JP5505240B2 - Polyamideimide resin and method for producing the same - Google Patents

Description

  The present invention relates to a polyamideimide resin and a method for producing the same.

  With the rapid miniaturization, high performance, and high functionality of electronic devices, various materials have been used in the printed wiring board field. A thermosetting resin such as a phenol resin, an epoxy resin, a polyimide resin, a bismaleimide-triazine resin or the like is generally used as an electrical insulating resin used in the printed wiring board field. In addition, as the electrically insulating resin, a thermoplastic resin such as a fluororesin or a polyphenylene ether resin may be used. Polyamideimide resin is excellent in heat resistance, and since it becomes a material excellent in adhesiveness by blending a thermosetting resin such as an epoxy resin, various developments have been advanced.

  Specifically, for example, a resin composition comprising a thermosetting resin such as an epoxy resin and a polyamideimide resin as essential components in order to have excellent thermal shock resistance, reflow resistance, and crack resistance and to improve fine wiring formation. A prepreg in which a fiber base material is impregnated with an object has been proposed (see, for example, Patent Document 1).

  In general, polyamideimide resin is synthesized by an isocyanate method by reaction of trimellitic anhydride and aromatic diisocyanate, or by an acid chloride method by reaction of aromatic diamine and trimellitic acid chloride. Yes. Here, in the isocyanate method, a polyamide-imide resin having various structures can be synthesized by using a wide variety of diamines, and a thermosetting resin can be blended with this to obtain a heat-resistant thermosetting resin.

  Specifically, for example, it has various imide structures by reacting aromatic diamine and siloxane diamine with trimellitic anhydride to make diimide dicarboxylic acid, and then manufacturing by an isocyanate method, and there are few by-products. A method of synthesizing a polyamideimide resin having a molecular weight sufficient for formation has been proposed (see, for example, Patent Documents 2 and 3).

JP 2003-55486 A JP-A-11-130831 JP 2006-124670 A

  However, the polyamideimide resins described in Patent Documents 1 to 3 above can be cured together with an epoxy resin to obtain a cured product having high adhesive strength to various adherends and excellent heat resistance. In order to utilize the reaction between the amide group of the imide resin and the glycidyl group of the epoxy resin, a heat treatment of 200 ° C. or higher, actually 230 ° C. or higher is required. Processing was necessary.

  The present invention solves the above-mentioned problems of the prior art, and when used together with an epoxy resin, it can be cured at a lower temperature than a conventional polyamideimide resin composition containing an epoxy resin, and has sufficient heat resistance and mechanical properties. It aims at providing the manufacturing method of the polyamide-imide resin which can obtain the hardened | cured material which has intensity | strength, and the said polyamide-imide resin.

  In order to solve the above problems, the present invention provides a polyamide-imide resin including a structure represented by the following formula (1).

  In formula (1), Ar represents an aromatic ring which may have a substituent other than a carboxyl group, and n represents an integer of 1 or more.

  According to the polyamide-imide resin of the present invention, when it is used together with the epoxy resin to form a polyamide-imide resin composition, it is heated at 180 ° C., which is a lower temperature condition than the conventional polyamide-imide resin composition. It can be cured under the conditions, and even in that case, a cured product having sufficient heat resistance and mechanical strength can be obtained. Moreover, according to the polyamideimide resin of the present invention, when a fiber base material is impregnated with a resin composition containing the polyamideimide resin and an epoxy resin and processed into a prepreg, or when processed into a B-stage film or the like Also, thermoforming is possible. Furthermore, according to the polyamide-imide resin of the present invention, a metal foil-clad laminate can be formed because it can be cured at a low temperature but can form a cured product having excellent adhesion and heat resistance to a metal foil or a fiber base material. It is useful as a printed wiring board material such as a board.

  In addition, since the cured product of the polyamideimide resin of the present invention can have sufficient bendability, it is useful for forming a printed wiring board that can be bent arbitrarily and can be stored in a high density in a housing of an electronic device. Furthermore, since the polyamide-imide resin of the present invention is excellent in film formability and can be made extremely thin, it is useful for forming a thin adhesive film used as a material for printed wiring boards.

  The polyamideimide resin of the present invention preferably includes a structure represented by the following formula (2).

  According to such a polyamideimide resin, the mechanical strength of the obtained cured product can be further improved. Further, when the film is formed, the mechanical strength of the film can be further improved.

  The polyamideimide resin of the present invention preferably contains an organopolysiloxane structure.

  When the polyamideimide resin includes such a structure, flexibility is improved. In addition, when the polyamideimide resin is used as a film, the film has high drying properties and facilitates low volatility differentiation of the film. In addition, the film can have a low elastic modulus and improve elongation. . Moreover, when the said polyamideimide resin contains such a structure, it becomes easy to make the said polyamideimide resin into the molecular weight which can form a film, and to make it soluble in a solvent.

  The present invention also provides a dicarboxylic acid compound, an aromatic polybasic acid that does not undergo dehydration and ring closure in a molecule represented by the following formula (3), and a diisocyanate compound, based on the total number of moles of the dicarboxylic acid compound. The aromatic polybasic acid is 0.01 to 1.0 times mol and the diisocyanate compound is 1.01 to 1.45 times mol with respect to the total number of moles of the dicarboxylic acid compound and the aromatic polybasic acid. A method for producing a polyamide-imide resin to be reacted is provided.

  In formula (3), Ar represents an aromatic ring which may have a substituent other than a carboxyl group, and m represents an integer of 3 or more.

  According to such a production method, the structure represented by the above formula (1) can be sufficiently incorporated into the main chain of the polyamideimide resin. Further, the molecular weight of the polyamide-imide resin can be adjusted, and the mechanical properties of the film when processed into a film or the like can be easily controlled. In addition, when the ratio of the aromatic polybasic acid is less than 0.01 times the total number of moles of the dicarboxylic acid compound, the effect due to the introduction of the side chain carboxyl group into the polyamideimide resin tends to be small, When it exceeds 1.0 times mol, it exists in the tendency which gelatinizes and an insoluble component produces | generates.

  In the method for producing the polyamideimide resin, the dicarboxylic acid compound preferably has an imide structure from the viewpoint of heat resistance.

