TW201035172A - Polyimide resin, method for producing the same, polyimide resin composition and cured product - Google Patents

Abstract

The present invention provides a heat-cured type resin composition that is excellent to heat resistance, dimension stability and mechanical physical properties upon coating a film as well as excellent to storage stability. Provided are polyimide resin, heat-cured type resin composition and cured product formed by curing the composition, the said polyimide resin is characterized by having the structures of general formula (1) (R1 is a residual group by deleting NCO group from diisocyanate), and general formula (2), preferably it has the structure obtained from using cyclohexanetricarboxylic acid and 4,4'-diisocyanate-3,3'-dimethyl-1,1-biphenyl. (in formula, X is a residual group by deleting two phenolic hydroxyl groups from phenolic-based compound having two and more of hydroxyl group s in one molecule.)

Description

201035172 VI. Description of the Invention: [Technical Field] The present invention relates to a coating which can have excellent heat resistance, flame retardancy, dimensional stability, mechanical properties (toughness, flexibility), and surface smoothness. A cured resin such as a film, which has excellent solubility in a solvent after long-term storage, and has excellent storage stability, and also has excellent compatibility with other resins, and a method for producing the same. Or a polyimide composition and a cured product thereof. [Prior Art] In recent years, electrical insulating materials such as heat-resistant coating materials, interlayer insulating materials for printed wiring boards, or insulating materials for semiconductors, and build-up materials used in the electrical industry. Up material), a prepreg resin, a heat-resistant adhesive, etc., are required to have excellent storage stability after being stored for a long period of time, and have excellent solubility in a solvent, and a cured product. Mechanical properties (toughness, flexibility), heat resistance, dimensional stability. In particular, in the field of electronic equipment such as computers, there is a strong demand for miniaturization of a flexible film substrate or a rigid substrate. Therefore, in response to these requirements, the mechanical properties of the protective layer, the adhesive layer, and the insulating layer of the substrate are improved ( Strength, flexibility, heat resistance, dimensional stability are indispensable. A polyimine resin which can be used for producing a cured product having superior heat resistance, mechanical properties, and dimensional stability is, for example, a polymerized imine resin having a structural residue by a lanthanoid compound ( Structural residue) A terminal structure obtained by bonding with a urethane bond, and a urethane bond formed by a reaction of a phenolic hydroxyl group with an isocyanate group of 201035172 (see, for example, Patent Document 1). However, the polyamidene resin disclosed in Patent Document 1 is not sufficiently compatible with other resins such as an epoxy resin, so that when it is mixed into a composition, there is a problem that the composition is gelled by insufficient stability. . (Patent Document 1) 'Japanese Patent Application Laid-Open No. 2007-2775 No. 1-8. SUMMARY OF THE INVENTION [Problem to be Solved] [The present invention provides a polyimine resin which can be used A cured product such as a coating film having excellent heat resistance, flame retardancy, dimensional stability, mechanical properties (toughness, flexibility), and surface smoothness is obtained, and the solubility in a solvent is good after long-term storage. The storage stability, and also has excellent compatibility with other resins such as epoxy resin; and a resin composition containing the polyimide resin. 〇 v [Means for Solving the Problem] The inventors of the present invention have found out the findings of the following items (1) to (7) by focusing on the results of the discussion. (1) a polyimine resin having a terminal structure obtained by bonding a structural residue of a phenolic compound to a urethane bond, and a structure in which a cyclohexane ring is directly bonded to a quinone ring; The polyimine resin disclosed in the above-mentioned Patent Document 1 is equivalent to the heat resistance, mechanical properties, and dimensional stability of the cured product, and the solubility in 201035172 in a solvent is also good after long-term storage. (2) A polyimine resin having a terminal structure obtained by bonding a structural residue of a phenolic compound to a urethane bond, and a structure in which a cyclohexane ring is directly bonded to a quinone ring 'There is a bl〇eked phenol structure at the end of the quinone imine resin via a urethane bond. By this, it is possible to further improve the compatibility with an epoxy resin or the like and to exhibit a wide range of properties and characteristics as a thermosetting resin composition. (3) The block type phenol structure at the end is dissociated from the main chain skeleton of the resin under high-temperature drying conditions at the time of producing the coating film, so that the viscosity is lowered, so that the surface smoothness of the surface of the coating film can be remarkably improved. (4) A polyimine resin having a terminal structure obtained by bonding a structural residue of a phenolic compound with a urethane bond, and a structure in which a cyclohexane ring is directly bonded to a quinone ring In the presence of a phenol compound such as a phenol resin, it can be stably produced without causing gelation by using an isocyanate method. (5) A polyimine resin having a terminal structure obtained by bonding a structural residue of a phenolic compound to a urethane bond, and a structure in which a cyclohexane ring is directly bonded to a quinone ring A coating film having superior heat resistance, dimensional stability, and mechanical properties can be obtained alone, and further cured by using a cured product containing the composition of the polyimide resin and the epoxy resin Excellent heat resistance, mechanical properties, dimensional stability. Further, the polyimine resin is not limited to an epoxy resin and has good compatibility with various resins, and has excellent long-term storage stability even when it is mixed with various resins to form a composition. ❹ 6) a terminal structure obtained by bonding a structural residue having a phenolic compound to a urethane bond as described above, and a polyfluorene which is a structure in which a cyclohexane ring is directly bonded to a quinone ring In the composition of the resin and the epoxy resin, the terminal block type phenol structure of the polyimine resin is dissociated from the main chain skeleton of the resin to produce a phenolic hydroxyl group under high-temperature drying conditions at the time of producing a coating film. And an isocyanate group, and wherein the phenolic hydroxyl group reacts with the epoxy resin to form a secondary hydroxyl group. The formed secondary hydroxyl group reacts with the dissociated isocyanate group to reform the urethane bond, thereby suppressing dielectric properties which are usually observed in the curing of the epoxy resin due to formation of a hydroxyl group. deterioration. Further, by forming a stronger crosslinked product by a double reaction of a phenolic hydroxyl group and an isocyanate group, the cured product of the above composition exhibits superior properties in terms of durability, mechanical properties, and the like. The present invention has been achieved based on the above findings. That is, the present invention provides a polyimine resin characterized by having a structure represented by the general formula (1) and a structure represented by the general formula (3).

Ri represents the residue after removal of the NCO group from the diisocyanate); 201035172 ο ΗΟ Χ-Χ-Ο Ν Ν Η ........... (2) (wherein, χ represents by A residue in which a phenolic compound having two or more phenolic hydroxyl groups in the molecule removes two phenolic hydroxyl groups). Further, the present invention provides a cured product obtained by hardening a polyimine resin as described above. Further, the present invention provides a thermosetting resin composition characterized by containing a polyimine resin as described above and an epoxy resin. Further, the present invention provides a cured product obtained by hardening the thermosetting resin composition as described above. Furthermore, the present invention provides a method for producing a polyimine resin, which comprises reacting a compound having a difunctional or higher phenolic hydroxyl group with a diisocyanate compound and cyclohexane tricarboxylic anhydride. [Effect of the Invention] The polyimine resin of the present invention has excellent storage stability and is excellent in solubility to a general-purpose solvent after long-term storage. And a composition containing the polyimine resin of the present invention or the polyimide resin and the epoxy resin, for example, when it is coated, the coating film has excellent dimensional stability and mechanical properties. (Strength and flexibility) Therefore, it can be used for a coating agent, a wiring interlayer insulating film, an adhesive, and the like. Further, the polyimine resin of the present invention is not limited to an epoxy resin and has good compatibility with various resins, and also has excellent storage stability. [Embodiment] 201035172 [Best Mode for Carrying Out the Invention] The polyimine resin of the present invention has the following structure represented by the formula (1) and a structure represented by the formula (3):

(1 represents a residue obtained by removing an NCO group from a diisocyanate);

0 IJ Η Ο —X— Ο Ν ❹ ❹ (wherein, Η ..... (2) X represents the removal of a phenolic compound having two or more phenolic hydroxyl groups in one molecule. Residues after two purifying hydroxyl groups). The cured product obtained by using the polyimine resin of the present invention has a superior solvent solubility and mechanical properties (toughness, flexibility), heat resistance, dimensional stability, etc., by the structure of the general formula (1). Significant effect of physical balance. In the polyimine resin of the present invention, the structural ratio of (1) to (2) is preferably from 1:99 to 40:60, more preferably from 2:98 to 30:70 by weight, since Excellent mechanical properties, and compatibility with other components such as epoxy resin tends to be good when the composition is formed. One of the above formula (1) represents a residue obtained by removing an NCO group from a diisocyanate. More specifically, R! has a polyimine resin having a structure of the following formula (3), (4) or (5) because it can attain the remarkable effects of the present invention, that is, A cured product having excellent heat resistance, flame retardancy, dimensional stability, mechanical properties (toughness, flexibility), surface smoothness, and the like, and can be obtained for solvent 201035172 solubility after long-term storage. It is also a reason for the good storage stability of the polyimide resin. (3)

(4)

(wherein '112 each independently represents a hydrogen atom, and a hydrocarbon group of from 1 to 9 '* represents a binding site). In the polyimine resin of the present invention, a polyimine resin having a structure of the above formula (5) as Ri of the formula (1) is preferred because it can obtain a low linear expansion coefficient, that is, The reason for the cured product having superior dimensional stability. R2 of the formula (5) is preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, still more preferably a hydrocarbon group having 1 carbon atom (methyl group). . Further, part or all of the hydroxyl groups of r2_ may be substituted by halogen or the like. The specific structure of the general formula (5) is, for example, a structure represented by the following general formulae (5-1) to (5-4). Among them, a structure represented by the formula () is preferred because it can obtain a polyimide resin for producing a cured product having superior dimensional stability.

ί 5-1) -ΙΟ- 201035172

(5-2)

(5-3) (5-4)

[In the above formula (5-1) to (5-4), the structure represented by the formula (2) of the polyimine resin of the present invention is preferably as follows The structure of the formula (2-1), the formula (2-2), the formula (2_4) or the formula (2-5) is shown as the structure of X because it can be obtained to have superior compatibility with other resins or storage. When it is made into a thermosetting resin composition, it can produce a polyimine resin which is excellent in hardenability and has excellent pot life in addition to heat resistance, mechanical properties, and dimensional stability. .

-(2-1) wherein R2 represents a single bond or a divalent linking group, and R3 represents hydrogen or an alkyl group having 1 to 5 carbon atoms)

(2-2) -11- 201035172, or as follows (wherein R4 represents a structure represented by the formula (2-3) represented by hydrogen or an alkyl group having 1 to 5 carbon atoms)

〇H OH OH ό""5 ^Rs -〇"R5" R6 FV a r6 Re b Re (wherein Rs represents a direct bond or a divalent linker; R6 may be the same and represents a hydrogen atom or a carbon atom The total number of alkyl groups 1 to 18 is 1 or more, and * is a linking group). Wherein, a more specific structure of the rule 2 of the general formula (2-1) and a carbonyl group, a sulfonyl group, a methylene group, an isopropylidene group, a hexafluoromethoxy group, a dimethylarylene group, and a fluorene-9- a divalent linking group such as a di- or tricyclo[5-alkyl-diyl group, etc., and may be a single compound or a complex. Further, R3 includes, for example, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms such as a methyl group, a butyl group or a pentyl group, and the like, and the like, including a polyphenol compound such as a phenol novolak fum varnish type resin, and A structural residue such as a naphthol, an alkylphenol, a formaldehyde-condensed polyphenol resin, or the like after removing two hydroxyl groups. Further, the structure of X of the formula (2) is preferably a mixture of the formula (-(2-5) is the same or excludes: a single bond; an isopropyl group, a side 2.1.2, 8] Ethyl group and propyl group. Further, R4 -12-201035172 which is 2-2) synthesized from a lipid or a cresol phenol is a structure of the formula (2-6) of the following formula (2-3). This is because it can be obtained for producing a polyimide resin having a superior heat-resistant cured product. By using a structure having a phosphorus atom derived from a specific phenol as a block type phenol structure as in the structure of the formula (2-6), the flame retardancy of the polyimide resin can be greatly improved.

(2-6) (* stands for the key node). The polyimine resin of the present invention is preferably a polyimine resin having a structure represented by the formula (6) because it has superior solvent solubility and can be obtained with superior mechanical properties and dimensional stability. Sulphur

(1 represents a residue obtained by removing an NCO group from a diisocyanate). The compound of the formula (6) is preferably a structure of the above formula (3), (4) or (5) because it can attain the remarkable effects of the present invention, that is, it can obtain superior heat resistance. A hardened material such as a flame retardant, dimensional stability, mechanical properties (toughness, flexibility), and a smooth surface coating film, and can be prepared for long-term storage and solubility in a solvent. The reason for the polyimide resin. In the polyimine resin of the present invention, it is preferably -13- 201035172 of the formula (6)

Ri polyimine resin having the structure of the above formula (5) because it can attain a low coefficient of linear expansion, i.e., a carbide having superior dimensional stability. R2 of the formula (5) is preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, still more preferably a hydrocarbon group having 1 carbon atom (methyl group). . Further, R2 - part or all of the hydroxyl group may be substituted by halogen or the like. The specific structure of the above formula (5) is exemplified by the structures represented by the above formulas (5-1) to (5-4). Among them, a structure represented by the formula (5-1) is preferable because it can obtain a polyimide resin for producing a cured product having excellent dimensional stability. If it has the above formula (1) and formula (6), the weight thereof is preferably from 5:95 to 90:10, more preferably from 10:90 to 60:40, because it can obtain a superior solvent. Solubility, and the resulting cured product also has a superior mechanical properties of the polyimide resin. The polyimine resin of the present invention preferably further has a structure represented by the formula (7) because it can be obtained for producing a polyimide resin having a good mechanical strength.

When the polyimine resin of the present invention has the structure of the above formula (7), the content of the formula (7) in the polyimine resin of the present invention is preferably from 1 to 30% by weight, more preferably It is preferably 2 to 20% because it can obtain superior solvent solubility, and the obtained cured product has a superior mechanical properties of a polyimide resin. More specifically, the polyimine resin of the present invention is more preferably a polyphenylene having a structure represented by the formula (8-1) and a structure represented by the formula (8-2). An amine resin because it can obtain superior solvent solubility, and the dimensional stability of the resulting cured product tends to be good.

