups, the advantages of the plasticizer are not formulated, and for example, it can be suppressed by using the polyimine oxide having the constituent units represented by the general formulae (1) and (2). The amount of the polar group contained in the resin composition of the alkoxide. Therefore, in the present invention, the value of m in the formula (1) is 〇75 or more, preferably 0.80 or more, and the value of m is less than 0.75, and the effect of suppressing the light curvature cannot be sufficiently obtained. Further, it is considered that by increasing the siloxane chain, the effect of reducing the hardening shrinkage caused by the decrease in the yttrium bond site of the polyimine oxime is also exhibited. In this way, the value of n in the formula (2) is 〇 to 25, preferably in the range of 〇 to 〇2. Thus, by using the diamino methoxy oxane represented by the above formula (4), a oxoxane skeleton is introduced into the polyiminimide, and the obtained polyamidiamine oxirane is given a heat-bonding bond. The fluidity of time can improve the filling of printed circuit lines. The specific example of the diamine-based oxy-oxygenation represented by the formula (4) is preferably a diamine-based oxirane represented by the following formulas (5) to (9), among which, it is more preferably a formula ( 5) The aliphatic diamine-based Weiyuan shown in $6. These diamine-based oxylates can be formulated in combination of two or more kinds. Further, when two or more kinds of diamino sulfoxanes are combined and formulated, it is preferably formulated with (5) _ ^ ^ times (6) based on 100 parts by weight of the total diamine methoxy oxane 322574 12 201130888. More than 90 parts by weight of the aliphatic diamine siloxane. Further, in the above formulas (4) to (9), the average weight, which is in the range of 1 to 20, is preferably in the range of 5 to 15 and the right is less than 1, and the filling property is lowered as an adhesive. If it exceeds 20', the adhesion decreases.

CH3 H3C H2N—H2C¥_S|i-0, s)—CH2%NH2 (5) CH3 h3c ch3 h3c H2N-fH2C-)?f-Si-0^lin-s,i-f CHa-^NH 2 --(6)

CH3 H3C ch3 h3c H2N-£)^s|i-〇41?s'i-^NH2 ·.. (7) ch3 h3c ch3 h3c H2N^-〇-H2c^Si-0^-si —CH2 —〇- ^^~ΝΗ2 . .(8) ch3 h3c pp H2N-f HzC-igf-Si-O-^-Si-f CH2-^3-NH2 - (9) 0 0 Composition shown in the general formula (2) In the unit, a ketone group-containing group R2 (a divalent aromatic diamine residue derived from an aromatic diamine) may be, for example, the following 13 322574 201130888 alone or in combination of two or more and formulas (10), (11) Shown. These systems are available for use.

[here, lanthanide independently represents a monovalent hydrocarbon group neooxy group having a carbon number of i to 6, X represents CO, and (1) independently represents an integer of 〇 to 4] for forming the above formula (1〇), (U) Aromatic two groups of bases and salts: for example, 4,4'-bis(3-aminophenoxy)benzophenone (BABp), 1'3-bis[4-(3-private benzene) Oxy) benzophenone (babb) and the like. Further, in the structural unit represented by the formula (2), as the other aromatic diamine for forming the raw material of the group R2, for example, 2,2-bis(4-aminophenoxyphenyl)propane may be mentioned. (BAPP), 2,2, divinyl-4,4,-diamine-based (VAB), 2,2,-dimethyl-4,4'-diaminobiphenyl (m_TB), 2,2,·diethyl-4,4'-diaminobiphenyl, 2,2,6,6,-tetradecyl-4,4,-diaminobiphenyl, 2,2'- Diphenyl-4,4,-diaminobiphenyl, 9,9.bis(4-aminophenyl) field, and the like. These aromatic diamines can be used individually or in combination of 2 or more types. The above-mentioned acid anhydride and diamine which are the raw materials of the polyimine oxime may be used alone or in combination of two or more. Further, an acid anhydride and a diamine other than the above may be used in combination. In order to improve the long-term heat resistance when using a polyimide resin as an adhesive, it is preferable to use a polar base as a raw material of aryl (tetra) tetra-anhydride and aryl (tetra) diamine. Therefore, in terms of aromatic tetra-slow anhydride and aromatic diamine, the apparent molecule is calculated according to the following mathematical formula (1)*(ii); the index of the amount of the polar group contained is p-value - All are below the force. It is preferable to use an aromatic diamine having a p value of 0.7 or less, and most preferably 0.6 or less. P value of aromatic tetracarboxylic anhydride = (Al/Bl) xioo... (i) P value of aromatic diamine = (A2/B2) χΙΟΟ... (ϋ) [herein]

Al = (number of polar groups in the base Ar) χ (based on 2 moles) Α 2 = (number of polar groups of the base & order) χ (the number of moles of the base) Β 1- (based on Ar Molecular weight) χ (molar number of the base) Β2-(molecular weight of the base R2) χ (the number of moles of the base R2)] is a polar group which is a reference for calculating the above ρ value, and is derived from an electric dipole moment. The size of the ) is divided into three stages. The i-th is divided into -x (where 'X is a function atom), _OH, _SH, _〇_, _s_, _s〇_, _丽·, -co-, -CN, _P=0, _PO_, etc. The number of each is calculated as i polar groups. The second division is ·δ〇2_, _c〇NH_, and the number of these is calculated as two polar groups 1 3 are divided into _s〇3H_, and the number of these systems is calculated as three polar groups. [Synthesis of Polyimine Oxygen Burning] - Polyimine oxime having a structural unit represented by the general formulae (1) and (2), the above aromatic tetracarboxylic anhydride, diamine oxime oxamine (required) When it is reacted in a solvent to form a polyamide resin of a precursor resin: 322574 15 201130888, it can be produced by heating a closed loop. For example, the acid needle component and the diamine component are about to be dissolved in an organic solvent, and X is stirred in a range of 0 to 100 ° C for 30 minutes to 24 hours to cause polymerization to obtain a polyfluorene. The body of the polyamine. In the reaction, the precursor is dissolved in a range of 5 to 30% by weight in the organic group, preferably in a range of 1 to 2% by weight. The organic solvent used in the polymerization reaction may, for example, be N,N_:methylformamide, n,ndimethylammoniumamine:DMAC), N-methyl-2-pyrrolidinone, 2-butanone, dimethyl Sulfone, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethylhydrazine, and the like. Further, two or more kinds of solvents may be used in combination, and the step may be a combination of an aromatic hydrocarbon such as xylene or toluene. The precursor to be synthesized can be generally used as a reaction solvent solution, and 2' can be concentrated, _ or substituted with other organic solvents as needed. Further, since the month's body is excellent in solvent solubility, it can be advantageously used. The method of imidizing the precursor is not particularly limited, and it is preferred to use, for example, a heat treatment in which the temperature is in the range of 80 to 300 C for a period of time to 24 hours. ^ When the polyamidene having the structural units represented by the general formulae (1) and (2) is oxidized, the ratio of the acid anhydride component and the diamine component to be used as the raw material is not particularly limited, but for example, When the terminal substituent of the ruthenium iodide is an amine group, that is, the acid anhydride group is sealed with a diamine, the acid needle component: the diamine component has a molar ratio of 1.000 from the viewpoint of suppressing the polarity of the polyimide resin. : 1.001 to 1.0 : U. Further, polyfluorene 322574 16 201130888 imidate oxime which is a structural unit represented by the above formulas (1) and (2) is a reaction of aromatic tetracarboxylic anhydride, diamine sulfoxane and aromatic diamine. When the obtained quinone imine structure is used, for example, as an adhesive for a cover film, in order to suppress the diffusion of copper, it is most preferable to have a structure which is completely imidized. However, a part of the polyimine may also be a proline, and in this case, the unreacted proline sites (-CONH- and -COOH) are regarded as polar groups which induce the diffusion of copper. That is, one of the proline acids was calculated by having a substituent of four polar groups (two of -CONH- and two of -COOH). In this manner, the P value to be described later is preferably 0.7 or less (more preferably 0.6 or less), and it is preferred to terminate the imidization. The ruthenium imidization ratio was measured by a Fourier transform infrared spectrophotometer (commercial product: FT/IR620), and the infrared absorption spectrum of the polyimide film was measured by a single reflection ATR method to be around 1015 cm·1. The benzene ring absorber was used as a reference, and was calculated from the absorbance of C=0 stretching of the quinone imine group derived from nSOcnf1. [Amine compound] In the polyimine resin of the present invention, the counterpart of the reaction with the ketone group of the polyamidoxime oxime having the structural unit represented by the above formulas (1) and (2) has The amine compound having at least two first-order amine groups as a functional group may, for example, be (I) an aromatic diamine, (II) a diamine sulfoxane, (III) an aliphatic amine, or a (IV) dioxime compound. (I) Aromatic diamine: The aromatic diamine can be exemplified by the following formulas (12) and (13). 17 322574 201130888