  In the method for producing the polyamide-imide resin, the dicarboxylic acid compound comprises diamine and trimellitic anhydride in an amount of 2.0 to 2.3 times mol of trimellitic anhydride relative to the total number of moles of diamine. It is preferable that it is the imidodicarboxylic acid compound obtained by making it react in a ratio.

  According to such a production method, the range of the molecular weight that can be designed for the polyamideimide resin is wide, and in particular, a high molecular weight resin can be obtained. Moreover, according to such a manufacturing method, various imide structures can also be introduced into the polyamideimide resin.

  In the method for producing the polyamideimide resin, it is more preferable that the dicarboxylic acid compound has an organopolysiloxane imide structure.

  By reacting the above dicarboxylic acid compound, the molecular weight of the resin can be controlled, and dimethylacetamide (DMAC), dimethylformamide (DMF), dimethylsulfoxide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone Polyamideimide resin soluble in solvents such as sulfolane and cyclohexanone can be obtained. And according to such a manufacturing method, the drying property when making it into a film form is higher, and the polyamide imide resin whose film formation property was further improved can be obtained. Moreover, according to such a manufacturing method, the polyamideimide resin with a lower elasticity modulus when it is set as a film can be obtained.

  In the method for producing the polyamideimide resin, the aromatic polybasic acid is preferably 1,3,5-tricarboxybenzene.

  According to such a production method, the aromatic amide group and the carboxyl group that becomes the reaction point of the polyfunctional glycidyl compound can be incorporated in the polyamide-imide resin in a balanced manner.

  This invention also provides the polyamideimide resin obtained by the manufacturing method of the above-mentioned polyamideimide resin.

  According to the polyamideimide resin obtained by the above-described production method, when used together with an epoxy resin, a cured product having excellent mechanical strength can be obtained more reliably by low-temperature curing. Moreover, according to such a polyamideimide resin, the mechanical strength of the film when the film is formed can be further improved.

  According to the present invention, when used together with an epoxy resin, the polyamideimide resin and the polyamide which can be cured even under a heating condition of 180 ° C. and can obtain a cured product having sufficient heat resistance and mechanical strength A method for producing an imide resin can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited to the following embodiments.

  The polyamideimide resin of the present invention includes a structure represented by the following formula (1). According to such a polyamideimide resin, when it is used together with an epoxy resin to form a polyamideimide resin composition, it can be cured under a heating condition of 180 ° C., which is a lower temperature condition than a conventional polyamideimide resin composition. And even in that case, a cured product having sufficient heat resistance and mechanical strength can be obtained. Moreover, according to the polyamideimide resin, heating is performed when a fiber base material is impregnated with a resin composition containing the polyamideimide resin and an epoxy resin and processed into a prepreg or processed into a B-stage film or the like. Molding is possible. According to the polyamide-imide resin, it is possible to form a cured product with excellent adhesion and heat resistance to metal foil and fiber base material while being capable of low-temperature curing. It is useful as a wiring board material. In addition, since the cured product of the polyamideimide resin can have sufficient bendability, it is useful for forming a printed wiring board that can be bent arbitrarily and can be stored in a high density in a housing of an electronic device. Furthermore, since the polyamideimide resin is excellent in film formability and can be extremely thinned, it is useful for forming a thin adhesive film used as a material for a printed wiring board.

  In formula (1), Ar represents an aromatic ring which may have a substituent other than a carboxyl group, and n represents an integer of 1 or more. Here, examples of the substituent other than the carboxyl group include an OH group and an alkyl group.

  Examples of the structure represented by the above formula (1) include structures represented by the following formula (2) and the following formula (4).

  In formula (4), s represents 1 or 2.

  Especially, when the said polyamideimide resin contains the structure represented by the said Formula (2), the mechanical strength of the hardened | cured material obtained can be improved further. Moreover, according to such a polyamideimide resin, the mechanical strength of the film when formed as a film can be further improved.

  The polyamideimide resin preferably contains an organopolysiloxane structure. In this case, the flexibility of the polyamideimide resin is improved, and the cured product can be reduced in elastic modulus. Thereby, the extensibility of the hardened | cured material obtained can be improved. In addition, when the resin composition is formed into a film, the film has high drying properties and facilitates low volatility differentiation of the film, and the film can have a low elastic modulus. Moreover, when the said polyamideimide resin contains such a structure, it becomes easy to make the said polyamideimide resin into the molecular weight which can form a film, and to make it soluble in a solvent.

  Examples of the organopolysiloxane structure include structures represented by the following formula (S-1).

In formula (S-1), R ¹ and R ² each independently represent a divalent organic group, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a monovalent organic group, u represents an integer of 1 or more. When u is 2 or more, the plurality of R ³ and R ⁴ may be the same or different.

  The divalent organic group is preferably an alkylene group, a phenylene group or a substituted phenylene group. Moreover, it is preferable that carbon number of the said bivalent organic group is 1-6. As the divalent organic group, an alkylene group having 1 to 3 carbon atoms is more preferable.

  The monovalent organic group is preferably an alkyl group, a phenyl group or a substituted phenyl group. Moreover, it is preferable that carbon number of the said monovalent organic group is 1-6. As said monovalent organic group, a C1-C3 alkyl group is still more preferable.

  U is preferably an integer of 1 to 50.

In the present embodiment, it is particularly preferable that R ¹ and R ² are all propylene groups, and R ³ , R ⁴ , R ⁵ and R ⁶ are all methyl groups from the viewpoint of availability of raw materials. .

The main chain of the polyamideimide resin may contain an alkylene group and / or an oxyalkylene group in addition to the above-described organopolysiloxane structure. That is, the main chain of the polyamideimide resin may contain any of the following (I), (II) and (III).
(I) Organopolysiloxane structure and alkylene group.
(II) Organopolysiloxane structure and oxyalkylene group.
(III) Organopolysiloxane structure, alkylene group and oxyalkylene group.