〇 (where m and η are each 1 to 100). Among them, the structural unit represented by (8-1) and (8-2) may be a polymer of random, block, alternating or the like in one molecule. When the polyimine resin of the present invention is a polyimine resin having a structure represented by the above formula (8-1) and a structure represented by the formula (8-2), the content thereof is Each is preferably in the range of 10 to 90% by weight, more preferably 20 to 80% by weight, because it can obtain a polyimide resin for producing a cured product having superior dimensional stability. The weight of the above formula (8-1) and formula (8-2) is preferably from 5:95 to 95:5, more preferably from 10:90 to 60:40, since it can be prepared to have a superior solvent dissolution. The reason for the stability of the polyimine resin with stability over time. Specific examples of the polyimine resin of the present invention are as follows. The polyimine resin of the present invention preferably has a structure represented by the following general formulae (9-1) to (9-4) because it can be obtained for the manufacture of superior heat resistance. The reason for the dimensional stability of the cured polyimine resin.

〇 II C-N--* Η

(9-1) (9-2) *__γ.

(9-3)

Wherein m, n, p and q are each 1 to 100, and Υ represents a structure represented by the following formula (3) or (4). The structural units of the above formulas (9-1) to (9-4) may be random, block, alternating, etc. polymers in one molecule. In this case, the structures of the above formulas (9-1) to (9-4) preferably each have a range of 5 to 70% by weight, more preferably 10 to 50% by weight 'because it is available It has excellent solvent solubility and can produce a polyimide resin having a cured product having excellent dimensional stability and mechanical properties. Specific examples of the poly-16 - 201035172 quinone imine resin having a structure represented by the above general formulae (9-1) to (9-4) include, for example, having the formula represented by the following formula (9) Structure of polyimine resin and the like.

The structural unit in the parentheses of 'm, n, p, q in the above formula (9) is a polymer which may be random, block, alternating or the like in one molecule. Further, the polyimine resin of the present invention preferably has a structure represented by the following formulas (丨0·1) to (1〇-6), and a weight average molecular weight of from 1,000 to 100,000. The quinone imine resin is obtained because it can obtain a polyimine resin having superior solvent solubility and a cured product having excellent heat resistance, mechanical properties, and dimensional stability. In the structure of the general formula (10-1), the cyclohexane ring is a polyimine resin which is directly bonded to the structure of the quinone ring and further has a biphenyl skeleton, which has excellent storage stability. After long-term storage, the solubility in a solvent is good, and the cured product exhibits characteristics of superior mechanical properties, heat resistance, and dimensional stability Q. -17· 201035172

(10-1) (10-2) (10-3)

Each of a1 to a6 in the above formula (10-1) to formula (10-2) is from 1 to 10,000. In addition, * represents a key node. γ in the general formula (10-4) to the general formula (1〇-6) represents a structure represented by the above formula (3) or formula (4). However, the structural unit -18- 〇 201035172 in the parentheses of the general formulae (12-1) to (12-6) may be a random, block, alternating or the like polymer in one molecule. Here, the structure included in the parentheses of a1 to a6 is preferably in the range of 9% by weight each, more preferably in the range of 5 to 70% by weight, since it is excellent in solvent solubility. And a polyimine resin which can obtain a cured product having dimensional stability and mechanical properties, having a weight average molecular weight of 1,000 as represented by the above formulas (10-1) to (10-6) The 100000 polyimine tree 'al to a6 is a repeat representing a structural unit and is from 1 to 10,000. The polyarylene resin having the structural unit represented by the general formulae (10-1) to (1〇_6) is a specific structural example suitable for solving the problem of the present invention, and such a binding element may contain a plurality of molecules in one molecule. Or may also contain other structures. Examples of the polyimine resin having a structure represented by the above formulas (10-1) to (10-6) and having a weight average molecular weight of 1,000 to 1,000 Å are shown below. Case 2 to the periphery, superior structure, the structure of the grease has an amine tree unit, and specifically Η0-Χ-0 and -Af a1 -a2- a2 -A4- a3 'A5~ a4

Nr a5 a6

o U -Ri - N^O-X-OH a7 In the formula (10-7), the residue structure of Ri after the isocyanate group is removed by the diisocyanate compound. The structure of the above formula (3), () or (5) is preferred because it can obtain a polyimide resin having excellent mechanical properties. A7 represents the number of repetitions and is in the range of 10,000, and is not limited to the order and number of occurrences of structural units included in the arc of 31 to a6 in parentheses. In the general formula (1C, 'Ai represents the structure represented by the above (10-1), a2 represents -(10-7) two (4 and the ruler is 1 in 用-7) -19- 201035172 ( 10-2) The structure represented by a3 represents the above (ι〇_3) structure, A* represents the structure represented by the above (1〇_4), the structure represented by A5 (10-5), a6 Further, the polyimine obtained by the reaction of the phenol isocyanate group at the end of the above formula (1〇_7) and the chain segment growth is represented by (1〇_6), and the polyimine resin having the following structure is shown. The representative hydroxy group represented by the above table is exemplified by HO-X-0 human N--A7-ΟX-Ri-N^OXH a7 〇人-a7- oX-Ri-N^o-X —OH H a7 .. a8 In the structural resin represented by the above formula (10-8), the structure represented by the formula "A7" is as follows:

Ai-j a2 a3 - a4 a5 - A6 a1 a2 a3 a < l· a5 In the formula (10-9), Αι to A6 are the same as the formula (10-7). Further, a to a6 represents a repeat of the structural unit and the structural unit of 1 al to a6 is not limited to the number of 丨丨 1| times in the a7 bracket. A7 represents a repeat of the structural unit and is from 1 to 100. This represents a repetition of the structural unit and is from 1 to 100. a structural unit of the formula (1 1〇-6) having a polyimine resin of the above formula (1〇-7) and the formula (10-8) and the like (10) to the formula (10-6) The content is preferably in the range of 5 to 70j, preferably in the range of 10 to 50% by weight, because it can obtain the solubility of ginger solvent, and the cured product obtained has a superior ruler of 1 - (10-8) 〇.醯imine--...(10-9). , ι to A6 phase to 10000 ° i sequence, appearance, a8 also 〖formula (10-1) to (children% 'more I have superior stability, -20- 201035172 mechanical properties of the Juyi In the polyimine resin having a structure represented by the general formula (10-1) to the general formula (10-6), it is preferred to contain 10 to 40% by weight of the general formula (10). The structural unit represented by -1) and (10-4) is a polyimine resin as a structural unit because it has superior solvent solubility and can be obtained by having a superior compatibility with other resins. In the polyimine resin having the formula (10-1) to the formula (10-6), it is preferred to contain 10 to 60% by weight of the formula (10-1) to (in the case of the amine resin). 10-3) The polyimine resin of the knot structure unit, because it can obtain a polyimide resin for producing a cured product having superior heat resistance or dimensional stability, in the above formula ( 10-7) The polyimine resin represented by the structure of the polyimine resin having the structure of (2-1) of X is as follows:

hAi^4_A2~H"A34fA44fA5-]4A6H-R,_i a1 a2 a3 a4 a5 station』y

(10-10) O In the polyimine resin represented by the above formula (10-8), an example of a polyimine resin having a structure of a structural formula of (2 -1 ) of X is as follows :

An example of a polyimine resin having a structure of the formula (2-2) having X in the polyimine resin represented by the above formula (10·7) is as follows: -21- 201035172

HO

Αι -a3 - 33

(10-12) 〇

An example of the polyimine resin having a structure of the formula (2-2) having X in the polyimine resin represented by the above formula (10-8) is shown by T:

(10-13) An example of a polyimine resin having a structure in which the structural formula of X is (2_6) in the polyimine resin represented by the above formula (1〇-7) is as follows:

An example of the polyimine resin having a structure of the formula (2-6) wherein X is represented by the above-mentioned polyimine resin represented by the above formula (10-8) is as follows:

The polyimine resin of the present invention is a residual carboxylic acid or a carboxylic acid having an acid anhydride compound whose terminal structure is derived from a raw material, in addition to the structure of the general formula (2), which does not impair the efficacy of the present invention. The structure of the anhydride. In addition to this -22-201035172, regarding the acid anhydride, it is described below. The polyimine resin of the present invention has a resin excellent in storage stability and has a property of being easily soluble in an organic solvent. The polyimine resin of the present invention can also be dissolved in a conventionally used polar solvent organic solvent such as N-methylpyrrolidone or dimethylformamide, but can also be dissolved in previously unusable gamma. An organic solvent having a weak solubility such as γ-butyrolactone. In the present invention, in the judgment of whether or not the polyimine resin used in the present invention is soluble in an organic solvent, the polyimine resin of the present invention is added to a concentration of 1% by weight in an organic solvent, and After standing at 25 ° C for 7 days, it was carried out by visual observation of the appearance. The polyimine resin used in the present invention is preferably a polyimine resin which is soluble in gamma-butyrolactone, and more preferably is soluble in gamma-butyrolactone at 25 ° C to become 10 The weight percent of the polyimide resin because it can obtain a polyimide resin having superior storage stability. If a polyimine resin which is soluble in gamma-butyrolactone is to be obtained, it can be obtained, for example, according to a method for producing a polyimide resin as described in the following. The polyimine resin used in the present invention may be a polyimine resin having a linear structure or a polyimide resin having a branched structure. Further, a polyester-modified polyester quinone imine or a urethane-modified urethane ruthenium may have a structure as a copolymerization component. The polyiminoimine resin of the present invention preferably has a weight average molecular weight of from 1,000 to 200,000, more preferably from 2,000 to 1,000,000, since it can be made tough after being dried or formed into a cured product, and is formed into a solution. It is easy to use -23-201035172, and it is possible to obtain a polyimine resin having a film or a molded article having excellent mechanical strength and dimensional stability. The molecular weight can be determined by gel permeation chromatography (GPC) or quantitative analysis of the amount of terminal functional groups. The measurement of the weight average molecular weight in the present invention is carried out by gel permeation chromatography (GPC) and measured under the conditions described below. Measuring device: HLC-8320GPC and UV8320 manufactured by Tosoh Corporation.

Pipe column: Two SuperAWM-H X manufactured by Dong Caoda Co., Ltd. Detector: RI (differential refractometer) and UV (254 nm). Data Processing: EcoSEC-WorkStation manufactured by East Soda Co., Ltd. 〇 Measurement conditions: Column temperature 40 °C Solvent D M F Flow rate 0.35 ml/min Standard: Standard curve was prepared from polystyrene standard samples.

Sample: A DMF solution having a converted resin solid content of 0.2% by weight was filtered by a microfilter (injection amount: 10 μΐ) ° from compatibility with other resins, solution stability or hardenability with epoxy resin The viewpoint of the present invention is that the acid value of the polyimine resin of the present invention is preferably in the range of 1 to 50 K〇Hrng/g, more preferably 1 to 30 KOH mg/g. The polyimine used in the present invention. The resin can be produced, for example, by the method of -24-201035172 as described below. Process 1: Using a polyhydric phenol compound (A) having two or more phenolic hydroxyl groups in one molecule, a polyisocyanate compound (B) containing a diisocyanate compound, and an acid anhydride compound (C) containing a cyclohexane tricarboxylic anhydride The method of imidization is directly applied. Process 2: using a polyisocyanate compound (B) containing a diisocyanate compound, and an acid anhydride compound (C) containing a cyclohexane tricarboxylic anhydride, and directly imidizing, the isocyanate group present at the terminal is combined with a bifurcation. A method in which a polyhydric phenol compound (A) having two or more phenolic hydroxyl groups is reacted. Process 3: After using the diamine compound (D) and the anhydride compound (C) containing cyclohexane tricarboxylic anhydride and directly imidating, after adding a diisocyanate compound as a terminal isocyanate, and having two in one molecule A method in which the above phenolic hydroxyl group polyphenol compound (A) is reacted. The preparation method of the above Process 1 to Process 3 is called "isocyanate method", and when the isocyanate method is used in the presence of the polyhydric phenol compound (A) to form a ruthenium imine resin, it can provide a gel. Stable resin. It can be inferred that the polyhydric phenol compound (A) will selectively react with an isocyanate group to form a block type phenol structure to inhibit the side reaction of the isocyanate group, and at a high temperature, partial dissociation is performed to effectively react with an acid anhydride or The carboxyl group is reacted to form a quinone bond or a guanamine bond. In particular, it is effective in the case of an aliphatic or alicyclic acid anhydride such as a hydrogenated trimellitic acid which is slow in reactivity. When the polyimine resin of the present invention is produced, it is preferable to reduce the amount of residual water -25 to 201035172 to maintain the physical properties in a good state, to easily control the reaction, and to easily produce various modified polyimine resins. Preferably, the above method 1 is adopted. Hereinafter, the polyhydric phenol compound (A) which can be used in the above Process 1 is described in detail, for example, hydroquinone, biphenol, tetramethylbiphenol, ethylene bisphenol, bisphenol A, bisphenol F, Bisphenol S, cyclohexylene bisphenol (biguanide Z), dimethylbutylene bisphenol, 4,4'-(1-methylethylidene) bis[2,6-dimethylphenol], 4 , 4'-(1-phenylethylidene)bisphenol, 5,5'-(1-methylethylidene)bis[1,1'-biphenyl-2-ol], naphthalenediol, Dicyclopentadiene modified bisphenol, 9, 10 • dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,l〇-dihydro-9-oxa-10-phosphorphenanthrene-10-oxide ) a reaction product with hydroquinone or the like. Further, as the polyhydric phenol compound (A), a phenol compound such as a phenol novolak resin, a cresol novolac type resin, or a nonylphenol novolak resin may be used. Further, in the method for producing a polyimine resin of the present invention, the use of a polyfunctional phenol compound having a trifunctional or higher functional group as the polyhydric phenol compound (A) may cause high viscosity or gelation of the resin. Therefore, it is preferred to use a polyhydric phenol compound (difunctional polyphenol compound) containing two phenolic hydroxyl groups. Among them, a bisphenol-based compound such as bisphenol A, bisphenol F or bisphenol S or a reaction product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and hydroquinone is preferred. Wait. Further, a functional phenolic compound such as phenol or cresol may be used in part without impairing the efficacy of the present invention. The above 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and hydroquinone reverse -26- 201035172 should be difficult to dissolve in the general solvent "9,10-dihydro-9-oxygen Although the reaction product of hetero-10-phosphaphenanthrene-10-oxide and hydroquinone is used as a flame retardant additive, the solubility in a solvent is generally poor, so that it is limited in use. In the method for producing a polyimine resin of the present invention, since it is used as the polyhydric phenol compound (A), the skeleton of the reaction product is introduced into the polyimide resin, and as a result, the polyimide resin is obtained. It is soluble in a general-purpose solvent such as γ-butyrolactone, and therefore it is a resin having superior storage stability, but it can improve flame retardancy. The polyphenol compound (formula) used in Process 1 is preferably used in an amount such that the polyimine resin of the present invention is contained in the resin in an amount of 1 to 40% by weight, more preferably 2 to 30% by weight. The amount is derived from the structure of the polyphenol compound (Α) because it can be made into a polyimide resin having superior hardenability and storage stability. Further, it is more preferable that the polyimine resin contains 2 to 10% by weight of a structure derived from a polyhydric phenol compound in its resin because agglomerates having superior dimensional stability and flame retardancy can be obtained. The reason for the imine resin.聚 The polyisocyanate compound (Β) used in the present invention includes, for example, an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and the like. The aforementioned aromatic polyisocyanate compound includes, for example, 4,4'-diphenylmethane diisocyanate. Diphenylmethane diisocyanate; p-phenylene diisocyanate, meta-phenyl diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolyl diisocyanate, 2,6-toluene Diisocyanatoacetate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldi-27- 201035172 phenyl-4,4'-diisocyanate, 3,3'-diethyl Diphenyl-4,4,diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, hydrazine, 3_bis(α,α-dimethylisocyanatemethyl)benzene, tetramethyl hydrazino Isocyanate, diphenylene ether-4,4,-diisocyanate and naphthalene diisocyanate; toluene diisocyanate such as 2,4-toluene diisocyanate or 2,6-toluene diisocyanate. -1 ) the difference between the biphenyl skeletons represented Cyanate ester and the like.