[herein R 1Q independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, z represents a single bond or a divalent hydrocarbon group having 1 to 15 carbon atoms, 0, S, C0, S0, S02, NH or CONH The selected divalent group, n2 independently represents an integer of 〇 to 4] such an aromatic diamine may, for example, be 4,4,-diaminodiphenyl ether, 2,_decyloxy-4,4-diamine Benzobenzidine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) stupid, 2,2,-bis[4-(4- Aminophenoxy)phenyl]propane, 2,2,-dimercapto-4,4,-diaminobiphenyl, 3,3,-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminobenzidine, diphenylamine, and the like. Further examples other than the aromatic diamine include, for example, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl.飒, bis[4-(3-aminophenoxy)phenyl], bis[4_(4-aminophenoxy)biphenyl, bis[4_(3-aminophenoxy)biphenyl , bisaminophenoxy)]biphenyl, bis[1·(3-aminophenoxy)]biphenyl, bis[4-('aminophenoxy)phenyl]methane, double [4_ ( 3-aminophenoxy)phenyl]decane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, double^ "Hemiamine phenoxy phenenzolone bis-"^-aminophenoxy] benzophenone, bis[4,4'-(4-aminophenoxy)]benzimidanilide , bis[4,4,_(3-aminophenoxy)]phenylanilide, 9,9-bis[4_(4-aminophenoxy) 322574 18 201130888 phenyl]芴, 9,9 - bis[4-(3-aminophenoxy)phenyl]indole, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-dual- [4-(3-Aminophenoxy)phenyl]hexafluoropropane, 4,4'-fluorenylene di-o-anilinium, 4,4,-methylene-2,6-di Toluidine, 4,4' -methylene-2,6-diethylaniline, 4,4,-diaminodiphenylpropanone, 3,3'-diaminodiphenylpropane, 4,4,-diamine Diphenylethane, 3,3'-diaminodiphenylethane, 4,4,-diaminodiphenyl fluorene, 3,3'-diaminodiphenylcarbamate, 4, 4'-Diaminodiphenylsulfanium scale, 3,3,-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl; E-wind, 3,3,-diaminodi Phenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4,-aminodiphenyl scaly, benzidine, 3,3, -diaminobiphenyl, 3,3,-dimercapto-4,4'-diaminobiphenyl, 3,3'-dimethoxyoxybenzidine, 4,4,-diamino-pair _ 联二笨,3,3''-diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine, 2,6-diamino acridine, anthracene, 4_bis (4. amine Benzophenoxy)benzene, anthracene, 3•bis(4_aminophenyloxy)benzene, 4,4'-[1,4·phenylphenylbis(1-fluorenylethylene)]diphenylamine, 4 , 4'-[1,3-phenylenebis(1_fluorenylethylene)]diphenylamine, bis(p-aminocyclohexyl)methane, bis(p-Iamino-t-butylphenyl) Jun, Bis(p-/5-methyl-(5-aminopentyl)benzene, p-bis(2.methylamineyipentyl)benzene, p-biguanide, 1 dimethyliaminopentyl Benzene, U•February, naphthylnaphthalene, 2,6-diaminonaphthalene, 2,4-bis(amino-t-butyl)methyl, 2,4-diaminotoluene, m-xylene _2,5-diamine, p-xylene-2,5_ ', m-xylylenediamine, p-xylenediamine, 2,6-diaminopyridine, H 匕疋2,5_monoamine _ 1,3,4_π and the like diazole, hexahydropyridinium and the like. use. The above aromatic diamine may be used singly or in combination of two or more kinds, and 322574 19 201130888 (II) diamino methoxy oxadiamine oxime oxane is preferably exemplified by the following diamine sulfite Or an oligomer thereof. (6) H2N — R]]' ?13 Rl5 S|丨一0~^irS丨卜 R12—洲2. .· (14)

Rl4

Rl6 (herein 'Ru and R12 represent a divalent hydrocarbon group, Rl3 to Ri6 represent a hydrocarbon group having a carbon number of j to 6, and mi represents a number of from 1 to 20, preferably from 1 to 1 Å). Such a diamine oxirane For example, diaminopropyltetramethyldioxane, a diamine oxirane represented by the above formulas (5) to (9), and the like can be given. One of the above amino azide oxides may be used singly or in combination of two or more. (III) Aliphatic amine: The aliphatic amine may, for example, be 1,4-diaminobutane, hydrazine, 5-diaminopentane, 1,6-diaminohexane or 2-methyl-l. 5-Diaminopentane, ls7-diaminoheptane, 1,8-diaminooctane, 13-bis(aminomethyl)cyclohexane, M-bis(aminomercapto)cyclohexane Alkane, 1,9-diaminodecane, diaminodecane, 1,11-monoaminoundecene, 1,12-diaminododecacarb, 4,4,·arylene Diamine-based diamine-based tris(2-aminoethyl)amine, ν, Ν,-bis(2-aminoethyl)-1,3-propanediamine, bis(3-amino group Propyl) ethylenediamine, Li bis(3-aminopropyl)hexahydropyrazine, diethylenetriamine, hydrazine-methyl-2,2'diaminodiethylamine, 3,3,- Amines containing a nitrogen atom such as diaminodipropylamine, ν, Ν-bis(3-aminopropyl)decylamine, bis(3-aminopropyl)ether, L2- 20 322574 201130888 Double ( 2-Aminoethoxy)Ethylene, 3,9-bis(3-aminopropyl)_2, 仏l〇_tetraoxaspiro[5.5]_10-carbonated amines containing oxygen atoms, 2, 2, sulfur bis(ethylamine) oxime amine having a sulfur atom, and the like. The above aliphatic amines may be used singly or in combination of two or more. (IV) Diterpenoid Compound: The diterpene compound may, for example, be represented by the following formula (5). Ο 〇 MU Η II η — NH 2 · (15) ΝΗ 2 - Ν - C ~ Ri7 - c In the formula (15), the R 1 系 may, for example, be a single bond, an aliphatic group or an aromatic group 4. If R17 is preferred by way of an example of a compound, the following compounds may be mentioned. For example, it may be diterpene oxalate, diammonium malonate, diterpene succinate, diammonium glutarate, diammonium adipate, diammonium pimelate, dinonime, and bismuth suberate. Dioxalate dihydrate, diterpene azelaic acid, dinonyl dodecanoate, diterpene maleate, diammonium fumarate, diammonium glycolate, disaccharide tartrate, apple Diterpenoids, bismuth citrate, diterpene bismuthate, diterpene bismuthate, diammonium 2,6-naphthoate, 4,4-di-benzate, 1,4-naphthyl Diterpenic acid, 2,6-π ratio biting bismuth, itaconic acid diterpene and the like. The above two compounds may be used singly or in combination of two or more types. Among the above-mentioned amine compounds having at least two first-order amine groups as functional groups, particularly preferred are diterpene compounds. When a diterpene compound is used, 322574 21 201130888 can shorten the hardening time of the adhesive resin composition as compared with the use of other amine compounds. It is considered that a product obtained by reacting a primary amine group of the diterpene compound with a ketone group is a molecular structure such as Semicarbazone, and a two-dimensional structure is formed by hydrogen bonding between molecules in the molecule. On the other hand, the stability of the product is improved, so that the equilibrium of the reaction is biased toward the product side, and the reverse reaction of the ketone group of the polyimine oxime which forms the raw material with the amine group of the dioxime compound is difficult to occur. Further, the combination of the amine compound such as the above (I) aromatic diamine, (II) diamine sulfoxane, (hydrazine) aliphatic amine, (IV) diterpene compound, and (II), (I) The combination of (III), (1) and (11) and (m), and #(I) to (IV) may be used in combination of two or more types. In particular, it is expected that the characteristics of the amine compound of (I) S (III) can be utilized by combining the amine compound of (HJ) and the compounding ratio of the (W). The shortening effect of the hardening time is obtained according to the compounding ratio of the compound of (IV). [Production of Polyimine Resin] The polyamidene resin of the present invention is a tree containing at least a sulfhydryl group as a constituent unit having a structural unit represented by the above formula (2). In the amination of a functional group, a ketone group of a polyamidiamine oxirane is combined with an amine group to cause a condensation reaction, and an adhesive: a core becomes a cured product. At this time, the amount of the amine compound added is more uniform, and the amine group of the first order is 0.004 mol to the total; the mercapto group is 1 mol, 芏丨 5 mol, and it is preferably 0·005 322574 22 201130888 Moor to! .2 moles, more preferably from 0.03 moles to 〇·9 moles, are preferably added to the amine compound in the same manner as the molars to G.5 moles. Compared with the addition of the amine group-based compound of the ketone group 4 r: i level which does not reach °. 004 mole, the cross-linking of the polyamidene stone produced by the amine compound is insufficient, so that the polyfluorene is contained. The binder of the imide resin resin composition tends to appear to be resistant to soldering, and if the amine compound is 7 = 1.5 mo! The unreacted amine compound acts as a thermoplastic, and has a tendency to lower the heat resistance of the fusion heat resistance in the same hardened material. The condition of the long-term resistance and the 'condensation reaction of the dish is as long as it is a thiol-based reaction of the amine compound in the polyamidene oxime (4) into a bribe (C=N bond), and No restrictions. It is also dependent on the type of the amine compound. 1 If the scale of the amine is used, it can also be condensed with the base of the polyamidene, but it is preferred to promote the condensation reaction by heating. When a di-aliphatic amine is used, for example, it is preferred to carry out heat reduction in the range of 6Q i 2 (Κ) 使用. When an aromatic amine is used, for example, it is preferred to carry out heat condensation in the range of 12 to 22 generations. The temperature at which the condensation is carried out is such that, for example, 12 〇 to 22 理由, for example, 12 〇 to 22 理由, for example, 12 〇 to 22 〇, for example, 12 〇 to 22 〇, for example, 12 〇 to 22 〇 使 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合 缩合Within the scope of 'more suitable to just fine. Within the scope of C. The reaction time is about ～24 hours to about 24 hours, and the end point of the reaction is, for example, Fourier transform, = external spectrophotometer (commercial product: FT/IR620 from Japan Spectrophotometer), infrared absorption spectrum, which can be borrowed from 167〇Cm l The reduction or disappearance of the absorption peak of the ketone group in the vicinity of the polyamidoxime, and the absorption peak derived from the imine group near 322574 23 201130888 1635 cm, which is a good result of dimerization _ base and amine-based amine group plus ',, and condensed 4 can be synthesized by U) polyimine yttrium (yield imidization), followed by addition of an amine compound to heat; diamine component, no About the ruthenium imine oxime oxane (b) pre-feeding an excess amount of the amine compound as a polyamido oxirane synthesis (醯imination) followed by the rest of the ruthenium (or ruthenium) The amine-based compound is heated together with the poly; or, after the composition of the imine oxime is applied to the substrate or formed into a thin ruthenium (c), the poly-ingering