  Here, as the alkylene group of (I) and (III), a linear or branched alkylene group is preferable, and the alkylene group preferably has 1 to 12 carbon atoms. Moreover, it is preferable that carbon number of the oxyalkylene group of (II) and (III) is 1-6, and it is more preferable that it is 2-4. In addition, the said oxyalkylene group may form a polyoxyalkylene structure by repeating 2 or more.

  It is particularly preferred that the main chain of the polyamideimide resin contains the above (III). In such a case, the alkylene group and the oxyalkylene group have at least one of the structures represented by the following formulas (A-1), (A-2), (A-3) and (A-4). It is particularly preferable to have it.

  In formula (A-1), a represents an integer of 2 to 70.

  In formula (A-2), b, c and d represent an integer of 1 or more. In addition, it is preferable that b + c + d is 5-40.

  The polyamideimide resin of the present invention can be produced, for example, by reacting a dicarboxylic acid compound, an aromatic polybasic acid that does not undergo dehydration and ring closure in the molecule represented by the following formula (3), and a diisocyanate compound. Here, the aromatic polybasic acid that does not undergo dehydration and ring closure in the molecule refers to those in which adjacent carboxyl groups do not undergo dehydration and ring closure under heating at 100 ° C. or higher or in the presence of a dehydrating agent.

  In formula (3), Ar represents an aromatic ring which may have a substituent other than a carboxyl group, and m represents an integer of 3 or more. Here, examples of the substituent other than the carboxyl group include an OH group and an alkyl group.

  The dicarboxylic acid compound is preferably diimide dicarboxylic acid obtained by reacting diamine and trimellitic anhydride. Here, the dicarboxylic acid compound is obtained by reacting diamine and trimellitic anhydride in a proportion of 2.0 to 2.3 times moles of trimellitic anhydride with respect to the total number of moles of diamine. It is preferable that it is an imidodicarboxylic acid compound obtained. According to such a production method, various imide structures can be introduced into the polyamide-imide resin, and the adjustment range of the molecular weight can be increased. In addition, the flexibility, heat resistance, strength, and the like of the polyamideimide resin can be controlled by selecting the structure of the diamine used for the reaction.

  Examples of the diamine include aliphatic diamines, aromatic diamines, and mixtures thereof.

  Examples of the aliphatic diamine include linear aliphatic diamines such as hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, and octadecamethylene diamine, and terminal aminated polypropylene glycol. The aliphatic diamine preferably contains an ether group from the viewpoint of achieving both low elastic modulus and high Tg, and terminal aminated polypropylene glycol is preferred. As the terminal aminated polypropylene glycol, Jeffamine D-230, D-400, D-2000 and D-4000 (product names) manufactured by Huntsman Co., Ltd. having different molecular weights are available.

  Examples of the aromatic diamine include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4- Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4- Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trifluoro) Methyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonyl-biphenyl-4,4 '-Diamine, 3,3'-dihydroxybiphenyl-4,4'-diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenyl sulfone, (4,4'-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether and the like.

  When the polyamideimide resin according to the present invention includes an organopolysiloxane structure represented by the above formula (S-1), the diamine has an organopolysiloxane structure by using a diamine having an organopolysiloxane structure. A dicarboxylic acid compound is obtained, and the polyamidoimide resin can contain an organopolysiloxane structure.

  Examples of the diamine having an organopolysiloxane structure represented by the above formula (S-1) include siloxane diamines represented by the following formula (S-2) or (S-3).

  U in Formula (S-2) represents an integer of 1 or more. In formula (S-3), v represents an integer of 1 or more, w represents an integer of 0 or more, and v + w is preferably 1 to 50.

  Examples of the siloxane diamine represented by the above formula (S-2) include KF8010 (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1,500) (above , Manufactured by Shin-Etsu Chemical Co., Ltd., product name), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2,200), (above, product name manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like. . Examples of the siloxane diamine represented by the above formula (S-3) include X-22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2,200) (Shin-Etsu Chemical Co., Ltd.) Company name, product name) and the like.

  When using the diamine which has an organopolysiloxane structure, it is preferable that the usage-amount of the diamine which has an organopolysiloxane structure is 10-80 mol% on the basis of the total number of moles of diamine, and is 20-60 mol%. Is more preferable, and it is still more preferable that it is 30-50 mol%.

  The polyamideimide resin containing any of (I), (II) and (III) is, for example, a diamine having an alkylene group and / or an oxyalkylene group and a diamine having the above organopolysiloxane structure as the diamine. Can be used.

  Examples of the diamine containing an alkylene group and / or an oxyalkylene group include, for example, low molecular diamines such as hexamethylene diamine, nonamethylene diamine, and diaminodiethyl ether, both terminal aminated polyethylene, and both terminal aminated polypropylene. Examples include oligomers and both-terminal aminated polymers. As the diamine containing an alkylene group, the alkylene group preferably has 4 or more carbon atoms, more preferably 6 to 18 carbon atoms. In this embodiment, it is particularly preferable to use a diamine having an alkylene group and an oxyalkylene group. Examples of the diamine include diamines such as the following formulas (B-1), (B-2), (B-3), and (B-4).

  In formula (B-1), a represents an integer of 2 to 70.

  In formula (B-2), b, c and d represent an integer of 1 or more. In addition, it is preferable that b + c + d is 5-40.

  As diamines of (B-1), (B-2), (B-3) and (B-4), Jeffamine D such as Jeffamine D2000, Jeffamine D230, Jeffamine D400 and Jeffamine D4000, respectively. Series, Jeffermin ED600, Jeffermin ED900, Jeffermin ED series such as Jeffermin ED2003, Jeffermin XTJ-511, Jeffermin XTJ-512 (above, manufactured by Huntsman, product name) and the like.

  The molecular weight of the diamine having an alkylene group and / or oxyalkylene group is preferably 30 to 20,000, more preferably 50 to 5,000, and still more preferably 100 to 3,000. When the molecular weight of the diamine having an alkylene group and / or an oxyalkylene group is within such a range, when the fiber base material is impregnated with the resin composition, the generation of wrinkles and warpage after drying is effectively performed. It becomes possible to decrease. Among these, Jeffamine is particularly preferred because it has an appropriate molecular weight and is excellent in the elastic modulus and dielectric constant of the resulting polyamideimide resin.