(wherein R 2 each independently represents a hydrogen atom, a hydrocarbon group having a carbon number of from 丨 to 9 which may be modified by fluorine.). The diisocyanate represented by the above formula (3 -1 ) includes, for example, 4,4'-diisocyanate-3,3'-dimethyl-1,1,-biphenyl, 4,4,-diisocyanate -3,3'-diethyl-1,1'-biphenyl, 4,4,-diisocyanate-2,2,-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate - 2,2'-diethyl-1,1'-biphenyl, 4,4,-diisocyanate-3,3'-bistrifluoromethyl-1,1'-biphenyl, 4,4'- Diisocyanate-2,2'-bistrifluoromethyl-1,1'.biphenyl, and the like. The aforementioned aliphatic polyisocyanate compound includes, for example, hexamethylene diisocyanate, diazonic acid diisocyanate, trimethylhexamethylene methylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl group. Methane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, etc. In addition, the polyisocyanate compound (Β) can also be used after the above polyisocyanate compound and various polyol components are in excess of the isocyanate group pre--28- 201035172 The isocyanate prepolymer obtained by the reaction is first carried out. The polyimine resin used in the present invention may also employ a branched structure to improve solvent solubility or compatibility with other resins. The method of branching is to use a trifunctional or higher polyisocyanate compound having an iso-cyanate ring or a biuret of the above-mentioned diisocyanate, for example, an iso-cyanate body belonging to the aforementioned diisocyanate compound. The body, the adduct body, the allophanate body, etc. may be used. The polyisocyanate compound (B) is preferably a diphenylmethane such as 4,4'-diphenylmethane diisocyanate, for the reason of having excellent solvent solubility, compatibility, mechanical properties, dimensional stability, and the like. Isocyanate, tolyl diisocyanate, diisocyanate of a biphenyl skeleton represented by the above formula (3-1), and the like. These compounds may be used singly or in combination of two or more. In particular, it is preferred to use a diisocyanate represented by the formula (3-1) to obtain a polyimine resin for producing a cured product having dimensional stability or improved mechanical properties, more preferably diphenyl. Methane diisocyanate or toluene diisocyanate can also improve solvent solubility or long-term storage stability. The amount of the diisocyanate represented by the formula (3-1) is the total amount of the polyisocyanate compound (B) used. The amount is preferably from 3 to 80% by weight based on the amount of 'because it can obtain a polyimide resin having superior dimensional stability. Among the diisocyanates represented by the above formula (3-1), preferred are 4,4'-diisocyanate-3,3'-dimethyl-indole, biphenyl diisocyanate, -29- 201035172 It is possible to obtain a polyimide resin having excellent solvent solubility and a cured product having excellent heat resistance, mechanical properties and dimensional stability. In addition, the diisocyanate compound represented by the above formula (3-1), 4,4'-diphenylmethane diisocyanate, toluene diisocyanate may be used singly or in combination, and may further have Other structural diisocyanate compounds, monoisocyanate compounds, or trifunctional or higher polyisocyanate compounds are used. The diisocyanate compound represented by the formula (3-1) and the diisocyanate compound represented by 4,4'-diphenylmethane diisocyanate or toluene diisocyanate preferably use 10% by weight or more of all the isocyanate compounds. Because it can obtain a cured product having mechanical properties, dimensional stability, and heat resistance such as superior mechanical strength or elongation at break; further, since a polyimide resin having excellent stability over time is also obtained For this reason, it is preferred to use from 1 to 80% by weight of the total isocyanate compound. In addition, by using toluene diisocyanate, the flame retardancy of the obtained cured product can be further improved. In addition, since it can be used to obtain a cured product having a particularly low coefficient of linear expansion (that is, a cured product having superior dimensional stability), thus 4,4'·diisocyanate-3,3'-dimethyl-1 The 1'-biphenyl is preferably used in an amount of from 30 to 80% by weight based on the total isocyanate compound. If 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl, and 4,4'-diphenylmethane diisocyanate or toluene diisocyanate are used, it is preferably used. 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl is 30 to 90% by weight of all isocyanate compounds, and • 30- 201035172 4,.4'·diphenylmethane Isocyanate or toluene diisocyanate wt%; more preferably 4 to 4'-diisocyanate-3,3'-di-all isocyanate compound 40 to 80% by weight 'diisocyanate and / or toluene diisocyanate is 20 In addition, regarding diphenylmethane diisocyanate, if the amount of 4,4'-diisocyanate-3,3'-di is not used, based on the polyisocyanate compound (B), Each is preferably from 1 to 70% by weight of '% by weight, more preferably from 30 to 60% by weight. The foregoing acid anhydride compound (C) is a cyclohexane tricarboxylic acid anhydride including, for example, cyclohexane-1,3,4-trimethylhexane-1,3,5-trisic anhydride-3,5-anhydride, cyclohexyl Alkanol-1,2 anhydride, etc. Among them, since it can be used to obtain mechanical properties having superior mechanical strength, elongation at break, and the like, it is preferred that the cyclohexyl ester represented by the formula (4-1) is from 1 to 7 armor. The base-1,1'.biphenyl is 4,4'-diphenylmethane to 60% by weight. When toluene diisocyanate methyl-1,1'-biphenyl, the total weight of the raw material is more preferably 10 to 60 ΐ carboxylic anhydride. Cyclohexane anhydride-3,4-anhydride, ring, 3-tricarboxylic anhydride-2,3-f Solvent solubility, excellent heat-resistant hardened product Π3,4-tricarboxylic anhydride -3,4-anhydride: ❹