compound is added to a specific shape (for example, coated) After any), heating or the like is performed. In the case of the above (b), the excess of the amine-based compound is extremely low in the molecular weight of the (10) imine ruthenium which is formed by the end-substituent in the production of the poly-branze oxidization. In the case of the compound, it is difficult to obtain sufficient heat resistance. Therefore, when the remaining amino group compound [the above (b)] is suitable, it is suitably used within the range which does not impair the present invention. Make at least 2 of the amine compounds! The amine earth is effectively reacted with a ketone group to form a (iv) bond, which is as described in the above (4) or in a manner in which the synthesis of the polyamine compound is carried out in the synthesis of the polyaniline sand oxynitride. In the above (c), the heat of the heat treatment is applied to the second (four) layer of the state in which the mixture of the man-based compound and the poly-bromide is mixed, and then, by thermal compression bonding to the circuit substrate having the wiring layer. The heat of the time waits ^ 322574 24 201130888 OK. When the polyimine resin of the present invention obtained as described above is used as an adhesive for a cover film or the like, even if it is repeatedly placed in a high-temperature environment, the adhesion can be maintained, and therefore, it is calculated according to the following formula (iii). The P value is preferably 0.7 or less, more preferably 0.6 or less. The P value is as shown in the formula (iii), and may be derived from the aromatic tetracarboxylic anhydride residue in the polyimine resin and the molar number and molecular weight of the aromatic diamine residue and the residues thereof. The number of polar groups is determined. P value={(A1+A2) / (B1+B2)} xlOO··· (iii) [here, A1, A2, B: [, B2 has the same meaning as described above, and the number of polar groups is Calculated in the same manner as the above p value] This P value is an index indicating the amount of the polar group contained in the polyimide resin, meaning that the larger the P value, the larger the amount of the polar group in the polyimide resin. . When an adhesive agent such as a cover film or the like is used, the polar group contained in the adhesive layer serves as a factor for inducing diffusion of copper derived from the copper wiring. That is, if a large amount of polar groups are contained in the subsequent layer, copper derived from the copper wiring diffuses widely into the adhesive layer between repeated heating. As a result, it is considered that the adhesion force of the adhesive layer is weak, and the cover film is easily peeled off. In the present invention, by setting the P value of the polyimide resin to 0.7 or less (more preferably 0.6 or less), the amount of the polar group contained in the polyimide resin can be lowered, and the decrease in the adhesion can be suppressed. . In the present invention, the group Ar (aromatic tetracarboxylic anhydride residue) and the base (aromatic diamine residue) of the polyfluorene imine oxime having the constituent units represented by the general formulae (1) and (2) The reason why the polar group contained in the base is 25 322574 201130888 P value is 'the amount of the polar group contained in the base & towel and base & towel, and the total amount of the polyimine resin is determined. Polarity. Therefore, the polar group contained in the residue of the diaminocarbyl residue or the amino compound and the polar group associated with the quinone imine are not considered in addition to the p value. [Action] Dehydration condensation reaction of a polyimine oxime group having a structural unit represented by the general formulae (1) and (2) with a hydrazine amine group of an amine compound, polyimine oxime The carbon atom of the ketone group in the oxane forms a C==N bond with the nitrogen atom of the amine group of the first-order amine group. As a result, it is considered that the chain-like polyimine oxime is crosslinked by the amine compound to form a network. The polymer. It is considered that it is difficult to produce intermolecular interactions in the polyamidoxime oxime system, so the alignment control of the polyimine oxime is difficult, but if such a crosslinked structure is produced, not only the table of polyfluorene oxime The high molecular weight of the observation can restrain the molecules of the polyimine oxime to some extent, so that the heat resistance of the polyimide resin is improved, and excellent solder heat resistance can be known. Further, by the fact that the vicinity of the nitrogen atom in the C=N bond is bulky, the nucleophilic energy of the nano atom of the polar group contained in the polyimine resin is lowered, and the diffusion of copper derived from the copper wiring to the adhesive can be suppressed. The layer can be obtained by using it in a high temperature environment and suppressing the decrease in the strength of the next. For this reason, the number of amine-based compounds used in the present invention must have at least 2 amine groups. The number of amine groups is preferably from 2 to 5, more preferably from 2 to 3. Further, in the amine compound having three or more amine groups, since the crosslinked structure in which the two amine groups form a C=N bond becomes sterically bulky, the remaining unreacted amine groups are difficult to react with the ketone group. Therefore, the number of amine groups is 2. Into the step, as described above, in the shortening of the hardening time of the adhesive resin composition 322574 26 201130888 吏 using a diterpene compound as an amination compound to produce a cross-linking from the amine-based compound used in the amine invention According to the view of Yi Fu, the weight average molecular weight I, & 7 s amine compound is 5,000 or less, 2, _ ' is most suitable (10) illusion, especially, especially It is an amine-based compound having (10) as a sub-quantity. If the molecule of the amine compound is terminated by one amine group of the amine compound, the chitosan is burned = only (four) bond 'because the periphery of the remaining amine group becomes a stereoscopic benefit, = amine The base becomes a tendency to make C==N bonds difficult. [Binder Resin Composition] The adhesive resin composition of the present invention contains a polyimine oxime [component] having the constituent units represented by the above formulas (1) and (2), and has at least 2 The amine compound [(b) component] having a 1-stage amine group as a functional group is an essential component. The adhesive resin composition is obtained by mixing or kneading the component (A) and the component (B), and/or heating in a state containing the component (a) and the component (B), the polyimine oxime The ketone group is condensed with the amine group of the amine compound to form a C=N bond. That is, the polyimine resin of the present invention is changed by the condensation of the chitosan oxide with the amine compound. The weight average molecular weight of the component (A) in the adhesive resin composition of the present invention is preferably from 1 Torr to 200,000, more preferably from 20,000 to 150,000. When the weight average molecular weight of the component (A) is less than 1 Torr, the regulation of the fluidity when the adhesive resin composition forms a solution becomes difficult, and the heat resistance of the cured product tends to decrease. Further, if the weight average molecular weight of 27 322574 201130888 exceeds 200,000, it tends to impair the solubility to the solvent. The resin composition of the subsequent agent is from 0. 004 mol to 1.5 mol per person, preferably from 0.005 mol to i 2 mol, more preferably from 0.03 mol to 〇, relative to the ketone oxime. · 9 moles, especially 〇〇 4 moles to 〇 5, Moer's way contains amine compounds. The remaining baggage of the invention may contain the above-mentioned polyamidoxime, an amine compound, and a plastic mold. However, it can be plasticized. The middle system contains many polar bases. It is feared that it will promote the diffusion of steel from copper wiring. Therefore, plasticizers should not be used as much as possible. Further, in the adhesive resin composition of the present invention, the molar ratio of the diamine-based oxime of the formula (4) in the total diamine component of the raw material is set to 75 mol% or more, even if it is not added. A plasticizer that provides sufficient flexibility to prevent distortion of the cover film. Therefore, when a plasticizer is used, it is preferred to blend in a range which does not impair the effects of the present invention. Further, in the adhesive resin composition of the present invention, in addition to the above-mentioned polyamidiamine oxime, an amine compound, and a plasticizer of an optional component, other resins such as an epoxy resin may be appropriately brewed as needed. Ingredients, hardeners, coupling agents, fillers, pigments, solvents, and the like. When any of these optional components is blended, the P value of the entire adhesive resin composition containing all the optional components can be determined by the following formula (iv) which deforms the above formula (iii). In this case, it is preferable to reduce the amount of the polar group contained in the adhesive resin composition by setting the p value of the entire adhesive resin composition to 〇.7 or less (more preferably 0.6 or less), thereby suppressing the decrease in the adhesion force. . p value={(Al+A2+An) / (Bl+B2+Bn)} xlOO... (iv) [herein A A2, B1, B2 have the same meaning as before, 28 322574 201130888 X (optional