  When using a diamine containing an alkylene group and / or oxyalkylene group, the amount of the diamine containing an alkylene group and / or oxyalkylene group is preferably 5 to 40 mol% based on the total number of moles of the diamine, More preferably, it is 10-30 mol%, and it is still more preferable that it is 15-25 mol%.

  When using together the diamine which has an organopolysiloxane structure, and the diamine containing an alkylene group and / or an oxyalkylene group, the usage-amount of the diamine containing an alkylene group and / or an oxyalkylene group is the diamine 100 which has an organopolysiloxane structure. The amount is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and still more preferably 30 to 40 parts by mass with respect to parts by mass.

  In the present embodiment, it is preferable to use an aromatic diamine, a diamine having an organopolysiloxane structure, and one or more selected from diamines containing an alkylene group and / or an oxyalkylene group. In this case, the amount of aromatic diamine used is preferably 40 to 95 mol%, more preferably 50 to 90 mol%, and more preferably 60 to 80 mol% based on the total number of moles of diamine. Is more preferable. Moreover, it is preferable that the sum total of the usage-amount of the diamine which has an organopolysiloxane structure and the diamine containing an alkylene group and / or an oxyalkylene group is 5-60 mol% on the basis of the total number of moles of diamine. More preferably, it is -50 mol%, and it is still more preferable that it is 20-40 mol%.

  In the step of producing diimide dicarboxylic acid from diamine and trimellitic anhydride, it is preferable to use an aprotic polar solvent as the solvent. Examples of the aprotic polar solvent include dimethylacetamide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, sulfolane, cyclohexanone, and the like. Especially, since the process of producing | generating diimide dicarboxylic acid requires high reaction temperature, it is especially preferable to use N-methyl- 2-pyrrolidone whose boiling point is high and the solubility of a raw material and the polymer obtained is favorable.

  About the usage-amount of a solvent, it is preferable that the mass which match | combined the diamine and trimellitic anhydride becomes the quantity used as 10-70 mass% with respect to the mass of a solvent. If this ratio is less than 10% by mass, a large amount of solvent is consumed, resulting in poor efficiency. If it exceeds 70% by mass, the diamine and trimellitic anhydride cannot be completely dissolved, making it difficult to perform a sufficient reaction. Tend to be.

  The amount of diamine and trimellitic anhydride used is preferably such that the amount of trimellitic anhydride added is 2.0 to 2.3 times the total number of moles of diamine. By using 2.0 to 2.3 times the molar amount of trimellitic anhydride with respect to the total amount of diamine, a reaction product (diimidedicarboxylic acid) having both carboxyl ends more reliably obtained in a high yield is obtained. Can do. As a result, since the reactive site with diisocyanate can be increased, it is easy to obtain a high molecular weight polyamideimide resin, and the mechanical strength of the resulting polyamideimide resin can be further improved.

  The reaction temperature in the reaction of diamine and trimellitic anhydride is preferably 50 to 150 ° C, and more preferably 50 to 90 ° C. At temperatures lower than 50 ° C, the reaction tends to be slow and industrially disadvantageous, and at temperatures higher than 150 ° C, the reaction with a carboxyl group that does not cyclize proceeds and the reaction that forms an imide is inhibited. Tend.

  In the diimide dicarboxylic acid production step, it is considered that due to the reaction between diamine and trimellitic anhydride, the anhydrous portion of trimellitic anhydride is once ring-opened and then dehydrated and closed to form an imide bond. Such dehydration ring closure reaction is preferably carried out by adding an aromatic hydrocarbon azeotropic with water to the resulting reaction mixture and raising the temperature at the end of the diimide dicarboxylic acid production step. By adding an aromatic hydrocarbon azeotropic with water to the reaction mixture, water generated by the dehydration ring-closing reaction can be efficiently removed.

  The dehydration cyclization reaction is preferably carried out until no water is generated. Completion of the dehydration ring-closing reaction can be carried out, for example, by confirming that a theoretical amount of water has been distilled off with a moisture determination receiver or the like.

  Examples of the aromatic hydrocarbon azeotropic with water include benzene, xylene, ethylbenzene, toluene and the like. Toluene is preferred because it has a low boiling point and is easy to distill off and has relatively low toxicity.

  It is preferable that the aromatic hydrocarbon azeotropic with water is added in an amount corresponding to 10 to 50% by mass with respect to the mass of the aprotic polar solvent. If the amount of aromatic hydrocarbon azeotropic with water is less than 10% by mass relative to the amount of aprotic polar solvent, the water removal effect tends to decrease, and if it exceeds 50% by mass, the product There is a tendency for certain diimide dicarboxylic acids to precipitate.

  The dehydration ring closure reaction is preferably performed at a reaction temperature of 120 to 180 ° C. If the temperature is lower than 120 ° C, water may not be sufficiently removed, and if the temperature is higher than 180 ° C, dissipation of aromatic hydrocarbons may not be prevented.

  Furthermore, it is preferable to remove the aromatic hydrocarbon azeotropic with water before reacting the diimidedicarboxylic acid with the diisocyanate. In the state containing the aromatic hydrocarbon, a polyamideimide resin having a molecular chain terminal as an isocyanate group may be precipitated during the reaction. Although there is no restriction | limiting in particular in the method of removing an aromatic hydrocarbon, For example, the method of distilling off aromatic hydrocarbon by raising temperature further after dehydration ring closure reaction is mentioned.

  Examples of the aromatic polybasic acid represented by the above formula (3) include 1,3,5-benzenetricarboxylic acid (trimesic acid, 1,3,5-tricarboxybenzene), 1,3,5-naphthalene. Aromatic tricarboxylic acids such as tricarboxylic acid, 1,3,7-naphthalenetricarboxylic acid, and 1,5,7-naphthalenetricarboxylic acid are listed. Among these, 1,3,5-benzenetricarboxylic acid (trimesic acid, 1,3,5-tricarboxybenzene) is particularly preferable from the viewpoints of availability and moldability of the polyamideimide resin.