(4-1) In addition, it may be mixed in the range in which the ring used in the present invention does not impair the hardening of the present invention, and preferably 5% by weight or less is derived from the use as the hexane- Impurities such as 1,2,4-tricarboxylic acid. In the above reaction of the cyclohexane tricarboxylate compound used in the present invention, the anhydride group and the isocyanate group are used to produce a cyclic anhydride of the raw material in, for example, 1% by weight of the tricarboxylic anhydride, which is separated from the isocyanic acid. Carbonation reaction -31 - 201035172 to form a quinone bond, while the isocyanate group and the carboxylic acid will be decarbonated to form a guanamine bond. In this way, the molecules will be connected in a line to form a molecule. The amount of the above cyclohexanetricarboxylic anhydride to be used is preferably from 5 to 100% by weight, more preferably from 10 to 80% by weight, based on the total of the acid anhydride compound (c) constituting the polyimine resin because A polyimide resin having excellent solvent solubility can be obtained, and a cured product having excellent mechanical properties and heat resistance can be obtained. Further, the amount of the above-mentioned cyclohexanetricarboxylic anhydride used is preferably from 2 to 60% by weight, more preferably from 5 to 50% by weight, based on the total mass of the raw materials constituting the polyimine resin. The acid anhydride compound (C) is an acid anhydride other than cyclohexane tricarboxylic acid anhydride insofar as it does not impair the efficacy of the present invention. Other acid anhydrides include, for example, a polycarboxylic acid anhydride having one acid anhydride group, or a polycarboxylic acid anhydride having two acid anhydride groups, and the like. The above polycarboxylic acid anhydride having an acid anhydride group includes, for example, an aromatic tricarboxylic anhydride such as trimellitic anhydride or naphthalene-1,2,4-tricarboxylic anhydride. When an aromatic tricarboxylic anhydride such as trimellitic anhydride or naphthalene-1,2,4-tricarboxylic anhydride is reacted with an isocyanate compound, it is also the same as the above-mentioned cyclohexanine trisin anhydride. The cyanate vine group will undergo a decarboxylation reaction to form a quinone imine bond, while the isocyanate group and the carboxylic acid will undergo decarbonation to form a guanamine bond. In this way, the molecules will be connected in a line to form a molecule. The above polycarboxylic acid anhydride having two acid anhydride groups includes, for example, pyromellitic dianhydride, benzophenone-3,3,4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3' , 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-2 , 2',3,3'-tetracarboxylic dianhydride, naphthalene-32- 201035172 -2,3,6,7·tetracarboxylic dianhydride, naphthalene-1,2,4,5·tetracarboxylic dianhydride, naphthalene- l,4,5,8-tetracarboxylic dianhydride, decalin-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-i, 2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene_1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4, 5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,3,9,10-tetracarboxylic dianhydride, hydrazine -3,4,9,10-tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-double ( 2,3-dicarboxyphenyl)ethane dianhydride, M-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride , 2,3-bis(3,4-dicarboxyphenyl)propane dianhydride, Bis(3,4-dicarboxyphenyl)ruthenic anhydride, bis(3,4-dimercaptophenyl)ether dianhydride; 2 glycol bis-dehydrated trimellitate, propylene glycol bis-dehydrated trimellitate ' Butanediol double-dehydrated trimellitate, hexamethylene glycol bis-dehydrated phenyl-H-formate, polyethylene glycol bis-dehydrated trimellitate, polypropylene glycol bis-dehydrated trimellitate, or Other alkylene glycol double-dehydrated trimellitate and the like. Among the acid anhydrides other than the aforementioned cyclohexane tricarboxylic anhydride, preferred are benzoic anhydride, pyromellitic dianhydride, benzophenone-3,3,4,4,-tetracarboxylic dianhydride, Diphenyl ether-3,3,,4,4,-tetracarboxylic dianhydride, biphenyl-3,3',4,4,-tetracarboxylic dianhydride, biphenyl-2,2,,3, 3,-tetracarboxylic dianhydride, and ethylene glycol double-dehydrated trimellitate; more preferred is trimellitic anhydride. The amount of use of the trimellitic anhydride as the acid anhydride in the case of using the trimellitic anhydride is preferably 5 to 90 mol% of the cyclohexane based on the molar amount of the entire acid anhydride compound (C). Tricarboxylic anhydride, from 20 to 90 mol% -33 to 201035172 of trimellitic anhydride; more preferably from 10 to 50 mol% of cyclohexane tricarboxylic anhydride, and from 40 to 90 mol% of trimellitic anhydride. Further, the amount of the above-mentioned cyclohexanetricarboxylic anhydride and trimellitic anhydride used is 2 to 60 mol%, preferably 2 to 60 mol%, based on the molar amount of all the raw materials for constituting the polyimine resin. It is 2 to 60 mol%. Further, in terms of the balance of solvent solubility, mechanical properties, and heat resistant physical properties, the above-mentioned cyclohexane tricarboxylic anhydride and trimellitic anhydride are preferably used, and cyclohexane tricarboxylic anhydride and benzophenone-3 are used. , 3', 4, 4'-tetracarboxylic dianhydride for use in hydrazine, cyclohexane tricarboxylic anhydride and pyromellitic dianhydride, etc.; more preferably cyclohexane tricarboxylic anhydride and selected from More than two kinds of groups consisting of trimellitic anhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and pyrogallanoic dianhydride, more preferably Three kinds of alkyl tricarboxylic anhydride, trimellitic anhydride, benzophenone-3,3,,4,4'-tetracarboxylic dianhydride. When used as an acid 'anhydride together with cyclohexane tricarboxylic anhydride and trimellitic anhydride and benzophenone-3,3',4,4'-tetracarboxylic dianhydride, it is used to form a quinone imine resin. The molar amount of all the acid anhydrides (C) is preferably from 5 to 90% by mole of cyclohexanetricarboxylic anhydride, from 2 to 80% by mole of trimellitic anhydride, and from 3 to 50% by mole. Dibenzophenone _3,3',4,4'-tetracarboxylic dianhydride; more preferably 10 to 80 mol% of cyclohexanetricarboxylic anhydride, 10 to 80 mol. /. Pyromellitic anhydride, 5 to 30 moles. /. Dibenzophenone - 3,3,,4,4,-tetracarboxylic dianhydride. Further, the above-mentioned amounts of cyclohexanetricarboxylic anhydride, trimellitic anhydride, and benzophenone-3,3,4,4'-tetracarboxylic dianhydride are used to constitute all of the polyimide resin. The molar amount of the raw materials is preferably from 2 to 60 mol%, from 2 to 60 mol% and from 2 to 60 mols, respectively. /. . -34- 201035172 In addition, aromatic, aliphatic, alicyclic dicarboxylic acid compounds, polycarboxylic acid compounds, monool compounds, glycols may also be employed without damaging the efficacy of the present invention. A compound or a trifunctional or higher polyhydric alcohol compound. Such aromatic, aliphatic, alicyclic dicarboxylic acid compounds and polycarboxylic acid compounds can be exemplified by phthalic acid, fumaric acid (fumaric acid), adipic acid, and lipoic acid (癸). Diacid), succinic acid (succinic acid), maleic acid (maleic acid), cyclohexanedicarboxylic acid, trimellitic acid (1,2,4-benzenetricarboxylic acid), pyromic acid ( 1,2,4,5-benzenetetracarboxylic acid), etc.; a monohydric alcohol compound, a diol compound, and a trifunctional or higher polyhydric alcohol compound are exemplified by methanol, ethanol, propanol, ethylene glycol, propylene glycol, and butyl Glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, hexanediol, decanediol, trimethylolpropane, pentaerythritol, polyether polyol, polyester polyol, Polycarbonate polyol, polydimethyloxane polyol, and the like. In the method for producing a polyimine resin, a polyhydric phenol compound (A) having two or more phenolic hydroxyl groups, a polyisocyanate compound (B), and an acid anhydride compound (C) are reacted. The molar number (ma) of the phenolic hydroxyl group of the polyhydric phenol compound (A) ^, the molar number (mb) of the isocyanate group in the polyisocyanate compound (B), and the hydroxyl group-free and carboxyl group in the acid anhydride compound (C) The total molar number (me ) is preferably one having the relationship represented by the following formula (1) because it is excellent in reproducibility for manufacturing and has excellent solvent solubility, storage stability, and hardenability, and The mechanical % is also a good hardened polyimine resin: 2 ^[(ma) + (me) ] / ( mb ) ^ 1 (formula). And, if at the same time as (1) above When it has a relationship of -35 to 201035172 represented by the following formula (2), a polyimine resin which can be used for producing a cured product having superior mechanical properties can be obtained: (ma) / (me) (Formula 2 When the polyimine resin of the present invention is produced by the above Process 1, 'specifically, for example, a polyhydric phenol compound (A), a polyisocyanate compound (B), and a polycarboxylic acid anhydride containing cyclohexane tricarboxylic anhydride ( C) Feeding, in a reaction vessel, and raising the temperature while stirring to carry out a decarboxylation reaction. The reaction can be carried out at a temperature ranging from 50 ° C to 250 ° C, and is preferably carried out at a temperature of from 70 ° C to 180 ° C from the viewpoint of the reaction rate and prevention of side reactions. The stability of the polyimine resin tends to be good, so the reaction is preferably continued until the isocyanate group is almost completely terminated. Further, for some residual isocyanate groups, an alcohol or a phenol compound may be added to complete the reaction. In the method for producing a polyimine resin of the present invention, since the reaction can be carried out uniformly, it is preferred to use an organic solvent. In this case, the organic solvent may be added to the reaction system in advance to carry out a reaction or a reaction. Further, in order to maintain an appropriate reaction rate, the ratio of the organic solvent in the system is preferably 98% by weight or less, more preferably 1% to 90% by weight based on the reaction system. Since the raw material component is a compound containing an isocyanate group. Therefore, these organic solvents are preferably aprotic polar organic solvents which do not have an active proton such as a hydroxyl group or an amine group. The organic solvent can be used, for example, dimethylformamide, monomethylammoniumamine, N-methyl-2-B than slightly sulphur ketone, dimethyl fluorene, -36-201035172 环丁枫, and A polar organic solvent such as γ-butyrolactone. In addition to the above solvent, an ether solvent, an ester solvent, a ketone solvent, a petroleum solvent, or the like may be used as long as it is soluble. Various solvents may be used in combination. The ether solvent used in the method for producing a polyimine resin used in the present invention includes, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol II. Ethylene glycol dialkyl ethers such as butyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, ruthenium triethylene glycol Polyethylene glycol dialkyl ethers such as diethyl ether and triethylene glycol dibutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol acetate Ethylene glycol monoalkyl ether acetates such as ether ether esters; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate Poly(ethylene glycol) monoalkyl ether esters such as butyl ether ester, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and triethylene glycol monobutyl ether acetate; propylene glycol II a propylene glycol dialkyl ether such as methyl ether, propylene glycol diethyl ether or propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol bis diethyl ether, dipropylene glycol dibutyl ether, and tri-propylene glycol Polypropylene glycol dialkyl ethers such as methyl ether, tri-propylene glycol diethyl ether, tri-propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol-ethyl ether acetate, propylene glycol monobutyl acetate Propylene glycol monoalkyl ether acetates such as ether esters; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, trimethyl propylene glycol monomethyl ether acetate, Polyvinyl acetate propylene glycol monoalkyl ether esters such as tri-propylene glycol monoethyl ether acetate, tri-propylene glycol monobutyl ether acetate; low molecular ethylene-propylene copolymer-37-201035172 composite copolymerized polyether Dialkyl ethers of diols; copolymerized polyether II Acetate a one alkyl ethers; copolymerized alkyl esters of polyether diols; and one copolymerized polyether glycol alkyl esters of alkyl ethers. The ester solvent includes, for example, ethyl acetate and butyl acetate. The ketone solvent includes acetone, methyl ethyl ketone, and cyclohexanone. Further, petroleum solvents may be used, including toluene, xylene or other high-boiling aromatic solvents, or aliphatic and alicyclic solvents such as hexane and cyclohexane. In the production of the polyimine resin of the present invention, the proportion of the organic solvent in the system in the case of using an organic solvent is preferably 98% by weight or less, more preferably 40% to 90% by weight based on the reaction system. The organic solvent used in the manufacture of the polyimine resin of the present invention, in particular, based on reducing the odor or toxicity of the solvent, the amount of residual solvent in the drying of the coating film and the hardening of the coating film, and the moisture absorption of the solvent of the coating film. For the reason of the amount or the like, it is preferred to use γ-butyrolactone. Further, in terms of the obtained polyimine resin, a structure which is soluble in γ-butyrolactone is also preferable. A polyimine resin which is soluble in γ-butyrolactone and has good properties in various physical properties (heat resistance characteristics, low linear expansion coefficient, mechanical properties) is, for example, used in the presence of a polyphenol compound (Α) 4,4,-diisocyanate-3,3'-dimethyl-1,1'-biphenyl diisocyanate, and diisocyanate compound containing 4,4'-diphenylmethane diisocyanate, and cyclohexane -1,3,4-tricarboxylic acid-3,4-anhydride, and trimellitic anhydride are obtained by reacting therewith. Further, at this time, a part or a total amount of 4,4'-benzophenone diisocyanate may be substituted with toluene diisocyanate. The polyhydric phenol compound (A) which is suitable for the production of a polyimine resin which is soluble in the aforementioned γ-butyrolactone and has various physical properties and is also a good property is exemplified by, for example, 'bisphenol A, bisphenol F , a bisphenol compound such as bisphenol S, or naphthalenediol, or biphenyl hydrazine, tetramethylbiphenol, or hydrogen awake, or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- a reaction product of an oxide and hydroquinone, and the like. In the manufacture of the above polyimine resin which is soluble in γ-butyrolactone and has various physical properties and also good properties, the polyphenol compound and 4,4'-diisocyanate-3,3'-dimethyl-1 , 1'-biphenyl, 4,4-diphenylmethane diisocyanate, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and trimellitic anhydride used in proportion 〇' The molar amount of all the raw materials of the polyimide resin is preferably from 2 to 60 mol% based on the molar amount. Further, these polyimine resins which are soluble in γ-butyrolactone and which have good properties in various physical properties (heat resistance characteristics, low linear expansion coefficient, mechanical properties) are more preferably polyhydric phenol compounds (Α). In the presence of 4,4'-diisocyanate-3,3'-dimethylbiphenyl, 4,4-diphenylmethane diisocyanate and cyclohexane-1,3,5-tricarboxylic acid-3,4 It can be obtained by reacting an anhydride, trimellitic anhydride, and benzophenone-3,3',4,4'-tetracarboxylic dianhydride. At this time, 4' 4,4- phenylmethane diisocyanate, cyclohexane-oxime, % tricarboxylic acid-3,4-anhydride, trimellitic anhydride, and benzophenone-3,3,,4,4' The use ratio of the tetracarboxylic dianhydride is preferably from 2 to 60 mol% based on the amount of the moles of all the raw materials constituting the polyimine resin. Further, at this time, a part or a total amount of 4,4'-diphenylmethane diisocyanate may be substituted with toluene diisocyanate. The polyhydric phenol compound (Α) used herein may, for example, be a bisphenol compound such as bisphenol a, biguanide F or bisphenol S, or naphthalenediol, or biphenol-39-201035172, tetramethylbiphenol. Or hydroquinone, or a reaction product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and hydroquinone. In particular, when it is desired to improve flame retardancy, it is preferred to use a reaction product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and hydroquinone as the polyhydric phenol compound. The so-called "hardened or hardened property" mentioned above and below in the present invention means that the present polyimine resin is included in addition to the hardened substance of the component which can react with the present polyimide. Or other resin, additive, inorganic material component, etc. which do not react with the present polyimide resin, and the cured film of the coating film or the molded article obtained by simply drying the solvent and the physical properties thereof. At the same time, it also includes: the polyimine resin is mixed with a hardener which can be reacted by heating or light and/or does not react with the resin, but is added with the component itself and hardened by heat or light. The hardened material and its hardened properties are included. The cured product of the present invention is obtained by hardening the polyimine resin of the present invention. Specifically, for example, the polyimine resin of the present invention is applied onto a substrate or formed into a molded article, and then heated at 100 to 300 ° C to prepare a dried coating film, a dried molded product, or The hardening reaction can be carried out to obtain a cured product such as a cured coating film or a cured molded article. The aforementioned substrate is a variety of materials that can be used without limitation. The substrate includes, for example, plastic, metal, wood, glass, inorganic materials, and the like. Further, in the polyimine resin of the present invention, another thermosetting resin component may be further added to form a thermosetting resin composition. Specifically, for example, an epoxy resin, a melamine resin, an isocyanate compound - 40 - 201035172, a decanoate, an alkoxy decane compound or the like may be added, but the thermosetting component is preferably an epoxy resin. The epoxy resin preferably has two or more epoxy groups in the molecule. Such epoxy resins include, for example, bisphenol type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, and the like, bisphenol type epoxy resins; phenol novolac epoxy resin, cresol a novolac type epoxy resin such as a novolac type epoxy resin or a bisphenol type novolac; and various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols^ An epoxide type; a biphenyl type epoxy resin such as an epoxide of 2,2',6,6'-tetramethylbiphenol; an epoxy resin having a naphthalene skeleton; an epoxy resin having a skeleton, etc. An aromatic epoxy resin or a hydrogenated product of such an aromatic epoxy resin; an aliphatic epoxy resin such as neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether; An alicyclic epoxy resin such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane formate or bis-(3,4-epoxycyclohexyl) adipate For example, an epoxy resin containing a hetero ring such as triglycidyl isocyanurate or the like. Among them, due to the availability of superior hard