An == (the number of moles of the number of polar groups in an arbitrary component) x (the molar content of arbitrary components is η == (the number of molecular weights of any component) ^ and if each is arbitrary When the components are added, the arbitrarily formed polar group is calculated in the same manner as the p-value reading form described above.] The remaining surface of the present invention is 100 parts by weight of the amine resin, and is an optional component. The blending amount is preferably 2 to 7 parts by weight, and the binder resin composition of the present invention obtained by the above method is excellent when used as an adhesive layer. The softness and the thermoplasticity are preferably used as a cover film for a wiring portion such as a 5f FPC or a hard/flexible circuit board, and are used as a cover film for a cover film. After coating the adhesive resin composition of the present invention on a single side in a solution state (for example, a varnish containing a solvent), for example, it is thermocompression bonded at a temperature of 60 to 220 C to form a film having a coating layer and an adhesive layer. The cover film of the invention. At this time, the heat during the thermocompression bonding is utilized. Further, the ketone group of the polyaniline oxime can be heated and condensed with the amine group of the amine compound. When the heat condensation is insufficient during the hot dust bonding, the heat treatment can be further followed by heat treatment to heat the condensation. When heat treatment is applied after thermocompression bonding, the heat treatment temperature is, for example, preferably from 60 to 220 ° C, more preferably from 80 to 200 ° C. Further, on any substrate, it is applied in a solution state (for example, a varnish containing a solvent). The adhesive resin composition of the present invention is dried, for example, at a temperature of from 8 Torr to 18 Å, and then peeled off to form an adhesive film, and the adhesive film is made of, for example, 6 322574 201130888. The cover film of the present invention having a film layer for covering and an adhesive layer can be formed by thermocompression bonding at a temperature of 2 Torr. At this time, the heat of the thermocompression bonding can also be used to make the melamine The first-stage amine group of the oxygen-burning oxime-based amine compound f is heated and condensed. As in the above manner, the hair styling agent resin composition is a sulfonyl group of a polyfluorene oxime and an amine group of an amine compound. It is processed into various forms in an unreacted state and used again. In the step, the adhesive resin composition of the present invention may be formed into a coating film in a solution state by screen printing on any substrate, and dried at a temperature of, for example, 8 Torr to i (10) c. 22 (rCi temperature heat treatment for a specific time 'to completely cure the coating film, or to form a cured product. At this time, it is also possible to heat and condense by heat at the time of hardening. [Cover film. Adhesive sheet] In the cover film of the present invention The film for covering is not limited, and for example, a polyimide film such as a polyimide resin, a polyether phthalimide resin or a polyamidoximine resin, or a polyamide film may be used. A polyester resin film or the like is used. Among these, a polyimide film having excellent heat resistance is preferably used. The thickness of the film layer for coating is not particularly limited, but is preferably, for example, 5 #m or more and 100. #m以下。 Further, the thickness of the adhesive layer is not particularly limited, but is preferably, for example, 1 〇em or more and % #m or less. Further, in the case where the adhesive resin composition of the present invention is formed into a film shape, a bonded sheet such as a multilayer FPC can also be used. When the adhesive sheet is used, the adhesive resin composition of the present invention is applied in a solution state on any of the base film, for example, after drying at a temperature of 80 to 18 (the temperature of TC is dried, the adhesive film of 322574 30 201130888 is peeled off). It can also be used as a bonding sheet as it is, and it can also be used in a state in which the adhesive film is laminated with any of the base film. When used as a bonding sheet, the polyimide can be made by heat during thermocompression bonding. The ketone group is heated and condensed with the amine group of the amine compound, and may be further subjected to heat treatment after thermocompression bonding to heat and condense. Further, the cover film or the adhesive sheet may have a release surface for the adhesive surface. The form of the release layer is not particularly limited as long as it is in the form of a non-destructive cover film or a bonded sheet, and for example, polyethylene terephthalate, polyethylene, polypropylene, or the like can be used. a resin film, or a resin film obtained by laminating such a resin film on paper, etc. The resin composition of the present invention is used for molding, and the heat treatment is carried out to produce the above-mentioned heating condensation reaction. The cover film or the adhesive sheet contains a polyfluorene fine resin obtained by a reaction of a polyimine oxime oxime with an amine compound, and thus has excellent solder heat resistance. More specifically, as shown in the later embodiment, Solder heat resistance (drying) is 26 〇〇c or more, preferably ((: above, more preferably 3 〇 (TC or more, solder heat resistance (moisture resistance) is 2 (8) c or more, more preferably 26 (rc or more, most It is preferably 28 〇 (>c or more. By having excellent solder heat resistance, it is possible to prevent the occurrence of soldering steps or peeling, and to contribute to the reliability of the manufactured circuit board and the like. Further, the circuit board of the present invention is not particularly limited as long as it has the above-described method. The cover film or the adhesive sheet is not particularly limited. For example, the circuit board preferably has at least a substrate. The cover layer of the present invention is formed by a metal such as steel formed by the pattern on the substrate. The substrate of the present invention is not limited to the surface of the substrate. The material used to cover (4) (4) with the Juyi (4) tree material, Yiyou Different = = The use of the cover-coating film and the inter-wiring adhesive layer of the present invention is filled in the wiring between the imidite and the amine-intimate adhesion, and by forming the layer containing the poly-ruthenium adhesive It can suppress the temperature of the poly-imine resin obtained by the reaction of β and β, and the diffusion of copper from the fine wire, even if it is repeated in the atmosphere, maintaining excellent adhesion between 150t. More specifically, the amount of the X-ray hour is small (4) after the heat test, and the measurement is carried out by using the following example: (The following description can be carried out to suppress the long-term resistance to 2·5 〇/°. As a result, the strength is maintained at 0, 2 ^, and the peeling of the film layer for covering and the film layer for covering (2) is equal to α & above °, especially by selecting the general formula (1) and the extremely high-quality "sulfanyl group R1" And the base R2 ' can obtain the degree of the amine component of 0.4 kN / m or more. Further, by making the diamine oxime to the totality of the raw material, even if the ratio is not more than 75 mol%, an excellent soluble blending plasticizer can be obtained, and warpage of the cover film can be prevented. In this case, the circuit board of the invention may be configured as a multilayer circuit board. The resin cylinder cover film 'adhesive sheet obtained from the adhesive of the present invention can also be used for the adhesive sheet. The production of the steel stripe circuit board is not particularly limited, and for example, it is necessary to process a metal foil of a metal foil laminate such as a g plate by a chemical etching method to a specific pattern after being processed into a specific pattern by a method of 322574 32 201130888. The partial build-up cover film is, for example, a method of thermocompression bonding using a hot stamping or the like. In this case, the crimping conditions are not particularly limited, but for example, the crimping temperature is preferably 130. (: above 220 C or less 'more preferably 14 〇. 〇 above, 2 〇〇. 〇 below, the pressure should be above 0.lMPa, below 4MPa. Also, in the state of the cover film, polyimide stone When the ketone group is not reacted with the amine group of the amine compound, the condensation reaction occurs by heat bonding the cover film to the circuit wiring, that is, the manner in which the adhesive layer of the cover film is adjacent to the wiring layer At the same time as the step of thermocompression bonding, the group of the component (A) contained in the adhesive layer may be condensed with the amine group of the component (B) to form a C=N bond. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. Further, in the following examples, unless otherwise stated, various measurements and evaluations are as follows. [Measurement of strength] Next, the adhesive surface of the test piece having a width of 10 nm and a length of 100 mm was placed on the shiny side of the copper foil (35 #m thickness) (excluding the rust preventive metal). Dusting at a temperature of 17 ° C, a pressure of 1 MPa, and a time of 1 minute The oven was heated at a temperature of 150 ° C for 24 hours (but 'the relevant example 21 was at a temperature of 200. (:, pressure IMPa, time 60 minutes, thermocompression bonding, followed by heat treatment) After using a tensile tester (manufactured by Toyo Seiki Co., Ltd., Strograph Ml), the force at the time of peeling at a speed of 50 mm/min in the direction of 180 is used as the adhesive strength. In the actual 33 322574 201130888, the test is made 0.2 kN/m or more. It is judged as "OK" when it is 0 35 kN/m or more. [Measurement of Weight Average Molecular Weight (Mw)] The weight average molecular weight is analyzed by gel permeation chromatography (manufactured by Tosoh Co., Ltd.' using HLC-8220GPC The measurement was carried out using polystyrene as the quasi-substance 'in the developing solvent, and the succinyldiamine was used. [Evaluation method of warpage] The evaluation method of the tortoise was carried out in the following manner. The Kapton thinner was coated with a polyimine adhesive at a thickness of 35 cm after drying. In this state, the Kapton film was placed below, and the average height of the four-corner warp of the film was measured to be 5 mm/under. As "good" When it is more than 5mm, it is "bad". [Evaluation method of solder heat resistance (drying)] Circuit processing of 5«^-Imine copper pavilion (Nippon Steel Chemical Co., Ltd., trade name: Espanex MC18-25-00FRM) Prepare a printed circuit board having a circuit having a wiring width/wiring interval (L/S) = 1 mm/lmm, and place the adhesive agent surface on the wiring of the printed circuit board at a temperature C, a pressure of 1 MPa, and a time of 1 minute. The conditions were pressed, and then heated in a baking phase at a temperature of 150 Torr for 24 hours (however, Example 21 was thermocompression-bonded at a temperature of 200 ° C, a pressure of 1 MPa, and a time of 60 minutes, and thereafter The heat treatment is omitted). The test piece to which the copper foil was attached was allowed to stand at 105 ° C and a relative humidity of 50% for 1 hour, and then immersed in a solder bath set at each evaluation temperature for 10 seconds, and the subsequent state was observed to confirm foaming, swelling, and peeling. Wait for the poor situation. For the thermal system, the temperature performance of the upper limit that does not produce 322574 34 201130888 is not good. For example, "320 °C" means that the evaluation is carried out in a solder bath of 32 ° C. No bad situation can be seen (see Table 2 below). To 4). [Evaluation method of solder heat resistance (moisture resistance)] Polyimide copper foil laminate (Nippon Steel Chemical Co., Ltd., trade name: Espanex MC18-25-00FRM) was subjected to circuit processing, and wiring width/wiring interval was prepared. (L/S)=1mm/lmm of the printed circuit board of the circuit, the test piece is placed on the wiring of the printed circuit board, and is pressed at a temperature of 1, pressure IMPa, and time of 1 minute, and then in an oven. The mixture was heated at a temperature of 150 C for 24 hours (however, in Example 21, thermocompression bonding was carried out under the conditions of a temperature of 200 ° C, a pressure of 1 MPa, and a time of 60 minutes, and the subsequent heat treatment was omitted). The test piece attached to the copper foil was allowed to stand at 85 ° C and a relative humidity of 85% for 24 hours, and then 'immersed in a solder bath set at each evaluation temperature for 10 seconds' to observe the subsequent state, and confirmed foaming, swelling, and peeling. Wait for the poor situation. The heat resistance is expressed by the temperature of the upper limit which does not cause a bad situation. For example, "28CTC" means 28 〇. The evaluation was carried out in the solder bath of 〇, and the poor condition was not observed (see Table 2 to the sentence below. [Tensile test] A sample of a film of polyimine resin was prepared at a thickness of 35/zm, and the width was cut out to 12.5 mmx. A short grid shape of 120 mm in length was used as a test piece, and a tensile tester (manufactured by Toyo Seiki Co., Ltd., Strograph R1) was used to measure at a head-to-head speed of 25 mm/min and a chuck-to-clip distance of l〇i.6 mm. The weight is divided by the cross-sectional area (〇.31mm2) of the test piece as the tensile strength. The abbreviation used in the present embodiment means the following compound. 322574 35 201130888 BTDA . 3,3 ,4,4 Ben S and the same four acid dianhydride (Polar base of BTDA: 1, p value = 〇 56) BPDA: 3,3,4,4-Phenyltetracarboxylic acid Erxuan (BPDA polar base: 〇, p Value = 〇) BAPP : 2,2-bis(4-aminophenoxyphenyl)propane (polar group of BAPP: 2, p value = 0.53) DAPE : 4,4'-diaminodiphenyl TPE-R: 1,3-bis(4-aminophenoxy)benzene p-PDA: p-phenylenediamine m-TB: 2,2'. dimethyl-4,4'.diamine linkage Stupid BAFL: bisaniline hydrazine HMDA : 1,6-hexamethylenediamine PSX-A: as shown in the above formula (5) The average value of the number of amines (but 'm) is 1 to 2 ,, the weight average molecular weight is 740) 77 N-12 : dodecanedioic acid dioxime (in the above formula (15) Ruler 17 is Ci〇h20) ADA: Dioxane adipate (R17 in the above formula (15) is c4H8) Synthesis Example 1 In a 1000 ml separation flask, 71.3 〇g of PSX_A (0.0964 mole) was charged. , 9.89g of ΒΑΡΡ (0·0241 mole), 38 66g of BTDA (0.120 mole), 168g of N_methylpyrrolidine@同同一曱, and mixed at room temperature for a few hours to obtain poly A solution of the amino acid solution. 322574 36 201130888 The poly-proline solution was heated to 19 (rc, heated for 20 hours, and stirred to obtain a polyimine solution a obtained by imidization. The weight average molecular weight (μ^) of the polyimine resin in the solution a was 122,000. The molar percentage of the diamine helium gas component to the total diamine component at this time was 80 〇/〇 (m value = 0.8). Further, the "m value" means the presence of a molar ratio (hereinafter, the same) of the constituent unit represented by the above formula (1) contained in the obtained polyamidene 0 resin. The p value indicating the amount of the polar group contained in the obtained polyamidene resin is 〇 55. Synthesis Example 2

In a 1000 ml separable flask, 71.30 g of PSX-A (0.0964 mol), 9.89 g of BAPP (0.0241 mol), 38.66 g of BTDA (0.120 mol), and l68 g of N_methyl_2 were charged. _Pyrrolidone and 112 g of diphenylbenzene were thoroughly mixed at room temperature for 1 hour to obtain a polyaminic acid solution. The polyamic acid solution was heated to a temperature of 6 hours and stirred to obtain a polyimine solution b which was imidized. The weight average molecular weight (Mw) of the polyimine resin in the obtained polyimine solution b was 36,700. The monoamine component of the monoamine compound was 80% (m value = 0.8). Further, the p value indicating the amount of the polar group contained in the obtained polyimine resin is 〇 55. Synthesis Example 3 In a 1000 ml separation flask, 73 41 g of PSX-A (0.0992 mol), 1 ig of BAPP (0.0249 mol), 36.46 g of BPDA (0.1239 mol), and 168 g of N were charged. - mercapto-2-pyrrolidone and 112 bis-diphenylbenzene were thoroughly mixed at room temperature for 1 hour to obtain a polyaminic acid solution. 322574 37 201130888 The polyglycine solution was heated to l9 ° C, heated for 6 hours, and stirred to obtain a polyimine solution c which was subjected to amination. The weight average molecular weight (Mw) of the polyimide resin in the obtained polyimine solution c was 27,900. The molar content of the diamine oxime component in this case was 80% (m value = 0.8). Further, the p value indicating the amount of the polar group contained in the obtained polyimine resin is 〇 18 . Synthesis Examples 1 to 3 are summarized in Table 1. [Table 1] Synthesis Example Polyimine tetraphthalic anhydride (mole) Aromatic diamine (mole) Diamine oxirane (mole) m value P value solution Mw 1 a 122,000 BTDA (ο. 120) BAPP (0. 0241) PSX-A (0. 0964) 0. 8 0. 55 2 b 36,700 BTDA (〇. 120) BAPP (0.0241) PSX-A (0. 0964) 0. 8 0. 55 3 c 27,900 Bpda (〇. 1239) BAPP (0. 0249) PSX-A (0. 0992) 0. 8 0. 18 Reference Example 1 The polyimine solution a obtained in Synthesis Example 1 was coated on a polyimide film. A single side (trade name: Kapton ENS, vertical X horizontal X thickness = 200 mm x 300 mm x 25 ym) was dried at 80 ° C for 15 minutes to form a cover film having an adhesive layer thickness of 35 m. Using a Fourier transform infrared conversion spectrophotometer (commercial product: FT/IR620 manufactured by JASCO Corporation), the ketone group derived from BTDA was confirmed at around 1673 cm-1 by measuring the infrared absorption spectrum of the adhesive layer in the cover film. absorb. Then, the obtained cover film was placed on a copper foil of the rust-preventive metal layer from which the surface had been removed at a temperature of 17 Torr. The pressure was measured under the conditions of I, pressure IMPa, and time of 1 minute, and the temperature was 15 (TC, time 24 hours), and an evaluation sample was obtained. Visual evaluation: The results are shown in Table 2. [Example 1] Synthesis example 1 The obtained polyimine solution a was formulated with 5 78 g of BA_.〇14 material) into the step (iv) for 1 hour to obtain a polyimine solution 1. The obtained polysiimine solution 1 was applied to a single side of a polyimide film (manufactured by DUp〇nt Co., Ltd., trade name: Kapton ENS, vertical canister thickness 2 2 mmx 30 mmx 25//m). The film was dried at 80 ° C for 15 minutes to form a cover film 1 having an adhesive layer thickness of 35 # m. The cover film i was placed on a copper foil of the rust-preventive metal layer on which the surface was removed, and was punched at a temperature of 17 Torr, a pressure of 1 MPa, and a time of 1 minute, and then at a temperature of 15 (rc, time 24 hours) in an oven. The condition was heated to obtain the evaluation sample 1. The strength of the copper and the cover film after hardening of the adhesive layer was 1.9 kNVm. Further, the warpage of the cover film was not problematic. A Fourier transform infrared spectrophotometer was used.售 分 分 分 分 分 FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT FT The absorption of the imine group was confirmed in the vicinity. Next, the evaluation sample 1 was subjected to heat treatment in an oven and the atmosphere for 15 hours and for 1000 hours. The subsequent strength of the copper foil and the cover film after the measurement was 0.08 kN/m. At this time, the peeling surface is the interface between the copper and the adhesive layer. 