  By the way, also when an aromatic polybasic acid having one hydroxyl group and two or more carboxyl groups is used, a side chain carboxyl group can be introduced into the polyamideimide resin. Examples of such aromatic polybasic acids include phenolic hydroxyl group-containing aromatic polybasic acids such as hydroxyisophthalic acid and 2-hydroxy-3,6-carboxynaphthalene. Since the hydroxyl group contained in the phenolic hydroxyl group-containing aromatic polybasic acid is more likely to react with the isocyanate than the carboxyl group, a polyamideimide resin containing a urethane bond in the main chain is obtained when the above compound is used. However, since the polyamideimide resin having a urethane bond is easily hydrolyzed, it is difficult to obtain sufficient heat resistance. From the viewpoint of obtaining excellent heat resistance, the aromatic polybasic acid represented by the above formula (3) should be a compound that does not have a hydroxyl group as exemplified above and has three or more carboxyl groups. Is preferred.

  Examples of the diisocyanate compound include 4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and o-xylylene diene. Examples include aromatic diisocyanates such as isocyanate, m-xylylene diisocyanate, and 2,4-tolylene dimer, aliphatic diisocyanates such as hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. From the viewpoint of improving the heat resistance of the polyamideimide resin, an aromatic diisocyanate is preferable.

  The addition ratio of each component in the reaction between the dicarboxylic acid compound, the aromatic polybasic acid that does not undergo dehydration and ring closure in the molecule represented by the formula (3), and the diisocyanate compound is as follows. Can be mentioned.

  The amount of the aromatic polybasic acid represented by the formula (3) is preferably 0.01 to 1.0 times the total number of moles of the dicarboxylic acid compound, The number of moles is preferably 1.0 times, and more preferably 0.1 to 0.6 times. In addition to the fact that the amount of aromatic polybasic acid added is less than 0.01 times the number of moles, it tends to be difficult to sufficiently introduce carboxyl groups as side chains of the polyamideimide resin, and the resin composition When varnish is used, a microgel may be formed in the varnish. On the other hand, when the addition amount exceeds 1.0 times the number of moles, it becomes difficult to suppress gelation during the reaction between the aromatic polybasic acid and the diisocyanate compound, and an insoluble component is generated, Unreacted aromatic polybasic acid is likely to precipitate in the varnish. In this case, the film property of the polyamideimide resin composition may deteriorate.

  Moreover, it is preferable to use the addition amount of the said diisocyanate compound by 1.01-1.45 time mole amount with respect to the total mole number of the said dicarboxylic acid compound and the said aromatic polybasic acid, More preferably, it is used in a molar amount of 1.45 times. By using a diisocyanate within the above range, the molecular weight of the obtained polyamideimide resin can be made film-forming, and a resin soluble in a synthetic solvent can be obtained.

  In the present embodiment, the aromatic polybasic acid is 0.01 to 1.0-fold mol and the diisocyanate compound is the dicarboxylic acid compound and the aromatic polybasic with respect to the total number of moles of the dicarboxylic acid compound. It is preferable to make it react in the ratio of 1.01-1.45 times mole with respect to the total number-of-moles of an acid.

  By reacting the above components at the above ratios, the structure represented by the above formula (1) can be incorporated into the main chain of the polyamideimide resin at an appropriate ratio. That is, two carboxyl groups react with the diisocyanate compound to form a main chain of the polyamide, and the remaining one or more carboxyl groups do not participate in the reaction with the isocyanate compound and are added to the side chain of the polyamideimide resin as a carboxyl group. Can leave. Moreover, the gelation during polycondensation can be suppressed by reacting the above components at the above ratios. Furthermore, the molecular weight of the polyamideimide resin can be adjusted, and the mechanical properties of the film when processed into a film or the like can be easily controlled.

  Further, by reacting each of the above components in the above proportions, dimethylacetamide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, sulfolane, cyclohexanone, etc. A polyamide-imide resin that can be dissolved in a solvent can be obtained, and can be sufficiently reacted with a polyfunctional glycidyl compound at a low temperature. In this embodiment, when the ratio of the aromatic polybasic acid is less than 0.01 times the total number of moles of the dicarboxylic acid compound, the effect of introducing the side chain carboxyl group into the polyamideimide resin tends to be small. If the amount exceeds 1.0 mole, gelation occurs due to reaction with isocyanate, and an insoluble component tends to be generated.

  In the present invention, since the dicarboxylic acid compound is not taken out in the process of producing the polyamideimide resin, it is assumed that all of the diamine compound is a dicarboxylic acid compound, and the mole of the dicarboxylic acid compound is By replacing the number with the number of moles of the diamine compound, the addition amount of the aromatic polybasic acid and the addition amount of the diisocyanate compound are calculated.

  The reaction temperature of the dicarboxylic acid compound, the aromatic polybasic acid, and the isocyanate compound is preferably 140 to 200 ° C, and more preferably 150 to 180 ° C.

  A production scheme of a preferred embodiment of the polyamideimide resin according to the present invention is shown below.

  In the above production scheme, the diamine having X preferably contains a diamine having an organopolysiloxane structure. Moreover, the diisocyanate compound which has Y can be arbitrarily selected from the diisocyanate mentioned above. E and f are integers of 1 or more. In addition, it is preferable that e is 20-200, It is more preferable that it is 40-120, It is still more preferable that it is 60-100. f is preferably from 2 to 40, more preferably from 4 to 25, and even more preferably from 6 to 20. According to such a production scheme, a polyamide-imide resin (β) including a structure represented by the above formula (1) that is soluble in a solvent can be produced. When two or more kinds of diamines are used, the polyamideimide resin contains two or more types of repeating units containing an imide skeleton.

  Moreover, in the said preparation scheme, although the structural unit derived from the dicarboxylic acid compound (α) and the structural unit derived from trimesic acid are exemplified as the polyamideimide resin (β). The structural unit derived from the dicarboxylic acid compound (α) and the structural unit derived from trimesic acid may be bonded randomly or alternately. In this case, the total number of structural units derived from the dicarboxylic acid compound (α) is preferably in the range of e, and the total number of structural units derived from trimesic acid is preferably in the range of f.