The Q-coated film is a thermosetting polyimine resin composition having mechanical properties, and therefore is preferably an aromatic epoxy resin, and more preferably a naphthalene epoxy resin. The epoxy resin of the naphthalene skeleton is one having a naphthalene skeleton and two or more glycidoxy groups in the molecule, and the novolac lacquer body of the naphthalene skeleton also belongs to the category. The blending amount of the polyimine resin used in the present invention and the epoxy resin may be 1/100 to 50/ by weight of the resin component (polyimine resin) / (epoxy resin). The ratio of 1 and more preferably 1/10 to 20/1 - 41 to 201035172 Specifically, the aforementioned melamine resin includes, for example, an alkoxylated melamine resin. The alkoxylated melamine resin can be reacted with an alcohol compound by using a part or all of a methylol compound obtained by a reaction of a three-till ring-containing amino compound such as melamine or benzoxamine with formaldehyde. The alkoxylated melamine resin obtained. As the alcohol compound to be used herein, a lower alcohol having a carbon number of about 1 to 4 can be used. Specifically, a methoxymethylolated melamine resin, a butylated methylolated melamine resin or the like can be used. The molecular structure may be completely alkoxylated, or a methylol group may remain, and an imine group may remain. The resin structure of the alkoxylated melamine resin used in the present invention is preferably a methoxyl group from the viewpoint of being compatible with the polyamidene resin and the hardenability at the time of curing. The methylated melamine resin is more preferably a methoxymethylolated melamine resin having a methoxylation ratio of 80% or more. Further, the resin structure of the melamine resin may also be a self-condensing multinuclear body. From the viewpoint of compatibility or stability, the degree of polymerization at this time is preferably from 1 to 5, more preferably from 1.2 to 3. The number average molecular weight of the alkoxylated melamine resin used in the present invention may be from 1 Å to 10,000. From the viewpoint of compatibility with the polyimide resin and hardenability at the time of hardening, it is preferably from 300 to 2,000, more preferably from 400 to 1,000. The alkoxylated melamine resin used in the present invention can be simultaneously fed with melamine or benzoguanamine, formaldehyde (formalin) and an alcohol to react, and -42-201035172 can also be used to preliminarily make melamine or benzoguanamine and formaldehyde. (Formalin) The reaction is carried out to obtain a methylolated melamine compound, followed by alkoxylation with an alcohol compound. Commercially available products of the alkoxylated melamine resin used in the present invention include, for example, a methoxymethylolated melamine resin, specifically, for example, a product CYMEL 300, 301 manufactured by Nihon Cytec Industries, Inc. 303, 305, etc. Further, the methoxyl-methylated melamine resin containing a methylol group includes, for example, commercially available from Nihon Cytec Industries, O Inc., CYMEL 370, 771, and the like. The methoxylated trimer amide resin containing an imide group includes, for example, CYMEL 325, 327, 701, 703, 712 and the like manufactured by Mitsui Chemicals, Inc. The methoxylated butoxylated trialtamine resin includes, for example, those commercially available from Nihon Cytec Industries, Inc., CYMEL 232, 235, 236, 238, 266, 267, 285, and the like. The butoxylated melamine resin includes, for example, a product manufactured by Nihon Cytec Industries, Inc., U-VAN 20SE60, and the like. The amount of the alkoxylated melamine resin used in the present invention, ^ can be obtained by the synergistic effect of the physical properties of the polyimide resin and the hardening of the alkoxylated melamine resin, and can make a particularly superior machine. The physical property and the high Tg (glass transition temperature) coexist. 'In terms of the solid content of the resin of the polyimide resin, it is preferably 1 to 30 parts by weight, more preferably 1 part by weight. It is more preferably from 1 to 10 parts by weight, particularly preferably from 2 to 7 parts by weight, to 20 parts by weight. As the isocyanate compound, for example, an aromatic isocyanate compound, an aliphatic isocyanate compound, an alicyclic isocyanate-43-201035172 ester compound, or the like can be used, and it is preferred to have two or more isocyanates in one molecule. A polyisocyanate compound based on a polyisocyanate. Further, a blocked isocyanate compound can also be used. The above alkyl alkoxydecane includes, for example, an alkyltrialkoxydecane, a dialkyldialkoxydecane, and the like. The aforementioned alkyltrialkoxydecane includes, for example, methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, methyltributyloxybutane, ethyltrimethoxydecane. , ethyl triethoxy decane, ethyl tripropoxy decane, ethyl tributoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tripropoxy decane, phenyl Tributoxy decane and the like. The aforementioned dialkyldialkoxydecane includes, for example, dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldipropoxydecane, dimethyldibutoxydecane, Diethyldimethoxydecane, diethyldiethoxydecane, diethyldipropoxydecane, diethyldibutoxydecane, diphenyldimethoxydecane, diphenyldiethyl Oxydecane, diphenyldipropoxydecane, diphenyldibutoxydecane, methylethyldimethoxydecane, methylethyldiethoxydecane, methylethyldipropoxy Decane, methylethyldibutoxydecane, methylphenyldimethoxydecane, methylphenyldiethoxydecane,methylphenyldipropoxydecane,methylphenyldibutoxy Decane, trimethyl methoxy decane, trimethyl ethoxy decane, triethyl methoxy decane, triethyl ethoxy decane, triphenyl methoxy decane, triphenyl ethoxy decane, etc. . Further, a condensate of an alkyl alkoxy decane such as the above-mentioned condensate of -44-201035172 alkyltrialkoxy decane or a dialkyl compound or the like can also be used. Further, the resin of the present invention may be added to a hardener or a reactive resin such as a polyester PPS resin, a PPE resin, a poly(arylene resin) or the like, a melamine resin, an amphoteric epoxy resin, or a cyanate ester compound. a curing catalyst or a hardening accelerator for dicyandiamide, decylamine or a derivative thereof, an imidazole, an amine phenol, an organic phosphine, a scale salt, a quaternary ammonium salt, and the like A foaming material, a leveling agent, a slip agent, a moisture improving agent, an antioxidant, an ultraviolet absorber, or the like is used to form a product. Further, the polyimine resin of the present invention is used as a resin composition as needed, such as a ceramium filler, an organic pigment, an inorganic pigment, an extender pigment, or a rust preventive. These are the above. ® The above-mentioned enamel fillers include, for example, barium sulfate, titanic acid powder, particulate cerium oxide, cerium oxide, talc, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, cerium oxide filling materials, and various particle diameters can be used. And the amount of physical properties of the resin or its composition can be added. The weight of these appropriate parts is such that it must be dispersed to be uniform after about 5 to 80% by weight. In particular, the composition uniformly forms a coating film or a flaky alkoxy decane on the surface, a phenoxy resin, a binder resin, a benzoating agent, a polybasic acid anhydride or a melamine, a class, a hydroxy group, and a light. The cation contact, as an additional additive, anti-settling agent, and refractory polyimide resin group, may be further added with various extender pigments, either alone or in combination with two kinds of acid bismuth, cerium oxide, magnesium carbonate, aluminum, and the like. It is not necessary to prevent the amount of the present invention from being surrounded by solids, but it is preferable to use the resin of -45-201035172 to be sufficiently smaller than the film thickness of the resin. However, if the slip resistance of the coating film or the sheet is to be improved, the partial particle diameter may be forced to be large. The dispersion method of the particle system lanthanum can be carried out by using a conventional two-roll type roll or a three-roll type roll, or by a bead ball mill, a high-speed disperser, or the like, and the particle surface can be dispersed in advance. The treatment agent is surface modified. The above organic pigments include: azo pigments; for example, anthraquinone blue, anthocyanin, green copper anthraquinone pigments, quinophthalone pigments, and the like. The foregoing inorganic pigments include, for example, chrome yellow, zinc chromate (zinc chrome yellow) ^, molybdenum orange chromate; ferrocyanide such as Prussian blue; titanium oxide, zinc oxide (zinc white) , red iron oxide (red dan), oxidized metal oxide such as chrome carbide green; cadmium yellow, cadmium red; for example, metal sulfides, selenides of barium sulfide; sulfates such as lead sulfate; for example, ultramarine cyanate; Carbonate, cobalt, purple; for example, phosphate of manganese violet; metal powder such as aluminum powder, zinc powder, brass powder, magnesium powder, iron powder, copper powder, nickel powder; carbon black, and the like. Further, any of other coloring agents, rust inhibitors, and body pigments may also be used. These may be used alone or in combination of two or more. The resin composition of the polyimine resin and the thermosetting resin composition of the present invention is prepared by using the polyimine resin of the present invention or a resin composition thereof to prepare a coated product or a molded article. ~300 T: It can be dried or hardened by heating. The substrate used in the method for forming the above coating film can be used without particular limitation. The substrate includes, for example, plastic, metal, wood, glass -46-201035172, inorganic materials, and composite materials thereof. Further, the polyimide resin of the present invention and the composition thereof can also be used for a resin and a composition layer (layer A) and support thereof for a manufacturing form suitable for a flexible circuit board. The form of a film (adhesive film) composed of a bulk film (layer B). The adhesive film can be applied to a resin film obtained by dissolving the polyimine resin of the present invention or a composition thereof in an organic solvent according to various methods, and applying the resin varnish to the support film. The crucible is then dried by heating or blowing hot air or the like to form a resin layer or a resin composition layer. The support film (layer B) is used as a support for the production of the adhesive film, and in the manufacture of the flexible circuit substrate, it is finally peeled off or removed. The support film includes, for example, a polyolefin such as polyethylene or polyvinyl chloride, polyethylene terephthalate (hereinafter, simply referred to as "PET"), polyethylene naphthalate, and the like. Polyester, polycarbonate, and metal foil such as release paper or copper foil. When used as a supporting ruthenium film for supporting copper foil, iron (III) chloride (ferric chloride), copper (II) chloride (copper chloride: copper (II)) Chloride) Etching liquid can be removed by etching. The support film may be subjected to a release treatment in addition to a mat surface treatment or a corona treatment, and it is more preferable to apply a release treatment in consideration of peelability. The thickness of the support film is not particularly limited, and is usually used in the range of 10 to 150 μm, more preferably 25 to 50 μm. -47- 201035172 Organic solvents for varnish include, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc.; ethyl acetate, butyl acetate, celecoxib acetate, propylene glycol acetate Acetate esters such as monomethyl ether ester and chlorhexidine acetate; sorbitan, butyl butyl alcohol, etc.; aromatic hydrocarbons such as toluene and xylene; dimethylformamide , dimethyl acetamide, N-methyl pyrrolidone, gamma-butyrolactone and the like. The organic solvent may be used in combination of two or more. The drying conditions are not particularly limited, but the content of the organic solvent in the resin composition is usually 5% by mass or less, preferably 3% by mass or less. The specific drying conditions are different depending on the hardenability of the resin composition or the amount of the organic solvent in the varnish. However, in the case of, for example, a varnish containing 3 to 60% by mass of an organic solvent, it is usually 80 to 12 (TC). It can be dried in about 3 to 13 minutes. Those skilled in the art can set the optimum drying conditions by simple experiment. The thickness of the resin and its composition layer (layer A) can usually be set at a range of 5 to 500 μm. A preferred range of the thickness of the A layer is different depending on the use of the adhesive film, but when the multilayer flexible circuit substrate is produced by the build-up method, the thickness of the conductor layer for forming the circuit is usually The thickness of the ruthenium layer corresponding to the interlayer insulating layer is preferably in the range of 1 Å to ΙΟΟ μιη. The ruthenium layer can also be protected by a protective film, which is protected by a protective film to prevent the resin from being 5 to 7 Å μm. The dust on the surface of the composition layer is adhered or injured, etc. The protective film is peeled off when laminated. The protective film can use the same material as the support film. The thickness of the protective film is not particularly limited, but The adhesive film obtained by using the polyimine resin or composition of the present invention is particularly suitable for the production of a multilayer flexible circuit substrate. In the following, a multilayer can be produced. The method of the flexible circuit board is described. The adhesive film is suitable for laminating on a flexible circuit board by a vacuum laminator. The flexible circuit board used here is needless to be mainly used for patterning processing. A conductor layer (circuit) on one or both sides of a substrate such as a polyester substrate, a polyimide substrate, a polyimide substrate, or a liquid crystal polymer substrate may be used for alternately forming circuits and A multilayer flexible circuit substrate in which a layer of an insulating layer is formed on one or both sides is further used in a plurality of layers. Further, from the viewpoint of the adhesion of the insulating layer to the circuit substrate, the circuit surface is preferably The roughening treatment is preliminarily applied to a surface treatment agent such as hydrogen peroxide/sulfuric acid, MEC Etch Bond (manufactured by MEC Co., Ltd.), etc. Commercially available vacuum laminating machines include, for example, Nikko Morton Stock Co., Ltd. A vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressing laminator manufactured by Meiki Co., Ltd. , a roll-type dry coater manufactured by Hitachi Plant Technologies, Ltd., a vacuum laminator manufactured by Hitachi AIC, I nc, etc. Regarding the laminated layer, if the adhesive film has a protective film, After the protective film is removed, the adhesive film is pressed and heated on one side, and is layered on the circuit substrate. The condition of the lamination is to preheat the adhesive film and the circuit substrate as needed, and the pressing temperature is preferably 70 to 14 (TC, the pressing pressure is preferably 1 to 11 -49 to 201035172 kgf/cm2, and the air pressure is The laminate may be laminated under reduced pressure of 20 mmHg or less. In addition, the method of laminating may be batch mode or continuous use of a roll. After the adhesive film is laminated on the circuit board, it is cooled to near room temperature and then the support film is peeled off. The polyimine resin or composition laminated on the circuit board is heated, and when the composition is a thermosetting resin composition, it is cured by heating. The heating (hardening) condition is usually selected at 150 ° C. To 220 ° C, 20 minutes to 180 minutes, more preferably in the range of 160 ° C to 200 ° C, 30 to 120 minutes. In addition, if the support film has a release treatment or stripping of polyoxyl In the case of the layer, the support film may be peeled off after heat-hardening the thermosetting polyimide resin composition, or after heating (hardening) and drilling. The polyimine resin or polyfluorene of the present invention is formed. The hardening of the imine resin composition After the layer, drilling may be performed on the circuit substrate by a drill, a laser, a plasma, or a combination thereof, as needed, to form a via-hole or a through-hole. In particular, it is usually a laser using a carbon dioxide gas laser or a YAG laser (Yttrium Aluminum Garnet Laser). Secondly, surface treatment is applied to an insulating layer (a cured product of a polyimide or a polyimide resin composition). The surface treatment can be carried out by a method used in the desmear treatment, and can be carried out simultaneously with the desmear treatment. Usually, the chemical used in the desmear treatment is an oxidant. The "oxidant" includes, for example, Manganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, etc. It is preferably used in the manufacture of a multilayer printed wiring board using a build-up method. It is generally used as an oxidizing agent for roughening -50-201035172 insulating layer, that is, an alkaline permanganic acid solution (for example, potassium permanganate or sodium permanganate in aqueous sodium hydroxide solution). Further, a treatment using a swelling agent may be applied. Further, after the treatment using the oxidizing agent, a neutralization treatment using a reducing agent is generally performed. After the surface treatment is applied, a conductor layer is formed by plating on the surface of the insulating layer. The conductor layer formation can be carried out by a combination of electroless plating and electrolytic plating. In addition, a plating resist which is inversely patterned with the conductor layer can be formed, and only electroless plating is used. The conductor layer is formed. After the conductor layer is formed and subjected to an annealing treatment at 150 to 200 ° C for 20 to 90 minutes, the peel strength of the conductor layer can be further increased and stabilized. A method of forming a conductor layer by pattern processing to form an electric circuit can be, for example, a subtractive process, a semi-additive process, or the like which is well known to those skilled in the art. In the case of the subtractive method, the thickness of the electroless copper-plating layer Ο w is 〇·1 to 3 μm, particularly preferably 0.3 to 2 μm. An etching resist is formed by forming an electroplating layer (panel plating layer) thereon to a thickness of 3 to 35 μm, preferably 5 to 20 μm. An etching solution such as ferric chloride (in) (ferric chloride) or copper chloride (bismuth) (copper chloride) is etched to form a conductor pattern, and then a "resistance resist" is removed to obtain a circuit board. Further, in the case of the semi-additive method, the electroless copper-clad layer is formed into an electroless copper-clad layer at a thickness of 0.1 to 3 μm, preferably 0.3 to 2 μm, to form a pattern resist (-51-201035172 pattern resist). The circuit board can be obtained by electroplating copper and then peeling off. a film in which a film of a support film is replaced by a heat-resistant resin layer (heat-resistant resin film), that is, a film composed of a polyimide film or a composition layer thereof (a layer of a layer) and a heat-resistant resin layer (layer C). It can be used as a base film for a flexible circuit board. Further, a film composed of a resin and a composition layer (layer thereof), a heat resistant resin layer (C layer), and a copper foil (D layer) can be similarly used as a base film of a flexible circuit board. In this case, the base film has a layer structure in the order of the ruthenium layer, the C layer, and the D layer. The base film described above and the heat resistant resin layer can be used to form a part of the flexible circuit board without being peeled off. A film in which an insulating layer (A' layer) composed of a cured product of the polyimine resin or the resin composition of the present invention is formed on a heat resistant resin layer (C layer) can be used as a base for a single-sided flexible circuit substrate. Film. Further, a film having a layer structure of the A' layer, the C layer, and the A' layer, and an A' layer, a C layer, and a copper foil (D layer) and having an A' layer, a C layer, and a D layer The film of the sequential layer structure can also be used similarly as a base film for a double-sided flexible circuit substrate. The "heat resistant resin" used for the heat resistant resin layer includes a polyimide resin, an aromatic polyamide resin, a polyamidolimine resin, a liquid crystal polymer, and the like. Particularly preferred are polyimine resin and polyamidolimine resin. Further, in terms of characteristics for the flexible circuit board, it is preferable to use a breaking strength of 100 MPa or more, an elongation at break of 5% or more, a thermal expansion coefficient of 20 ppm or less at 40 to 150 ° C, and The glass transition temperature Tg is -52 to 201035172 200 ° C or higher, or a decomposition temperature of 300 ° C or more. A heat-resistant resin that meets the above characteristics is suitable for use in a commercially available film-like heat-resistant resin: for example, a polyimide film "UPILEX-S" manufactured by Ube Industries, Ltd., Toray • Polyurethane film "KAPTON" manufactured by DuPont-Toray Co., Ltd., polyimide film "APICAL" manufactured by Kaneka Corporation, Teijin special film "ARAMICA" manufactured by Teijin Advanced Films O Limited, liquid crystal polymer film "VECSTAR" manufactured by Kuraray Co., Ltd., and Sumitomo Bakelite Co. , Ltd.) Polyetheretherketone film "SUMILITEFS-1100C" manufactured by the company. The thickness of the heat resistant resin layer is usually from 2 to 150 μm, preferably from 10 to 5 μm. A heat-resistant resin layer (layer C) may also be used by an applied surface treatment. The surface treatment includes: dry treatment of rough surface treatment, corona discharge treatment, plasma treatment, etc.; chemical treatment of solvent treatment, acid treatment, alkali treatment, etc.; and sandblasting treatment, mechanical honing treatment, and the like. In particular, from the viewpoint of adhesion to the layer A, it is preferred to apply a plasma processor. The base film for a single-sided flexible circuit board composed of the insulating layer (A') and the heat-resistant resin layer (C) can be produced in the following manner. First, a resin varnish obtained by dissolving the resin composition of the present invention in an organic solvent is prepared in the same manner as in the case of the above-mentioned adhesive film, and then the resin varnish is applied onto a heat-resistant resin film, and heated or blown with hot air or the like. The organic solvent is dried to form a polyimide layer or a resin composition layer. The conditions of the organic solvent -53 - 201035172, drying conditions, and the like are the same as those of the above-mentioned adhesive film. The thickness of the polyimide layer or the resin composition layer is preferably in the range of 5 to 15 μm. Next, the polyimide layer or the resin composition layer is dried by heating to form an insulating layer of a polyimide or a polyimide composition. The conditions for the heat hardening are usually selected from the range of from 20 minutes to 180 minutes at 150 ° C to 220 ° C, and more preferably from 30 ° to 120 minutes at from 160 ° C to 200 ° C. When a base film of a film for a double-sided flexible circuit board composed of three layers of an insulating layer (A' layer), a heat resistant resin layer (C) layer, and a copper foil (D layer) is to be produced, it is heat-resistant. A layer of a resin composition is formed on a copper-clad laminated film composed of a resin layer (C layer) and a copper foil (D layer), and then it may be produced in the same manner as described above. The "copper-clad laminate film" includes a cast double layer CCL (Copper-clad laminate), a sputtering double layer CCL, a laminated double layer CCL, and a three layer CCL. The "two-layer CCL" commercially available as a copper foil having a thickness of 12 μm and 18 μm is used: ESP ANEX SC (manufactured by Nippon Steel Chemicals Co., Ltd.); NEOFLEX I&lt;CM&gt; , NEOFLEX I &lt; LM &gt; (manufactured by Mitsui Chemicals, Inc.); S'PERFLEX (manufactured by Sumitomo M. et al Mining Co., Ltd.), and the like. In addition, the commercially available three-layer CCL includes: NIKAFLEX F-50VC1 (manufactured by Nikkan Industries Co., Ltd.), etc. -54- 201035172 Manufactured of an insulating layer (A' layer), a heat resistant resin layer (C layer), and an insulating layer ( The base film of the film for a double-sided flexible circuit board which consists of three layers of A' layer can be performed by the following. First, a resin varnish obtained by dissolving the polyimine resin or the resin composition of the present invention in an organic solvent is prepared in the same manner as in the case of the above-mentioned adhesive film, and then the resin varnish is applied onto the support film. The organic solvent is then dried by heating or blowing hot air or the like to form a polyimide layer or a resin composition layer. The conditions of the organic hydrazine solvent, drying conditions, and the like are the same as those of the above-mentioned adhesive film. The thickness of the polyimide layer or the resin composition layer is preferably in the range of 5 to 15 μm. Next, the adhesive film was laminated on both sides of the heat resistant resin film. The conditions for the buildup are the same as those described above. Further, when a resin composition layer is provided in advance on one surface of the heat-resistant film, only one side may be laminated. Next, the resin composition layer is heat-hardened to form an insulating layer of a layer of a polyimide or a resin composition. The conditions for heat hardening are usually selected from 150 ° C to 220 ° C ^ and selected from the range of from 20 minutes to 180 minutes, more preferably from 160 ° C to 200 ° C and from 30 to 120 minutes. Hereinafter, a method of manufacturing a flexible circuit board from a base film for a flexible circuit board will be described. In the case of a base film composed of the A' layer, the C layer, and the A' layer, first heat-hardened, and then drilled on a circuit board by a drill, a laser, a plasma, or the like to form a conduction. Double-sided through holes. In the case of a substrate film composed of the A' layer, the C layer and the D layer, the holes are drilled in the same manner to form micropores. Special -55- 201035172 is a drill that is usually used for lasers such as carbon dioxide gas lasers or YAG lasers (Yttrium Aluminum Garnet Laser). Next, the surface treatment of the insulating layer (the layer of the polyimide film or the layer of the resin composition) is applied. Regarding the surface treatment, it is the same as the above-mentioned adhesive film. After the surface treatment is performed, a conductor layer is formed by plating on the surface of the insulating layer. The formation of the conductor layer using plating is the same as that of the above-mentioned adhesive film. After the conductor layer is formed and subjected to a cold treatment at 150 to 200 ° C for 20 to 90 minutes, the peel strength of the conductor layer can be further increased and stabilized. Next, a conductor layer is formed by patterning to form a circuit as a flexible circuit substrate. When a base film composed of the A layer, the C layer, and the D layer is used, the copper foil of the D layer is also formed into a circuit. The method of forming the circuit can be, for example, a subtractive method, a semi-additive method, or the like which is well known to those skilled in the art. The details are the same as in the case of the aforementioned adhesive film. According to the single-sided or double-sided flexible circuit board obtained as described above, for example, the multilayer flexible circuit board can be produced by multilayering the adhesive film of the present invention. Further, the polyimine resin or resin composition of the present invention can also be used as a material for forming a stress relaxation layer between a semiconductor and a substrate. For example, in the same manner as described above, all or a part of the insulating layer of the uppermost portion of the substrate is formed by using the adhesive film obtained by using the polyimine resin or the resin composition of the present invention, and a semiconductor can be connected thereto. A semiconductor device in which a semiconductor and a substrate are adhered via a cured product of the polyimide resin or a cured product of the resin composition. In this case, the thickness of the polyimine resin layer of the adhesive film or the thickness of the tree-56-201035172 lipid composition layer can be appropriately selected in the range of 10 to ΙΟΟΟμηη. The polyimine resin or resin composition of the present invention can be formed by coating a conductor layer, and a circuit layer can be formed by simply forming a conductor layer on the insulating layer for stress relaxation provided on the substrate. <<Embodiment>> Next, the present invention will be more specifically described by way of examples and comparative examples. In the following, "parts" and "%" mean "quality" unless otherwise stated. 〔 [Example 1] A raw material as shown in Table 1 was fed into a flask equipped with a stirring device, a thermometer and a condenser. While stirring, the temperature was raised to 80 ° C under the heat of the heat, and it was dissolved and reacted at this temperature for 1 hour, and further heated to 160 ° C for 2 hours, and then reacted at this temperature. 5 hours. The reaction is carried out simultaneously with the foaming of the carbon dioxide gas to make the inside of the system a transparent liquid which is brown. As a result, a solution of a polyethylenimine® resin (A1) having a resin solid content of 16% and a solution acid value of 2.1 (KO H mg/g) at a viscosity of 7 Pa·s at 25 ° C (polyimine) was obtained. The resin is dissolved in the resin composition of γ-butyrolactone). In addition, the acid value of the solid component of the resin is 13.1 (ΚΟΗ mg/g). Further, as a result of measurement by gel permeation chromatography (GPC), the weight average molecular weight was 29,000. -57- 201035172 Table 1 Raw Material Name (abbreviated) Raw Material Molecular Weight Feeding Molar Number Feeding Weight (g) MDI 250 0.25 62.5 DMBPDI 264 0.74 195.4 TMA 192 0.52 99.8 BTDA 322 0.1 32.2 TMAH 198 0.3 59.4 HCAHQ 324.3 0.08 25.9 GBL (Reaction solvent) 2070.0 Remarks of Table 1 (the same applies hereinafter): MDI: Diphenylmethane diisocyanate DMBPDI: dimethylbiphenyl diisocyanate (structure shown below)