322574 39 201130888 Further, a double-sided copper-forming circuit for the polyimide film is prepared [wiring width/wiring interval (L/S)=25/zm/ 25//m] printed substrate, will be in the embodiment The obtained cover film 1 was placed on the circuit surface of the printed circuit board, and was pressed at a temperature of 170 ° C, a pressure of 1 MPa, and a time of 1 minute, and then heated in an oven at a temperature of 150 ° C for 24 hours. A wiring board covered with ruthenium was provided. [Example 2] The same procedure as in Example 1 was carried out except that 5.78 g of DAPE (0.029 mol) was blended instead of BLAST having 5.789 g of the first embodiment. After the imine solution 2, the cover film 2 was obtained, and the evaluation sample 2 was obtained. The adhesive strength of the copper foil and the cover film after the adhesive layer was hardened was USkN/m. Further, the warpage of the cover film was not problematic. The sample 2 was evaluated and subjected to heat treatment in an oven and an atmosphere for 15 hours for 1000 hours. The subsequent strength of the copper foil and the cover film after the measurement was 0.63 kN/m. At this time, the peeling surface was copper and the adhesive layer. Further, in the same manner as in the example i, a printed circuit board having a circuit [wiring width/wiring interval (L/S) = 25/zm/25 μm] was prepared, and the cover 得到 2 obtained in the second embodiment was placed. The circuit surface of the printed circuit board is subjected to thermocompression bonding to obtain The wiring board 2 of the cover film was obtained. [Example 3] The same procedure as in Example 1 was carried out except that 5.78 g of p_PDE (0.053 mol) was blended instead of the 5.78 g of BAPP formulated in Example 1. After the imine solution 3, the cover film 3 was obtained, and the evaluation sample 3 was obtained. The adhesive strength of the copper foil and the cover film after the adhesive layer was hardened was 322574 40 201130888 1.0 kN/m. Further, the warpage of the cover film was not problematic. Next, 'Evaluation Sample 3' is heat treated at 1 $ 〇 ° C for 1000 hours in the tank and in the atmosphere. The subsequent strength of the copper foil and the cover film after the measurement was 0.54 kN/m. The peeling surface at this time is the interface between the copper and the adhesive layer. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring width/wiring interval (L/S) = 25 μm/25/zm] was prepared, and the cover film 3 obtained in Example 3 was placed on a printed substrate. The circuit surface of the circuit surface is subjected to thermocompression bonding to obtain a wiring substrate 3 having a cover film. [Example 4] The same procedure as in Example 1 was carried out except that 5.78 g of m-TB (0.027 mol) was used instead of the 5.78 g of BAPP which had been formulated in Example 1, to obtain a polyimine solution 4 The cover film 4 was obtained, and the evaluation sample 4 was obtained. The adhesive strength of the copper foil and the cover film after the hardening of the layer was L18 kN/m. Moreover, the warpage of the cover film is also no problem. Next, the evaluation sample 4' was subjected to heat treatment in an oven or in the atmosphere for 1 hour and 1000 hours. The subsequent strength of the copper foil and the cover film after the measurement was 0.46 kN/m. The peeling surface at this time is the interface between the copper and the adhesive layer. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring width/wiring interval (L/S) = 25 μm / 25 / zm] was prepared, and the cover film 4 obtained in Example 4 was placed on a printed substrate. The circuit surface is subjected to hot pressing #' to obtain a wiring substrate 4 having a cover film. [Example 5] The same procedure as in Example 1 was carried out except that 5.78 g of TPE-R (0.020 mol) was used instead of the 5.78 g of BAPP prepared in Example 1, and the same method was obtained. After the amine solution 5, the cover film 5 was obtained, and the evaluation sample 5 was obtained. The adhesive strength of the copper foil and the cover film after the hardening of the layer was 2.0 kN/m. Also, there is no problem with the warpage of the cover film. Next, for the evaluation sample 5, heat treatment was performed for 15 Torr and 1000 hours in an oven and the atmosphere. The subsequent strength of the copper foil and the cover film after the measurement was 0.66 kN/m. The peeling surface at this time is the interface between the copper and the adhesive layer. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring width/wiring interval (L/S) = 25 # m/25 μm] was prepared, and the cover film 5 obtained in Example 5 was placed. The circuit surface of the printed circuit board is thermocompression bonded to obtain a wiring substrate 5 having a cover film. [Example 6] The same procedure as in Example i was carried out except that 5.78 g of BAFL (0.017 mol) was blended instead of the 5.78 g of BAPP formulated in Example 1, to obtain a polyimine solution 6 Covering the film 6, an evaluation sample 6 was obtained. The adhesive strength of the copper foil and the cover film after the hardening of the layer was 1.22 kN/m. Moreover, the warpage of the cover film is also no problem. Next, the evaluation sample 6 ' was subjected to heat treatment in a water tank and the atmosphere for 1, 1000 hours. The subsequent strength of the copper foil and the cover film after the measurement was 0.65 kN/m. The peeling surface at this time is the interface between the copper and the adhesive layer. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring width/wiring interval (L/S) = 25 μm / 25 vm] was prepared, and the cover film 6 which was applied in Example 6 was placed. The circuit surface of the printed circuit board is thermocompression bonded to obtain a wiring board 6 having a cover film. Reference Example 2 322574 42 201130888 A PAPP-added polypene was obtained in the same manner as in Example 1 except that the polyimine solution c obtained in Synthesis Example 3 was used instead of the polyimine solution a in Example 1. Imine solution. This polyimine solution was coated on one side of a polyimide film (trade name: Kapton ENS, vertical X horizontal x thickness = 200 mm x 3 mm x 25 vm), and dried at 8 ° C for 15 minutes. A cover film having an adhesive layer thickness of 35/ί/ι is formed. The cover film was evaluated in the same manner as in Example 1. The results of Examples 1 to 6 and Reference Examples 1 to 2 are summarized in Table 2. In Table 2, the strength 1 indicates the adhesion strength between the copper foil and the cover film after the adhesive layer is cured, and the strength 2 indicates the copper foil and the cover film after heat treatment at 150 ° C for 1,000 hours in the atmosphere. Strength (the same is true in Tables 4 and 5). Further, the molar ratio in Table 2 means the molar ratio of the first-order amine groups in the ketone-based 1 molar amine compound in the polyethylenimine oxime (in Tables 3 and 4 and The same is true in Table 5. [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Reference Example 1 Reference Example 2 Polyimine solution aaaaaaa C Amine compound BAPP DAPE p-PDA m-TB TPE-R BAFL No BAPP Mobi ratio 0.23 0.48 0.88 0.45 0.33 0.28 0 - Then intensity 1 (k N/tn) 1.9 1. 55 1_ 0 1· 18 2.0 1. 22 1. 35 1.52 Then strength 2 (k N/m) 0.80 0.63 0.54 0. 46 0.66 0.65 0. 59 0. 55 Solder heat resistance (dry) 320t 3201 320°C 320Ό 320t: 320t 2703⁄4 220°C Solder heat resistance (wet resistance) 300^C 280〇C 280t: 280^C 280Ϊ 2803⁄4 Not determined, not measured, warp, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good The coating film 7 was obtained in the same manner as in Example 1 except that the polyimide 7 solution was obtained in the same manner as in Example 1 to obtain Evaluation Sample 7. The results of the evaluation are shown in Table 3. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring width/wiring interval (L/S) = 25 μm/25/zm] was prepared, and the cover film 7 obtained in Example 7 was placed on a printed substrate. The circuit surface of the circuit surface is subjected to hot pressing to obtain a wiring substrate 7 having a cover film. [Example 8] The same procedure as in Example 2 was carried out except that the polyimine solution b obtained in Synthesis Example 2 was used instead of the polyimine solution a in Example 2, and then the polystyrene solution 8 was obtained. The cover film 8 was obtained, and the evaluation sample 8 was obtained. The results of the evaluation are shown in Table 3. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring width/wiring interval (L/S) = 25^111/25//111] was prepared, and the cover film 8 obtained in Example 8 was placed. The circuit board 8 on the printed circuit board is thermocompression bonded to obtain a wiring board 8 having a cover film. [Example 9] The polyimine solution 9 was obtained in the same manner as in Example 3 except that the polyimine solution b obtained in Synthesis Example 2 was used instead of the polyimine solution a in Example 3. The cover film 9 was obtained, and the evaluation sample 9 was obtained. The results of the estimation are shown in Table 3. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring 44 322574 201130888 width/wiring interval (L/S) = 25//m/25//m] was prepared, which was obtained in the ninth embodiment. The cover film 9 is placed on the circuit surface of the printed circuit board, and is thermocompression bonded to obtain a wiring substrate 9 having a cover film. [Example 10] A polyimine solution 10 was obtained in the same manner as in Example 4 except that the polyimine solution b obtained in Synthesis Example 2 was used instead of the polyimine solution a in Example 4. Thereafter, the cover film 10 was obtained, and the evaluation sample 10 was obtained. The results of the evaluation are shown in Table 3. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring width/wiring interval (L/S) == 25 // m/25 μm] was prepared, and the cover film 10 obtained in Example 10 was prepared. The circuit board placed on the printed circuit board is thermocompression bonded to obtain a wiring board 10 having a cover film. [Example 11] The polyimine solution 11 was obtained in the same manner as in Example 11 except that the polyimine solution b obtained in Synthesis Example 2 was used instead of the polyimine solution a in Example 5. The cover film 11 was obtained, and the evaluation sample 11 was obtained. The results of the evaluation are shown in Table 3. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit width (wiring width/wiring interval (L/S) = was prepared, and the cover film 11 obtained in Example 11 was placed on the circuit surface of the printed circuit board to perform heat. The wiring board 11 provided with the cover film was obtained by pressure bonding. [Example 12] A polyimine was obtained in the same manner as in Example 6 except that the polyimine solution b obtained in Synthesis Example 2 was used instead of the polyimine solution a in Example 6. Solution 9 & ^ * After the collection of 12, the cover film 12 was obtained, and the evaluation sample 12 was obtained. The results of the s flat evaluation are shown in Table 3. Further, in the same manner as in the first embodiment, a printed circuit board having a circuit [wiring width/wiring interval (L/S) = 25/m/25/zm] was prepared, and the cover film 12 obtained in Example 12 was placed. The circuit surface of the printed circuit board is thermocompression bonded to obtain a wiring substrate 12 having a cover film. Reference Example 3 The polyimine solution b obtained in Synthesis Example 2 was applied to a single side of a polyimide film (manufactured by Dupont Co., Ltd., trade name: Kapt〇n ENS, vertical yttrium thickness 2 200 mm x 300 mm x 25 // m). The film was dried at 8 (rc for 15 minutes to form a cover film having a thickness of 35/m. The cover film was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3. Example 7 to Example The results of Example 12 and Reference Example 3 are summarized in Table 3. [Table 3] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Reference Example 3 Polyimine solution bbbbbbb Amine compound added BAPP DAPE p-PDA ra-TB TPE-R BAFL No molar ratio 0.23 0.48 0. 88 0.45 0. 33 0. 28 0 Solder heat resistance (dry) 300t: 3003⁄4 3001 30(TC 30(TC 3001C <200* Group C Qu Liangliang Liangliangliang [Example 13] In addition to the blending of 〇.12g (0·28 mmol) instead of the BAPP that has been deployed to implement 5.78g of Example 322574 201130888, the rest of the In the same manner as in the first embodiment, after the polyimine solution 13 is obtained, the cover film 13 is obtained. Evaluation Sample 13. The evaluation results are shown in Table 4. [Example 14] Except that 0.58 g of BAPP (1.4 mmol) was used instead of the 5.78 g of BAPP which had been formulated in Example 1, the other examples and examples In the same manner, after obtaining the polyimide reaction solution 14, the cover film 14 was obtained, and the evaluation sample 14 was obtained. The evaluation results are shown in Table 4. [Example 15] In place of the preparation of 1.15 g of BAPP (2.8 mmol) The coating film 15 was obtained in the same manner as in Example 1 except that 5.78 g of BAPP in Example 1 was prepared, and the evaluation film 15 was obtained. The evaluation results are shown in Table 4. [Example 16] Polyimine was obtained in the same manner as in Example 1 except that 3.46 g of hydrazine (8.4 mmol) was used instead of the 5.78 g of BAPP prepared in Example 1. After the solution 16, the cover film 16 was obtained to obtain an evaluation sample 16. The evaluation results are shown in Table 4. [Example 17] In addition to the formulation of 11.53 g of hydrazine (0·28 mol), the compound of Example 1 was prepared. The same procedure as in Example 1 except that 5.78 g of BAPP was obtained, and after the polyimine solution 17 was obtained, The cover film 17 was obtained, and the evaluation sample 17 was obtained. The evaluation results are shown in Table 4. [Example 18] 47 322574 201130888 In addition to the blending of I7.29g of BAPP (〇.〇42 Moer), the preparation of Example 1 was replaced. The same procedure as in Example i except for 5.78 g of BAPP was carried out to obtain a cover film 18, and an evaluation sample 18 was obtained. The results of the evaluation are shown in Table 4. [Example 19] A polyimine solution 19 was obtained in the same manner as in Example 1 except that 23.05 g of BAPP (〇.〇56 mol) was blended instead of the 5.78 g of BAPP which had been formulated in Example 1. Thereafter, a cover film 19 was obtained, and an evaluation sample 19 was obtained. The results of the evaluation are shown in Table 4. [Example 20] The same procedure as in Example , was carried out except that 28.82 g of BAPP (0.070 mol) was added in place of the 5.78 g of BAPP prepared in Example 1, and after obtaining a polyimine solution, The cover film 2 was obtained, and the evaluation sample 20 was obtained. The results of the evaluation are shown in Table 4. [Example 21] In the polyimine solution obtained in Synthesis Example 1, a 78 g of BAPP (0.014 | ear) was blended in a stepwise manner for 1 hour to obtain a poly-imine solution 2 to obtain the obtained poly The quinone imine solution 21 was applied to a single side of a polyimide film (trade name: Kapt〇n ENS, vertical X horizontal X thickness = 2 〇〇 min x SOOmm x SSem manufactured by Dupont Co., Ltd.) at 8 Å. The crucible was dried for 15 minutes to form a cover film 21 having a thickness of 35 #m. The cover film 21 was placed on a copper foil having a rustproof metal layer on which the surface was removed, and thermocompression bonding was carried out under the conditions of a temperature of 2 Torr, a pressure of 1 MPa, and a time of 60 minutes to obtain an evaluation sample 322574 48 201130888. The bonding strength of the hardened copper foil to the cover film was 20 kN/m. Moreover, the warpage of the cover film is also no problem. After the infrared absorption spectrum of the adhesive layer of the evaluation sample 21 was measured, the absorption reduction of the _ group derived from BTDA was confirmed in the vicinity of 1673 cm-i. Further, the absorption of the imine group was confirmed in the vicinity of 1635 cm-1. From the results of the measurement, in the evaluation sample 21, the condensation reaction of the ketone group and the amine compound (BAPP) in the polyimine resin was estimated to occur at the same time as the thermocompression bonding of the cover film and the copper foil. The evaluation results of the evaluation sample 21 are shown in Table 4. The results of Examples 1 to 21 are summarized in Table 4. [Table 4] Example 13 14 15 16 17 18 19 2 0 2 1 Polyimine solution aaaaaaaaa MPP addition amount (g ) 0. 12 0. 58 1. 15 3.46 11.53 17.29 23. 05 28. 82 5. 78 Moerby 0.005 0. 023 0.047 0. 14 0.47 0. 70 0.93 1. 17 0. 23 Next strength 1 (k N/m) I. 25 1.24 1.07 0.98 0.71 0. 75 0.72 0. 54 2.0 Then strength 2 ( k N/m) 0. 45 0. 47 0.42 0. 49 0.61 0. 63 0.61 0. 42 0.83 Solder heat resistance (dry) 2801 3203⁄4 320t: 320t: 320t: 320t 320*0 320T: 320^ Solder heat resistance ( Moisture resistance) 26〇t: 260t: 28〇t: 280*t 280t: 260X: 260t 26 (TC 300°C) Liang Liangliang Liangliang Liangliangliang from Table 2 to Table 4, in Polyimine Resin After the addition of the amine-based compound, the coating film of Examples 1 to 21 in which the condensation reaction of the ketone group and the amine compound in the polyimide resin is carried out is one of soldering heat resistance (drying) of 28 (TC or more) The heat resistance (moisture resistance) is 26 〇. Above 〇, even after heat treatment in the atmosphere, 150C, 1000 hours, it can be obtained to increase the 〇2kN/m by 49 322574 201130888. Strong n can also inhibit the tortuosity of the cover film. [Example 22] M6g of N-12 (0.004 mol) was prepared in the polyimine solution a obtained in Synthesis Example 1 and further stirred for 1 hour. The solution of the obtained polyimine solution was applied to a polyimide film (a product name: Kapton ENs, thickness = 2 〇〇 1 ^ 300 mm x 25 / zm manufactured by Dupont Co., Ltd.). On one side, the cover film 22 was formed by drying at 8 (rc for 15 minutes to form an adhesive layer thickness 35 " m. This cover film 22 was placed on the copper foil of the rust-preventive metal layer from which the surface was removed, at a temperature of 17 (rc, The conditions of pressure IMh and time i minutes were subjected to thermocompression bonding, and then heated in an oven at a temperature of 150 C, hour @6 hours to obtain an evaluation sample 22. The warpage of the cover film was also no problem. Fourier transform infrared spectroscopy was used. A photometer (commercial product: FT/IR620 manufactured by JASCO Corporation) was used to measure the infrared absorption spectrum of the adhesive layer of the sample i, and the absorption of the ketone group derived from BTaDA was confirmed to decrease in the vicinity of 1673 cm-i. The adhesion strength of the copper foil and the cover film after the adhesion of the adhesive layer of the sample 22 was evaluated to be 1.85 kN/m. Thereafter, the evaluation sample 22 was heat-treated at 15 ° C for 1 hour in an oven and the atmosphere, and the subsequent strength of the treated copper foil and the cover film was measured to be 7373 kN/m. [Example 23] A polyimine solution 23 was obtained in the same manner as in Example 22 except that 3.47 g of N-12 (0.013 mol) was added instead of the N6 which had been mixed with M6g in Example 22. Thereafter, the cover film 23 was obtained, and an evaluation sample 322574 50 201130888 was obtained; the adhesive layer of the It# sample 23 was hardened (4) and the cover film was joined = 62 rm. The heat treatment of the sample 23 in the oven and the cover film in the atmosphere is followed by an hour. The connection strength between