  According to such a method, in all steps from the reaction of diamine and trimellitic anhydride to the production of the polyamideimide resin according to the present embodiment, the synthesis reaction is efficiently advanced without taking out the reaction product. It is preferable.

  Here, the weight average molecular weight of the polyamideimide resin according to the present invention is preferably 20,000 to 150,000, more preferably 40,000 to 100,000, and 50,000 to 80,000. More preferably. When this weight average molecular weight exceeds 150,000, when it is used as a varnish, the varnish becomes waxy and difficult to handle, and processing into a film becomes difficult. If it is less than 20,000, film formation becomes difficult and the strength of the film after thermosetting tends to be insufficient.

  In addition, the weight average molecular weight of the polyamide-imide resin in the present invention is determined by converting the chromatogram of the molecular weight distribution of the polyamide-imide resin measured by GPC (gel permeation chromatography) (25 ° C.) using standard polystyrene. It is done.

  In the polyamideimide resin according to the present invention, from the viewpoint of the life of the polyamideimide resin, the acid value is preferably 2.3 to 12.0, more preferably 3.5 to 9.0, and more preferably 5.5 to 5.5. 8.0 is more preferable.

  The acid value is defined as the number of mg of potassium hydroxide (KOH) necessary to neutralize 1 g of resin, and is determined by neutralization titration. The polyamideimide resin according to the present invention can be obtained by reacting a dicarboxylic acid compound, an aromatic polybasic acid that does not undergo dehydration and ring closure in the molecule represented by the above formula (3), and a diisocyanate compound. When the aromatic polybasic acid is not contained in the reaction system, if the isocyanate compound is used in excess, the theoretical acid value of the resin is 0, and the actually measured acid value is usually 3 or less. In contrast, when the above aromatic polybasic acid is used in combination, for example, when an aromatic tricarboxylic acid is used as an example, the acid value is (i) the reaction of all three carboxyl groups of the aromatic tricarboxylic acid. <Ii) When two carboxyl groups of an aromatic tricarboxylic acid are reacted <(iii) When one carboxyl group of an aromatic tricarboxylic acid is reacted <(iv) Three aromatic tricarboxylic acids It becomes larger in the order in which the carboxyl group is not reacted. (I) is a case where substantial gelation has occurred. In the method for producing a polyamide-imide resin according to this embodiment, optimization of the molar ratio of the dicarboxylic acid compound and the aromatic tricarboxylic acid, and the reaction temperature and reaction The reaction (i) can be suppressed by appropriately setting the concentration. (Ii) is a reaction produced by the polyamideimide resin according to the present invention having an aromatic carboxyl group in the side chain. (Iii) is a reaction in which a high molecular weight product cannot be obtained. (Iv) is a case where the aromatic tricarboxylic acid remains without reacting, and unreacted aromatic tricarboxylic acid precipitates as the reaction system is cooled. The theoretical acid value is determined by the blending ratio of the dicarboxylic acid compound, the aromatic polybasic acid represented by the above formula (3), and the diisocyanate compound. By actually measuring the acid value, the polyamideimide resin according to the present invention is obtained. It is preferable to confirm the generation.

  The polyamideimide resin of the present embodiment can be subjected to a thermosetting reaction with, for example, a polyfunctional glycidyl compound. The polyfunctional glycidyl compound in this case is not particularly limited as long as it is a glycidyl compound having two or more functional groups in one molecule, but is preferably an epoxy resin having two or more glycidyl groups. According to the epoxy resin, it can be cured at a temperature of 180 ° C. or less, and it can react with the carboxyl group of the polyamideimide resin to further improve the thermal, mechanical, and electrical characteristics.

  Examples of the epoxy resin include polyglycidyl ethers obtained by reacting polychlorophenols such as bisphenol A, novolak phenol resins, orthocresol novolac phenol resins or polyhydric alcohols such as 1,4-butanediol with epichlorohydrin, phthalates Examples thereof include polyglycidyl esters obtained by reacting polybasic acids such as acids and hexahydrophthalic acid with epichlorohydrin, N-glycidyl derivatives of amines, amides or compounds having a heterocyclic nitrogen base, alicyclic epoxy resins, and the like. .

  The epoxy resin has more glycidyl groups and more preferably 3 or more.

  Here, the said polyfunctional glycidyl compound can be used individually by 1 type or in combination of 2 or more types.

  When the polyfunctional glycidyl compound is an epoxy resin having two or more glycidyl groups, it is preferable to use a combination of curing agents for the epoxy resin. In this case, the suitable content of the curing agent varies depending on the number of glycidyl groups. Specifically, the more glycidyl groups, the lower the content.

  Although the said hardening | curing agent will not be restrict | limited if it reacts with an epoxy resin or accelerates | stimulates hardening, For example, amines, imidazoles, polyfunctional phenols, acid anhydrides, etc. are mentioned.

  Examples of the amines include dicyandiamide, diaminodiphenylmethane, and guanylurea.

  Examples of the imidazoles include alkyl group-substituted imidazoles and benzimidazoles.

  Examples of the polyfunctional phenols include hydroquinone, resorcinol, bisphenol A and their halogen compounds, novolak type phenol resins and resol type phenol resins which are condensates with formaldehyde.

  Examples of the acid anhydrides include phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, and the like.

  These curing agents can be used alone or in combination of two or more.

  The content of these curing agents is preferably such that when the curing agent is an amine, the equivalent of the active hydrogen of the amine and the epoxy equivalent of the epoxy resin are substantially equal. When imidazole is employed as the curing agent, it is preferably not used in an equivalent ratio with active hydrogen but empirically in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. When employing polyfunctional phenols and acid anhydrides, it is preferable to use them in a proportion of 0.6 to 1.2 equivalents of phenolic hydroxyl groups or carboxyl groups with respect to 1 equivalent of epoxy resin. If the content of the curing agent is small, uncured epoxy resin remains, and Tg (glass transition temperature) tends to be low. When this content is too much, unreacted curing agent remains, and the insulation tends to be lowered. Here, the blending amount of the epoxy resin is preferably set as appropriate in consideration of the epoxy equivalent, the reaction with the amide group of the polyamideimide resin, and the reaction with the carboxyl group of the polyamideimide resin.