TMA: trimellitic anhydride BTDA: benzophenone tetracarboxylic dianhydride TMAH : hydrogenated trimellitic anhydride (structure shown below)

HCAHQ: Reaction product of 9,10-dihydro-9-oxa-10-phosphonium-10-oxide with hydroquinone (structure shown below) -58- 201035172

0=P-〇/ HO

OH GBL: γ-butyrolactone The solution of the obtained polyimine resin (Al) is applied to a KBr plate, and the infrared absorption spectrum (Fig. 1) of the sample after the volatile solvent is measured, which is an isocyanate. The 2270 cnT1 absorbed by the characteristic disappeared completely, and the characteristic absorption of the quinone ring was confirmed at 725 cm·1, 1 780 cm·1 and 1 720 cm·1. Further, the amount of carbon dioxide gas generated was 80.96 g (1.84 m) by the change in the weight of the contents of the flask. Therefore, it can be concluded that the total amount of 1.84 moles of the total amount of the carboxylic acid and the acid anhydride group has been converted into a quinone bond and a guanamine bond. Further, as a result of analysis using C13-NMR (Fig. 2), it was confirmed that it was a polyimine resin represented by the structure shown below. In addition, the infrared absorption spectrum of the polyimine resin (A1) is shown in Fig. 1, and the C13-NMR chart is shown in Fig. 2.

But eight of the above structures! The structural unit to A6 is as follows. Further, a1 to a6 represent the molar ratio of the existence ratio of the structural unit, and can be concluded as follows. A7 is a repeating unit, and each structural unit in parentheses is not randomly bound without being limited by its order or repetition number (the same below): · -59- 201035172 al : a2 : a3 : a4 : a5 : A6=24.4: 42.2: 8.1: 8.2: 14.3:2.7. Structural unit.Al