the steel box and the ruthenium film after the measurement was 0.62 kN/m. [Example 24] In the U, the 2 molars were replaced with the examples obtained to obtain the poly-g, Μ, and the rest of the system was the same as in Example 22. After the 24 imine material 24, the film 24 was obtained and evaluated. The sample was attached to the cover film after the hardening of the strong sample 24 (4) and the cover film was 1.36 kN/m. Thereafter, the evaluation sample 24 was subjected to heat treatment in an oven and an atmosphere: 522 hours, and the treated (4) and the coating were followed by a strength of 〇.58 kN/m. [Example 25] The ADH (〇.007 Moer) was replaced with the following formula to obtain the arm 酼 g Ν _12, and the rest was the same as in Example 22, 25. After the imidate 25, the cover film 25 is obtained, and the evaluation sample is strong: the copper layer after the adhesive layer is hardened and the cover film is connected, and then the evaluation sample 25 is placed in the tank and the atmosphere. The winning strength is 0.7kN/m. [Example 26] 322574 51 201130888 A polyimine was obtained in the same manner as in Example 22 except that the 3.47 generation surface (0._mole) was used instead of the Ν·12 to which U6g in Example 22 was blended. The solution was 26 胄, and the % of the cover film was obtained, and it was estimated that "the adhesion strength of the copper ruthenium and the cover film after the adhesion of the adhesive layer of the evaluation sample 26 was 1.32 kN/m. Thereafter, the evaluation sample 26 was placed in an oven, large. 5 The heat treatment of the shoe and the hour was carried out. The subsequent strength of the steel film after the treatment was determined to be 0.56 kN/m. [Example 27 1 In addition to the formulation of 5.78 g of ADH (0.033 mol) instead of having been formulated in Example 22 The same procedure as in Example 22 was carried out except that 1.16 g of N-12 was obtained, and after obtaining the polyimide reaction solution 27, the cover film 27 was obtained, and the steel sample box after the evaluation of the adhesive layer of the evaluation sample 27 was obtained. The adhesion strength to the cover film was 1.02 kN/m. Thereafter, the evaluation sample 27 was subjected to heat treatment in an oven and the atmosphere for 15 generations and 诵 hours. The subsequent strength of the copper ruthenium and the cover film after the measurement was 〇.48 kN. /m. Reference Example 4 A cover film was obtained in the same manner as in Example 1. The obtained cover film was obtained. It was placed on a copper foil with a rustproof metal layer on the surface removed, and was pressed at a temperature of 17 〇c, a pressure of 1 MPa, and a time of 1 minute. Thereafter, it was heated in a batch box at a temperature of 15 (TC, time of 6 hours, The evaluation results of the evaluation sample 2 are shown in Table 5. The results of Example 22 to Example 27 and the reference phase 4 are summarized in Table 322574 52 杂 201130888 5 [Table 5] Example Reference Example 2 2 2 3 2 4 2 5 2 6 2 7 4 Polyimine solution aaaaaaa Amine compound N-12 N-12 N-12 ADH ADH ADH BAPP Moerby 0. 07 0. 22 0. 37 0. 12 0. 33 0. 55 0. 23 Then intensity 1 (k N/m) 1. 85 1.62 1. 36 1. 65 1. 32 1. 02 1. 9 Then intensity 2 (k N/m) 0, 73 0. 62 0 58 0. 7 0. 56 0. 48 0. 76 Welding heat resistance (dry) 280 ° C 320t: 320〇C 300°C 320〇C 260t: 200°C Welding heat resistance (wet resistance) 220^ 260° C 240〇C 200 死230°C 220°C Undetermined ———— 良良良良良良 From Table 5, after adding a ruthenium compound to the polyamidene resin, the ketone group and the amine group are rich. The implementation time of the condensation reaction of the compound, F nor based coating film on hardening property (moisture resistance) after the press significantly shortened as 2〇〇. = The heat resistance (drying) is 260 ° C or more, and after the heat treatment at the time of solder heat resistance, it is entered into the atmosphere, at 150 ° C, and at 1000 °. Further, = 刁 is excellent in that 0.2 kN/m is greatly improved, and the bell curvature of the cover film can be suppressed by way of example. However, the present invention is not limited to the purpose of the present invention, and the embodiments of the present invention are described in detail. A person skilled in the art can make many changes without exceeding the scope of the present invention, and the like also includes, for example, in the above embodiment, the use of the polyimine resin of the present invention 322574 53 201130888 can be exemplified. For example, a cover film for a circuit board such as FPC or an adhesive for a bonding sheet, but it may be used for formation of a resin other than the above-described applications such as tape automatic bonding (TAB) or wafer size packaging (CSP). [Simple description of the diagram] None. [Main component symbol description] None 0 54 322574

Claims (1)

201130888 VII. Patent application scope: 1. A polyimine resin, which is a straight system. It is a constituent unit having the following general formulas (1) and (2): OAVO ΟΛΥΟ N R2· T ΟΛΥΟ Ar ΟΛΥΟ Ν In each case, ΑΓ represents a tetravalent aromatic group derived from an aromatic tetracarboxylic anhydride, and R1 represents a divalent diamine-based oxyfluoride residue 'R2 derived from a diamine-based oxyhydrogenation represented by an aromatic The divalent aromatic monoamine residue produced by the group diamine contains a ketone group in Ar and/or Han 2, m and n represent the molar ratio of each constituent monoterpene, and m is 〇75 to 丨〇. In the above range, the aforementioned ketone group of the polyamidofluorene alkane having n in the range of 0 to 0.25 is reacted with an amine group having an amine compound having at least two primary amino groups as a functional group to form C= The N bond, the polyamidofluorene oxirane has a crosslinked structure by the aforementioned amine compound. 2. The polyimine resin according to claim 1, wherein the amino compound is a diterpene compound. 3. An adhesive resin composition comprising the following (A) and (B); (A) having a structural unit represented by the following general formulae (1) and (2) and having a weight average molecular weight of 1 〇 〇〇〇 200 200 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 322 R R R R R R R R R R R R R R R R R R The tetravalent aromatic group 'R represents a divalent diamine-based oxyfluoride residue derived from a diamine oxime-oxygen, and R2 represents a divalent aromatic diamine residue derived from a scented diamine, and a ketone group is contained in Ar and/or & m, n represents a molar ratio of each constituent unit, m is in the range of 0.75 to lo, η is in the range of 0 to 0.25; and (Β) has at least An amine compound having two first-order amine groups as a functional group; and the above-mentioned i-stage amine group is in a range of from 0.004 mol to 1.5 mol in total with respect to the ketone 1 mol in the above (Α) component, Contains the aforementioned component (B). 4. The adhesive resin composition according to claim 3, wherein the amine compound is a diterpene compound. A hardened material obtained by hardening a binder resin composition as described in claim 3 or 4. A cover film for laminating an adhesive layer and a film film for covering, characterized in that: 322574 2 201130888 'The aforementioned adhesive layer is an adhesive resin composition as described in claim 3 or 4 of the patent application scope. Formed by. A circuit board comprising a substrate, a wiring layer formed on the substrate, and a cover film according to claim 6 in which the wiring layer is coated. 8. The circuit board according to claim 7, wherein the wiring layer and the cover film have a peel strength of 〇.2 kN/m or more after the long-term heat resistance test at 150 ° C for 1,000 hours in the air. . A method for producing a polyimine resin, comprising: a step of preparing a polyimine solution containing a ketone group-containing polyamidooxane; and adding at least 2 to the polyimine solution a step of a group 1 amine group as a functional group of an amine group; a step of subjecting a ketone group of the above polyamidiamine oxirane to a condensation reaction of a first amine group of the aforementioned amine compound. 10. The method for producing a polyimine resin according to claim 9, wherein the amino compound is a diterpene compound. 11. The method for producing a polyimine resin according to claim 9 or claim 10, wherein the ketone group is 1 mol, and the total of the amine groups is 0.004 to 1.5 mol. The amine compound is added in a manner within the range of the ear. The method for producing a polyimine resin according to any one of claims 9 to 11, further comprising an acid anhydride component containing an aromatic tetracarboxylic dianhydride and a diamine-containing hydrazine a step of reacting a diamine component of an oxyalkylene and an aromatic diamine to form the polyamidoxime oxime; 3 322574 201130888 and at least one of the aromatic tetracarboxylic dianhydride and the diamine component of the raw material s same base. A method for producing a circuit board, comprising: a substrate, a wiring layer formed on the substrate, and a cover film covering the wiring layer, wherein: the third or fourth item of the patent application is prepared a step of coating and drying the adhesive resin composition in a solution state on a cover film layer to form a cover film of an adhesive layer; and disposing the cover film so that the adhesive layer is adjacent to the wiring layer, The step of thermocompression bonding is carried out; and the ketone group of the component (A) and the amine group of the first component of the component (B) are subjected to a condensation reaction to form a C=N bond simultaneously with the thermocompression bonding. 4 322574 201130888 • IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: No. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: L r Ν 0 people YO Μ ΟΛΥΟ oArYo ΟΛΥΟ Π 3 322574