  Moreover, a part of the said hardening | curing agent can also be contained as a hardening accelerator. A suitable content when used as a curing accelerator can be set similarly to the content of the curing agent.

  The content of the polyfunctional glycidyl compound in the case where the polyamidoimide resin and the polyfunctional glycidyl compound according to the present invention are subjected to a thermosetting reaction is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the polyamidoimide resin. 3 to 100 parts by mass, more preferably 5 to 40 parts by mass. If the content is less than 1 part by mass, the solvent resistance tends to be reduced. If the content exceeds 200 parts by mass, the Tg is reduced by the unreacted glycidyl compound, resulting in insufficient heat resistance. Or the flexibility tends to decrease.

  The resin composition containing the polyamide-imide resin, the polyfunctional glycidyl compound, and other curing agents as required can be excellent in adhesion to metal foil and fiber base material and heat resistance. In addition, the resin composition is cured by a heat treatment at a lower temperature of 180 ° C., whereas a conventional resin composition composed of a polyamide-imide resin and an epoxy resin requires a heat treatment of 200 ° C. to 250 ° C. Even in this case, a cured product having sufficiently high mechanical strength and excellent heat resistance can be obtained. The present inventor considers the reason why such an effect is obtained as follows.

  In a polyamideimide resin composition containing a conventional polyamideimide resin and a polyfunctional glycidyl compound, the amide group in the polyamideimide resin serves as a crosslinking point. Therefore, the curing reaction by heating is an addition reaction of a glycidyl group and an amide group and an insertion reaction of the glycidyl group into the amide group and tends to require a temperature of 200 ° C. or higher. In contrast, in the case of the polyamideimide resin composition according to this embodiment, the glycidyl group can preferentially react with the carboxyl group rather than the amide group, and can be sufficiently cured by heating at about 180 ° C. Become. Thereby, according to the polyamide-imide resin of the present invention, it is considered that a cured product having high mechanical strength and sufficient adhesiveness and heat resistance was obtained even under curing conditions at lower temperatures. In addition, the presence of an amide group and a carboxyl group makes it possible to increase the cross-linking density as compared to the case of only the amide group, and the mechanical strength of the cured product is high even at low temperatures, and both adhesiveness and heat resistance are compatible. The present inventor speculates that this is one of the factors that made this possible. In addition, such inference is that after the formation of the polyamideimide resin, the two carboxyl groups of the trifunctional or higher aromatic polybasic acid that does not undergo dehydration and ring closure during the synthesis of the polyamideimide resin react with the diisocyanate. This is based on the knowledge of the present inventors that the subsequent carboxyl groups do not react with isocyanate but remain as aromatic carboxyl groups without reacting with side chains.

  As mentioned above, although the polyamide imide resin in this embodiment was demonstrated, the said polyamide imide resin can be used for a prepreg, metal foil with resin, an adhesive film, and a metal foil clad laminated board, for example. For example, the prepreg, the metal foil with resin, the adhesive film and the metal foil-clad laminate formed by the resin composition containing the polyamideimide resin and the polyfunctional glycidyl compound in the present embodiment can be cured by a heat treatment at 180 ° C. It can have sufficient mechanical strength after thermosetting. In addition, these can be bent arbitrarily and can form a printed wiring board that can be stored in a high density in the casing of an electronic device, and are excellent in adhesion to metal foil and fiber base material and heat resistance. Useful as a material.

  Examples are described below, but the present invention is not limited to these examples.

Example 1
Reactive silicone oil KF8010 (manufactured by Shin-Etsu Chemical Co., Ltd., product name, amine equivalent 415) in a 1-liter separable flask equipped with a 25 mL water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer 41.5 g (0.05 mol), BAPP (manufactured by Shikoku Kasei Co., Ltd., product name) 20.5 g (0.05 mol), TMA (trimellitic anhydride) 40.3 g (0.21 mol), non-aromatic diamine 314 g of NMP (N-methyl-2-pyrrolidone) was charged as a protic polar solvent and stirred at 80 ° C. for 30 minutes.

  Next, 120 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that water is accumulated in the moisture determination receiver about 3.8 mL or more and that water is no longer distilled, remove the distillate collected in the moisture determination receiver, about 190 The temperature was raised to 0 ° C. to remove toluene. Thereafter, the mixture was cooled to 50 ° C., and 2.1 g (0.01 mol) of trimesic acid as a trifunctional aromatic polybasic acid, and 33.0 g (0.132 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate. The reaction was carried out at 160 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin was obtained. The weight average molecular weight of the polyamideimide resin was 104,000, and the solid content of the varnish was 28% by mass. The actually measured acid value of the varnish was 5.1 mgKOH. Table 1 shows the main components and blending amounts thereof, the weight average molecular weight of the polyamideimide resin, the solid content of the varnish, the theoretical acid value and the actually measured acid value of the varnish. In addition, the measuring method of the actually measured acid value of the polyamide-imide resin in this example will be described later.

(Example 2)
Reactive silicone oil KF8010 (manufactured by Shin-Etsu Chemical Co., Ltd., product name, amine equivalent 415) in a 1-liter separable flask equipped with a 25 mL water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer 24.9 g (0.03 mol), BAPP (manufactured by Shikoku Chemicals, product name) 28.7 g (0.07 mol), TMA (trimellitic anhydride) 40.3 g (0.21 mol), non-aromatic diamine As a protic polar solvent, 341 g of NMP (N-methyl-2-pyrrolidone) was charged and stirred at 80 ° C. for 30 minutes.

  Next, 120 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that water is accumulated in the moisture determination receiver about 3.8 mL or more and that water is no longer distilled, remove the distillate collected in the moisture determination receiver, about 190 The temperature was raised to 0 ° C. to remove toluene. Thereafter, the mixture was cooled to 50 ° C., and 2.1 g (0.01 mol) of trimesic acid as a trifunctional aromatic polybasic acid, and 33.0 g (0.132 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate. The reaction was carried out at 160 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin was obtained. The weight average molecular weight of the polyamideimide resin was 88,600, and the solid content of the varnish was 25% by mass. Moreover, the measured acid value of the varnish was 5.4 mgKOH.