Structural unit A2 H3C

Structural unit A3

Structural unit A5 structural unit Α6

In the above structural units Αι to A6, * represents a bond point to the molecular main chain. The solvent solubility, storage stability, coating workability, film film forming property (-60-201035172 surface smoothness), heat resistance, and mechanical properties of the obtained polyimide resin (A) solution were evaluated according to the following methods. Physical properties, flame retardancy and dimensional stability. The results are shown in Table 5. (1) Solvent solubility and storage stability The solvent solubility test and the storage stability test are to evaluate the solvent solubility of the polyimide resin (A1) immediately after preparation and the solvent solubility after standing for a long period of time. Way to implement. The newly prepared polyimine resin composition was adjusted to a solution having a resin concentration of 10% with gamma-butyrolactone, and then 25 ml of the solution was placed in a covered glass bottle to observe the appearance thereof. The assessment is based on the following evaluation criteria. The result was taken as the solvent solubility of the polyimine resin composition immediately after preparation. Then, the covered glass bottle containing the composition of the polyimide resin was allowed to stand at 40 ° C for 30 days, and the appearance thereof was observed and evaluated as the solvent solubility over time by the following evaluation criteria: 〇: The resin solution is transparent and fluid; △: Although there is fluidity, turbidity occurs; X: no transparency or fluidity. (2) Evaluation of coating workability ■ Polyimide resin (A1) was coated on a tinplate with a 0.1 52 mm coater at room temperature. Then, the appearance of the coating was evaluated on the basis of the following evaluation criteria. In addition, when the solid content was blended in the resin solution prepared in the following examples and comparative examples, the temperature of the resin solution was raised to 120 ° C to dissolve the solid component and then applied. 〇: a flat surface that is transparent and has a glossy surface; Δ: a flat surface although opaque; X: an opaque surface with a non-flat surface. -61 - 201035172 (3) Evaluation of film-forming property (surface smoothness) After the polyimide film (A1) was coated on a tinplate with a film coater to a dry film thickness of 30 μm, The test piece was prepared by drying at 110 ° C for 30 minutes. The test piece was allowed to stand at 25 ° C for 24 hours, and the appearance of the coating film was evaluated on the following evaluation criteria: 〇: no abnormality such as cracks was observed in the coating film; Δ: some cracks were observed in the coating film; : Cracks occur in the entire film. (4) Evaluation of heat resistance The polyimide resin (A1) was coated on a glass epoxy resin substrate of a laminated copper foil to have a film thickness of 30 μm, and then dried in a dryer at 200 °C. After drying for 60 minutes, it was cooled to room temperature to prepare a test piece. The test piece was immersed in a molten solder bath at 260 ° C for 30 seconds, and then cooled to room temperature. A total of three times of solder bath immersion operation was carried out, and then the appearance of the hardened coating film was evaluated on the following evaluation criteria: 〇: no abnormality was observed in the coating film; Δ: some expansion, peeling, etc. were observed in the coating film. Abnormal; X: Abnormalities such as swelling and peeling were observed in the coating film. (5) Evaluation of mechanical properties The mechanical properties were evaluated by a tensile test of a coating film (film) to determine elastic modulus, breaking strength, and elongation at break. &lt;Production of test piece&gt; The polyimide film (A1) was applied onto a tinplate substrate to obtain a film thickness of 30 μm from -62 to 201035172. Next, the coated plate was dried in a dryer at 50 ° C for 30 minutes, and dried at a drying machine for 30 minutes and a dryer at 200 ° C for 60 minutes to prepare a coating film (film). After cooling to room temperature, the coating film (film) was cut into a desired size and separated from the substrate to be used as a sample for measurement. <Tens test method> Five samples for measurement were produced, and the following conditions were carried out. Tensile test to determine the modulus of elasticity, breaking strength and elongation at break. The elastic modulus is lower than that of the elastic modulus, which means that it has a superior softness. The higher the elongation at break, the higher the elongation. A film of superior softness, and the higher the breaking strength, the stronger the film. The measuring machine: TENSILON of Toyo Baldwin Co., Ltd. Shape: l〇mm χ 70 mm Interval: 20 mm Stretching speed: 10 mm/min Measured atmosphere: 22 ° C, 45% RH Θ ( 6 ) Tg and measurement of linear expansion coefficient &lt;Manufacture of test piece for test &gt; Polyimine resin (A1) Coating on a tinplate substrate to form a cured film thickness 20 μm, and then dried in a dryer at 70 ° C for 20 minutes, after hardening at 200 ° C for 1 hour and after cooling, the peeled hardened coating film was cut into a width of 5 mm and a length of 30 mm. As a sample for measurement. -63- 201035172 &lt;Tg and method for measuring linear expansion coefficient&gt; Using a thermal analysis system TMA-SS6000 manufactured by Seik Inc., the sample and the temperature increase rate were l〇°. C / min, load 30 mN strip (thermo-mechanical analysis: Thermal Mechanical Analysis. In addition, Tg is changed from the temperature-size measured at TMA to the temperature and Tg at its temperature. The sample length is from 50 to 220 ° C. The higher the Tg, then the more excellent the heat resistance, the smaller the size, and then the better the dimensional stability. (7) The evaluation of flame retardancy will be The amine resin (A1) has a film thickness of 20 μm after the tin-plated iron substrate is formed, and is cured in a dryer at 70 ° C for 1 hour at 200 ° C and cut into a width by a cold hardened coating film. It is 10 mm and the length is 70 m' The sample is fixed. The end of the rectangular sample is fixed to the jig, and the other end is perpendicular to the lower direction. Then, the lower end is ignited with a lighter and burned. This operation is repeated 5 times, and the following base is used. : All the samples in 5 times will not ignite after ignition; 〇: 2 to 4 of the 5 samples will not extinguish themselves after ignition; △: 1 of 5 times after the sample is ignited After the length of the Instruments is 1〇mm, the TMA;) method is used to determine the linear expansion coefficient of the linear expansion coefficient, and the coating is applied to the hard g dry for 20 minutes. One of the longitudinal directions of the stripping m is set to evaluate the burning of the sample with the ground surface: burn to the jig and burn to the jig from the burning to the jig -64 - 201035172 self-extinguishing; X: all the samples in 5 times After ignition, it will completely burn to the fixture. [Example 2] A raw material as shown in Table 2 was fed into a flask equipped with a stirring device, a thermometer and a condenser. While stirring, the temperature is raised to 80 ° C under the heat of the heat, and it is dissolved and reacted at this temperature for 1 hour, and further heated to 1 60 ° C for 2 hours, and then reacted at this temperature. 5 hours. The reaction is carried out simultaneously with the foaming of the carbonic acid gas, so that the system becomes a transparent liquid of brown enamel. As a result, a solution of a polyimine resin (A2) having a resin solid content of 16% and a solution acid value of 1.8 (KOH mg/g) having a viscosity of 7 Pa·s at 25 ° C was obtained (polyimine resin was dissolved). Resin composition of γ-butyrolactone). In addition, the solid content of the resin has an acid value of 11_25 (KOH mg/g). Further, the result was measured by gel permeation chromatography (GPC), and its weight average molecular weight was 39,000. Table 2 Raw material name (abbreviation) Raw material molecular weight Feeding molar number Feeding weight (g) MDI 250 0.25 62.5 DMBPDI 264 0.74 195.4 TMA 192 0.52 99.8 BTDA 322 0.1 32.2 TMAH 198 0.3 59.4 BPF 200 0.08 16.0 GBL (reaction solvent) 2017.8 Remarks of Table 2 (the same below):

BPF: bisphenol F The solution of the obtained polyimine resin (A2) was applied to KBr plate-65-201035172, and the infrared absorption spectrum of the sample after the volatile solvent was measured, which was characteristic absorption of the isocyanate group. 2270 cnT1 completely disappeared, and the characteristic absorption of the imidium ring was confirmed at 725 cnT1, 1 7 8 0 crrT1 and 1 720 cnT1. Further, the amount of carbon dioxide gas produced was 80.96 g (1.84 m) as a result of the change in the weight of the flask feed. Therefore, it can be concluded that the total amount of isocyanate groups in the same manner as in Example 1 has been converted into a quinone bond and a guanamine bond and is represented by the following structural formula: h〇-^^〇Xh

-R'-H again. The structural units of the structural units 1 to a6 in the formula a7 are the same as those of the structural unit disclosed in the first embodiment. Further, a1 to a7 represent the molar ratio of the existence ratio of the structural unit, and can be concluded as follows: al : a2 : a3 : a4 : a5 : a6 = 24.4 : 42.2 : 8.1 : 8.2 : 14.3 : 2.7 . The evaluation of the solution of the obtained polyimine resin (A2) was evaluated in the same manner as in Example 1, and the results are shown in Table 5. [Example 3] A raw material as shown in Table 3 was fed into a flask equipped with a stirring device, a thermometer and a condenser. While stirring, the temperature is raised to 80 ° C during heat dissipation, and it is dissolved and reacted at this temperature for 1 hour, and further heated to 160 ° C for 2 hours, and then reacted at this temperature. 5 hours. The reaction is carried out simultaneously with the foaming of the carbonic acid gas, so that the inside of the system becomes a transparent liquid of brown color. As a result, a solution of polyethylenimine-66-201035172 resin (A3) having a viscosity of 8 Pa at 25 ° C and a resin solid content of 16% and a solution acid value of 2.3 (KOH mg/g) was obtained. The imine resin is dissolved in the resin composition of γ·butyrolactone). In addition, the acid value of the solid component of the resin was 14.3 (ΚΟ Η mg/g). Further, the weight average molecular weight was 35,000 as measured by gel permeation chromatography (GPC). Table 3 Raw material name (abbreviation) Molecular weight of raw material Feeding molars Feeding weight (g) MDI 250 0.25 62.5 DMBPDI 264 0.75 198.0 TMA 192 0.6 115.2 TMAH 198 0.4 79.2 BP 200 0.1 18.6 GBL (reaction solvent) 2023.9

〇BP: biphenol was applied to a KBr plate by a solution of the obtained polyimine resin (A3), and the infrared absorption spectrum of the sample after the volatile solvent was measured, and the 2270 cnT1 which is characteristic absorption of the isocyanate group completely disappeared. And the characteristic absorption of the quinone imine ring was confirmed at 725 cm·1, 1 7 8 0 cm·1 and 1 7 2 0 c πΓ 1 . In addition, the amount of carbonation gas produced was 80.96 g (1.84 m) by the change in the weight of the flask feed. Therefore, it can be concluded that the total amount of isocyanate groups in the same manner as in Example 1 has been converted into a quinone bond and a guanamine bond and is represented by the following structural formula: -a2- a1 a2 -A4- -a5- A4 a5

The structural units of the structural units A1, a2, a4, and a5 in the formula -R-N a7 are the same as those in the structural unit disclosed in the first embodiment. Further, al, a2, a4, and a5 -67 to 201035172 are the molar ratios of the existence ratio of the structural unit and can be concluded as follows: al : a2: a4: a5 = 30: 45: 10 : 15. The evaluation of the solution of the obtained polyimine resin (A3) was evaluated in the same manner as in Example 1, and the results are shown in Table 5. [Example 4] A raw material as shown in Table 4 was fed into a flask equipped with a scrambler, a thermometer and a condenser. While stirring, the temperature was raised to 80 ° C under the heat of the heat, and it was dissolved and reacted at this temperature for 1 hour, and further heated to 160 ° C for 2 hours, and then reacted at this temperature. 5 hours. The reaction is carried out simultaneously with the foaming of the carbonic acid gas, so that the inside of the system becomes a transparent liquid of brown color. As a result, a solution of a polyimine resin (A4) having a resin solid content of 16% by weight and a solution acid value of 2.7 (KOH mg/g) at a viscosity of 25 ° C (polyimine resin) was obtained. A resin composition dissolved in γ-butyrolactone). In addition, the acid value of the solid component of the resin was 16.9 (Κ0Η mg/g). Further, the result was measured by gel permeation chromatography (GPC), which had a weight average molecular weight of 23,000. Table 4 Raw material name (abbreviation) Raw material molecular weight Feeding molar number Feeding weight (g) TDI 174 0.25 43.5 DMBPDI 264 0.74 195.4 TMA 192 0.52 99.8 BTDA 322 0.1 32.2 TMAH 198 0.3 59.4 HCAHQ 324.3 0.08 25.9 GBL (reaction solvent) 1970.2 -68- 201035172 The solution of the obtained polyimine resin (A4) will be applied to a KBr plate, and after the volatile solvent is determined, @sample &amp;&amp;&amp;#线1^%% spectrum result 'is an isocyanate group The characteristic absorption of 2270 cnT1 completely disappeared and the characteristic absorption of the quinone imine ring was confirmed at 725 cm-1, 1780 cm'1, and 1720 cnT1. In addition, the amount of carbon dioxide produced was 80.96 g (1.84 m) as a function of the change in the weight of the flask feed. Therefore, it can be concluded that the total amount of isocyanate groups in the same manner as in Example 1 has been converted into a quinone bond and a guanamine bond and is a representative structural formula as shown below:

The structural units of the structural units A], A2, and A3 in the formula are the same as those of the structural unit disclosed in the first embodiment. The structural unit A'4, A'5, A'6 is a structural unit represented by the following formula. In addition, a to a3, and a, 4 to a, 6 are the molar ratios of the existence ratio of the structural unit, and can be concluded as follows: al: a2: a3: a, 4: a, 5: a, 6 = 24.4: 42.2: 8.1: 8.2: 14.3: 2.7. -69- 201035172 Structural unit A'4

The evaluation of the solution of the obtained polyimine resin (A4) was carried out in the same manner as in Example 1, and the results are shown in Table 5. Table 5 Examples Example 1 Example 2 Example 3 Example 4 Polyimine resin A1 A2 A3 A4 Solvent solubility 溶剂 Solvent solubility 〇〇〇〇 Coating work 〇〇〇〇 coating Membrane membranous heat resistance 〇〇〇〇 Mechanical physical rupture strength (MPa) 170 168 160 195 Elongation at break (%) 54 48 55 25 Elastic modulus (MPa) 3500 3300 3400 4000 Tg (°C) 280 275 278 268 Linear expansion coefficient (: Ppm / ° C) 20 21 20 28 Flame retardancy ◎ 〇〇 ◎ -70- 201035172 [Examples 5 to 7] Modifications were made as shown in Table 6 to obtain this The thermosetting resin compositions 1 to 4 of the invention. The same evaluation as in Example 1 was carried out, and the results are shown in Table 7. However, the number of formulas in Table 6 represents the amount of resin solids. Table 6 Example 5 Example 6 Example 7 Example 8 Thermosetting resin composition 1 2 3 4 Polyimine resin A1 90 90 A2 90 A4 90 Epoxy resin HP4032 10 HP4700 10 10 10 EMZ 0.5 0.5 0.5 0.5 Remarks in Table 6: HP4032: 1,6-dihydroxynaphthalene epoxidized resin. Epoxy equivalent = 141 Q. Its representative structure is as shown in the following formula:

HP4700: Awake varnish of 2,7-dihydroxynaphthalene epoxidized resin. Epoxy equivalent = 163. Its representative structure is as shown in the following formula: -71- 201035172

EMZ: hardening catalyst, 2-ethyl-4-methylimidazole. Table 7 Example 5 Example 6 Example 7 Example 8 Thermosetting resin composition 1 2 3 4 Solvent solubility 〇〇〇〇 Solvent solubility 〇〇〇〇 Coating work 〇〇〇〇 coating film Film formation 1 Heat resistance 〇〇〇〇 Mechanical physical strength (MPa) 165 168 160 195 Elongation at break (%) 35 38 55 25 Modulus of elasticity (MPa) 3400 3600 3400 4000 Tg 285 295 298 288 Linear expansion coefficient (i) pm/°C) 49 50 47 51 Flame retardant 比较 [Comparative Example 1] 3 3 7.8 g of GBL (Y-butyl) was fed into a flask equipped with a stirring device, a thermometer and a condenser. Lactone), 225 g (0.9 mol) of MDI (diphenylmethane diisocyanate), and 192 (1 mol) of TMA (trimellitic anhydride), while stirring, heat up to 2 hours under the heat of cooling After 60 ° C, it was allowed to react at this temperature for 5 hours. The reaction is carried out simultaneously with the foaming of the carbonic acid gas, so that the inside of the system becomes a transparent liquid of brown color. Although -72- 201035172 is to measure the viscosity at 25 °C, the viscosity cannot be determined due to crystallization. The resin has a solid content of 50%. This is simply referred to as a solution of "polyimine resin (al)". In addition, according to the acid value of the resin solution [16.6 (KOH mg/g)], it can be concluded that the average molecular weight is 3,400. The solution of the obtained polyimine resin (al) was applied to a KBr plate, and the infrared absorption spectrum of the sample after the volatile solvent was measured. The 2270 cnT1 which is characteristic of the isocyanate group completely disappeared, and was 725 cm. · 1, 1 780 cm·1 and 1 720 crrT1 confirmed the characteristics of the 醯imine ring 〇 absorption. Further, the amount of carbon dioxide gas produced was 79.2 g (1.8 m) as a result of the change in the weight of the flask feed. Therefore, it can be concluded that all of the 1.8 moles of the total amount of the isocyanate groups have been converted into the oxime bond and the guanamine bond, except for the solution of the obtained polyimide resin (al), and the others are The polyimine resin (a 1 ) was evaluated in the same manner as in Example 1. The results are as shown in Table 8: [Comparative Example 2] ^ In a flask equipped with a stirring device, a thermometer and a condenser, 345.9 g of GBL (y-butyrolactone), 237.5 g (0.95 mol) of MDI (diphenylmethane diisocyanate), and 192 were fed. (1 mol) of TMA (trimellitic anhydride) was heated to 160 ° C for 2 hours while stirring, and then allowed to react at this temperature for 5 hours. The reaction is carried out simultaneously with the foaming of the carbon dioxide gas to make the inside of the system a brownish transparent liquid. Although it is desired to determine the viscosity at 25 ° C, the viscosity cannot be determined due to crystallization. The resin has a solid content of 50%. This is abbreviated as a solution of "polyimine resin (a2) -73 - 201035172 j. In addition, according to the acid value of the resin solution [8.1 (KOH mg / g)], the average molecular weight is 6900. The solution of the obtained polyimine resin (a2) was applied to a KBr plate, and the infrared absorption spectrum of the sample after the volatile solvent was measured, and the characteristic absorption of 22 70 cnT1 belonging to the isocyanate group disappeared completely, and at 725. Cm'1 &gt; 1 7 8 0 cnT1 and 1 720 cm'1 were confirmed to belong to the characteristic absorption of the quinone ring. In addition, the amount of carbon dioxide produced by the change in the weight of the flask was traced to 83.6 g (1.9 m). Therefore, it can be concluded that all of the 1.9 moles of the total amount of the isocyanate groups have been converted into the quinone bond and the guanamine bond, except for the solution of the obtained polyimide resin (a2). Then, the polyimine resin (a2) was evaluated in the same manner as in Example 1. The results are shown in Table 8. [Comparative Example 3] 292.32 g of GBL was fed in a flask equipped with a stirring device, a thermometer and a condenser. (Y-butyrolactone), 190 g (0.76 m) MDI (diphenylmethane diisocyanate), 130.56 (0.68 mol) of TM A (trimellitic anhydride), and 38.64 g (0.12 mol) of BTDA (benzophenone tetracarboxylic dianhydride) while stirring Note that after heating for 2 hours under heat dissipation, the temperature was raised to 1 60 ° C, and then reacted at this temperature for 5 hours. The reaction was carried out simultaneously with the foaming of carbonic acid gas, and as a result, the system was stained from the transparent liquid of brown color, although it was determined. Viscosity at 25 ° C, but the viscosity cannot be determined due to crystallization. The solid content of the resin is 50%. It is simply referred to as a solution of polyimine resin (a3 ) (polyimine resin is not dissolved in γ-butyl) In -74- 201035172 ester resin composition). In addition, according to the acid value of the resin solution [7.7 (KOH mg / g)], it can be concluded that the average molecular weight is 7300. The obtained polyimine The solution of the resin (a3) was applied to a KBr plate, and the infrared absorption spectrum of the sample after the volatile solvent was measured. The 2270CHT1 which is characteristic of the isocyanate group completely disappeared, and was 725 cuT1, 1 780 CHT1 and 1 720 cm + Confirmed to belong to the imine ring Characteristic absorption. In addition, the amount of carbon dioxide produced by the change in the weight of the flask is 66.88 g (1.52 mol). Therefore, it can be concluded that the total amount of the isocyanate group is 1.52 mol. The polyimine resin (a3) was evaluated in the same manner as in Example 1 except that a solution of the obtained polyimide resin (a3) was used. The results are shown in Table 8. [Comparative Example 4] 14 g of DMAC (dimethylammoniumamine) and 98.4 g (0.24 mol) of TMEG® (ethylene glycol double dehydrated benzene) were fed into a flask equipped with a stirring device, a thermometer and a condenser. Triseoester), 40 g (0.16 mol) of BPS (bisphenol S), 40 g (0.16 mol) of MDI (diphenylmethane diisocyanate), and 26.9 g (0.16 mol) of HDI (six Methyl diisocyanate) was heated to 80 ° C while stirring, and reacted and dissolved at this temperature for 1 hour, and then heated to 1 20 ° C for 2 hours, at this temperature. It was allowed to react for 1 hour. The reaction is carried out simultaneously with the foaming of the carbon dioxide gas, so that the system becomes a transparent liquid of brown color. The solution of the solid content of the resin was adjusted to 55% by DMAC to obtain a solution of the polyimine resin (a4) having a viscosity of 100 Pa·s at 25 ° C at -75 to 201035172. The solution of the obtained polyimine resin (a4) was applied to a KBr plate, and the infrared absorption spectrum of the sample after the volatile solvent was measured. The 2270CHT1 which is characteristic of the isocyanate group completely disappeared, and was 725 cnT1. 1 780 cm·1 and 1 720 cm·1 confirmed the absorption of the characteristic of the quinone ring. Further, the amount of carbon dioxide gas produced was 21.1 g (0.48 mol) as a result of the change in the weight of the flask feed. Therefore, it can be concluded that the total amount of the anhydride group of TMEG (ethylene glycol double-dehydrated trimellitate) of 0.48 moles has been converted into a quinone bond, and the remaining isocyanate group is compared with BPS (bisphenol S). A urethane bond is formed and bonded to the resin. The polyimine resin (a4) was evaluated in the same manner as in Example 1 except that the obtained solution of the polyimine resin (a4) was used. However, regarding the evaluation of solvent solubility and solvent solubility over time, since the synthesis solvent was changed to DMAC, gamma-butyrolactone was changed to DMAC for evaluation. The results are shown in Table 8. [Comparative Example 5] 80 parts of a polyimine resin (a4) and 20 parts of N6 80 (a cresol novolak type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.) The epoxy equivalent was 214, the softening point was 8 1 ° C), and 5 parts of triphenylphosphine was prepared for comparison as the "polyimine resin composition (a5)" for comparison. The polyimine resin composition -76 - 201035172 (a 5 ) was evaluated in the same manner as in Example 1 except that the obtained polyimide resin composition (a5) was used. However, regarding the evaluation of solvent solubility and solvent solubility over time, since the synthesis solvent was changed to DM AC, gamma-butyrolactone was changed to DMAC for evaluation. The results are shown in Table 8. [Comparative Example 6] In a flask equipped with a stirring device, a thermometer and a condenser, 172.9 g (0.9 mol) of TMA (p-trimellitic anhydride) and 31 g (0.1 mol) of 3, 3', 4 were fed. 4'-diphenyl ether tetracarboxylic dianhydride, 264.3 g (1 mol) of DMBPDI and 2155 g of GBL (Y-butyrolactone), while stirring, heat up to 1 50 °C for 2 hours while paying attention to heat dissipation. . Although the reaction was carried out at this temperature, fouling occurred from the flask system one hour after the temperature was raised to the maximum temperature. Further, although the reaction was carried out after the reaction was carried out at this temperature for 6 hours, the solvent and the solid resin component were separated at room temperature to become uneven, and the synthesis was immediately stopped. [Comparative Example 7] In a flask equipped with a stirring device, a thermometer and a condenser, 96 g (0.5 mol) of TMA (p-trimellitic anhydride), 101 g of 10.5 mol () of lipoic acid, 115 g ( 0.46 moles of MDI (diphenylmethane diisocyanate), 87 grams (0.5 moles) of TDI, and 399 grams of solvent (50% solids concentration) of cyclohexanone as solvent, plus 0.02 moles Nitrobicycloundecene was used as a catalyst and allowed to react at 140 ° C for 3 hours. Further, after adding 5 g (0.02 mol) of MDI (diphenylmethane diisocyanate), the reaction was carried out at 140 ° C for 2 hours, and then diluted with cyclohexanone to a solid concentration of 25%, and then taken out to obtain A solution of a polyimine resin (a7). The same evaluation as in Example 1 was carried out, and the results are shown in Table-77-201035172. However, since "the evaluation of solvent solubility and solvent solubility over time" was changed to cyclohexanone, the gamma-butyrolactone was changed to cyclohexanone for evaluation. Table 8

Comparative Example Comparative Example Comparative Example Comparative Example 1 2 3 4 5 Resin (resin composition) al a2 a3 a4 a5 Solvent solubility XXX Solvent solubility 〇〇 〇 Gelation coating workability XXX 〇〇 Heat resistance X 〇 mechanical physical fracture strength (MPa) -*1) — *1) _*2) 110 elongation at break (%) — *1) — Μ) _*2) 15 elastic modulus (MPa) —*1 )~*1) — *2) 2600 Tg (°c) _*2) 203 Linear expansion coefficient ~*1) ~*1) _*2) 75 Flame retardancy-*1) __ *2) X Due to coating The cloth is not so good that it is impossible to obtain a uniform film, so it cannot be evaluated. 2)

Since the film is so weak that it cannot be divided into II, it cannot be evaluated. -78- 201035172 Table 9 Comparative Example Comparative Example 6 7 Resin (Resin Composition) a6 a7 Solvent Solubility X Solvent Solubility X 〇 Coating Workability X 〇 Heat Resistance _ *1) X Mechanical Physical Breaking Strength ( MPa) _*1) 76 elongation at break (%) _*1) 12 modulus of elasticity (MPa) _*1) 2800 Tg _*1) 187 coefficient of linear expansion (PPin/°C) _*i) 97 due to The coating property was poor so that a uniform coating film could not be obtained, and thus it was impossible to evaluate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an infrared absorption spectrum of the polyimine resin of the present invention obtained in Synthesis Example 1. Fig. 2 is a nuclear magnetic resonance absorption spectrum of the polyimine resin of the present invention obtained in Synthesis Example 1. [Main component symbol description] Μ . -79-

Claims (1)

N— Η 12) 201035172 VII. Patent Application Range: i A polyimine resin characterized by a structure of the general formula and a structure represented by the general formula (2): i? CN— Η (1 represents Residue 0-Χ-0 〇 after removal of NCO group by diisocyanate (wherein X represents a residue obtained by removing two phenolic hydroxyl groups by having two or more lanthanide compounds in one molecule) 2 . In the polyimine resin of the first aspect of the patent, Ri in the formula D has the following general formula (3), (4) or (3) (4) (5) (wherein R 2 each independently represents a hydrogen atom, a hydrocarbon group of carbon, * represents a bond point.) • A polyimine resin as claimed in claim 1; 1) I has a representation represented by the following formula (5 _ 1 ) (1) Phenolic hydroxy hydrazine; the structure of the formula (5) The number is from 1 to 9 in the formula (1 structure: -80-201035172 h3c ch3 Qr^0r ...-...---(5-1) (* represents the bond point). 4. As claimed in the patent range 1 to The polyimine resin of any one of the three items further has a structure represented by the following formula (6): (Ri represents a residue after removal of the NCO group from the diisocyanate). The polyimine resin according to any one of claims 1 to 4, which further has a structure represented by the following general formula (7): η 〇 η 6. The polyimine resin according to claim 4, wherein the structural unit represented by the τ column formula (8 -1 ) and the structural unit represented by (8 -2 ): -81 - 201035172 ◎ ο II C-N Η 8-(8-2 (wherein m and η are each 1 to 100). 7. The polyimine resin according to item 4 of the patent application, which has the structure represented by the following formula (9): 0 H3C\ /CH3 ..... (9) 〇 (wherein m, n, p, q are each 1 to 100, and Y represents the general formula (3) or general formula (4) ) the structure represented). , for example, the polyimine resin of claim 1 which has the structural unit represented by the following columns and has a weight average molecular weight of from 1 100 to 100,000: -82 - 201035172 (wherein a1, a2, a3, a4, a5, and a6 are each 1 to 1 0000, Y represents a structure represented by the general formula (3) or the general formula (4), and * represents a guanamine bond or The bond point of the quinone imine bond). 9. The polyimine resin according to item 8 of the patent application, wherein each of -83-201035172 10 to 40% by weight of the structural unit represented by the formula (10-1) and the formula (10- 2) The structural unit represented. The polyimine resin according to any one of claims 1 to 9, wherein X of the formula (2) is a formula (2-1), a formula (2-2), and a formula (2) -4) or the structure of formula (2-5): Η OH - Re R6 OH Rs--^-H Re OH R« Rs R6 J b (2-1 ) (2-2) (2-4) (2-5) [wherein R 2 represents a single bond or a divalent linking group, and r 3 represents hydrogen or an alkane having 1 to 5 carbon atoms R4 represents hydrogen or an alkyl group having a carbon number of 丨 to 5, or a structure represented by the following formula (2-3); R5 represents a direct bond or a divalent linking group; and Rs may be the same or different, And represents a hydrogen atom or a number of carbon atoms from 1 to 18; a, b, c total is 1 or more '* is a linking group] (2-3) -84- 201035172 11. The polyimine resin according to claim 10, wherein X of the formula (2) is a structure represented by the following formula (2-6): (* stands for the key node). 1 2 . The polyimine resin according to any one of claims i to n wherein the acid value of the resin is from 1 to 50. 1 3 · If you apply for a patent scope! The polyimine resin of any one of items i to 2 is dissolved in gamma-butyrolactone at 25 ° C at a concentration of 10% by weight. A cured product obtained by hardening a polyimide resin according to any one of claims 1 to 13. A method for producing a polyimine resin, which comprises a polyhydric phenol compound (A) having two or more phenolic hydroxyl groups, a polyisocyanate compound (B) containing a diisocyanate compound, and a cyclohexane-containing compound. The anhydride compound (C) of the tricarboxylic anhydride is reacted. A thermosetting resin composition characterized by containing the polyimine resin and epoxy resin according to any one of claims 1 to 13. A cured product obtained by hardening a thermosetting resin composition according to claim 15 of the patent application. -85-