(Example 3)
Reactive silicone oil KF8010 (manufactured by Shin-Etsu Chemical Co., Ltd., product name, amine equivalent 415) in a 1-liter separable flask equipped with a 25 mL water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer 24.9 g (0.03 mol), BAPP (manufactured by Shikoku Kasei Co., Ltd., product name) as an aromatic diamine, 20.5 g (0.05 mol), Wandamine WHM (manufactured by Shin Nippon Chemical Co., Ltd., product name) 4.2 g ( 0.02 mol), 40.3 g (0.21 mol) of TMA (trimellitic anhydride) and 312 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent were added and stirred at 80 ° C. for 30 minutes.

  Next, 120 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that water is accumulated in the moisture determination receiver about 3.8 mL or more and that water is no longer distilled, remove the distillate collected in the moisture determination receiver, about 190 The temperature was raised to 0 ° C. to remove toluene. Thereafter, the mixture was cooled to 50 ° C., and 2.1 g (0.01 mol) of trimesic acid as a trifunctional aromatic polybasic acid, and 33.0 g (0.132 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate. The reaction was carried out at 160 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin was obtained. The weight average molecular weight of the polyamideimide resin was 86,000, and the solid content of the varnish was 26% by mass. Moreover, the measured acid value of the varnish was 5.9 mgKOH.

(Example 4)
Reactive silicone oil KF8010 (manufactured by Shin-Etsu Chemical Co., Ltd., product name, amine equivalent 415) in a 1-liter separable flask equipped with a 25 mL water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer 24.9 g (0.03 mol), BAPP as aromatic diamine (manufactured by Shikoku Kasei Co., Ltd., product name) 28.7 g (0.05 mol), D2000 (manufactured by Huntsman, product name, amine equivalent 1,000) 0 g (0.02 mol), 40.3 g (0.21 mol) of TMA (trimellitic anhydride) and 437 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes. did.

  Next, 120 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that water is accumulated in the moisture determination receiver about 3.8 mL or more and that water is no longer distilled, remove the distillate collected in the moisture determination receiver, about 190 The temperature was raised to 0 ° C. to remove toluene. Thereafter, the mixture was cooled to 50 ° C., and 2.1 g (0.01 mol) of trimesic acid as a trifunctional aromatic polybasic acid, and 33.0 g (0.132 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate. The reaction was carried out at 160 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin was obtained. The weight average molecular weight of the polyamideimide resin was 78,100, and the solid content of the varnish was 25% by mass. The actually measured acid value of the varnish was 4.7 mgKOH.

(Examples 5 and 6)
The synthesis was performed in the same manner as in Example 1 except that trimesic acid (1,3,5-benzenetricarboxylic acid), diisocyanate and NMP were used in the amounts shown in Table 1. Table 1 shows the weight average molecular weight, the solid content of the varnish, the theoretical acid value of the varnish, and the actually measured acid value of the obtained polyamideimide resin.

(Comparative Example 1)
Reactive silicone oil KF8010 (manufactured by Shin-Etsu Chemical Co., Ltd., product name, amine equivalent 415) in a 1-liter separable flask equipped with a 25 mL water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer 50.5 g (0.06 mol), BAPP as aromatic diamine (2.2-bis [4- (4-aminophenoxy) phenyl] propane)) 57.5 g (0.14 mol), TMA (trimellitic anhydride) 80.7 g (0.42 mol) and 580 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes.

  Next, 100 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 mL or more of water has accumulated in the moisture determination receiver and that no water has been distilled, remove the distillate that has accumulated in the moisture determination receiver. The temperature was raised to 0 ° C. to remove toluene. Then, it cooled to 50 degreeC, MDI (4,4'- diphenylmethane diisocyanate) 60.1g (0.24 mol) was injected | thrown-in as aromatic diisocyanate, and it was made to react at 190 degreeC for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin was obtained. Table 1 shows the weight average molecular weight of the polyamideimide resin, the solid content of the varnish, the theoretical acid value and the actually measured acid value of the varnish.

  Since the polyamideimide resin of Comparative Example 1 did not contain an aromatic polybasic acid, the theoretical acid value was 0, and the actually measured acid value was as small as 2.0 mgKOH. On the other hand, the difference between the theoretical acid value and the actually measured acid value in Examples 1 to 6 is smaller than the difference between the theoretical acid value and the actually measured acid value in Comparative Example 1, and the polyamideimide resin in Examples 1 to 6 is Both were almost as designed.

  In the above Examples and Comparative Examples, the weight average molecular weight of the polyamideimide resin is converted by using standard polystyrene for the chromatogram of the molecular weight distribution of the polyamideimide resin measured (25 ° C.) by GPC (gel permeation chromatography). Sought by. As an eluent of GPC, a solution in which 0.06 mol / L of phosphoric acid and 0.03 mol / L of lithium bromide monohydrate were dissolved in a tetrahydrofuran / dimethylformamide = 50/50 (volume ratio) mixed solution was used. As the column, a column in which two GL-S300MDT-5 (manufactured by Hitachi High-Technologies Corporation, product name) were directly connected was used.

  Here, in Table 1, D2000 is a diamine constituting the polyoxypropylene imide structure of the synthesized polyamideimide resin. KF8010 is a reactive silicone oil. TMSA refers to trimesic acid. Mw is the weight average molecular weight of the polyamideimide resin, and NV indicates the solid content of the varnish. The evaluation of the film in Table 1 will be described later.

(Example 7)
321.4 g of NMP solution of polyamideimide resin of Example 1 (resin solid content 28% by mass) and 20.0 g of HP4032D (product name, manufactured by DIC Corporation) as an epoxy resin (methyl ethyl ketone solution having a resin solid content of 50% by mass) And 1-cyano-ethyl-2-phenylimidazole (2PZ-CN) 0.1 g, and stirred for about 1 hour until the resin is uniform, and then left at room temperature for 24 hours for defoaming. Thus, a resin composition varnish was obtained.

(Example 8)
360.0 g of NMP solution of polyamideimide resin of Example 2 (resin solid content 25% by mass) and HP4032D (product name of DIC Corporation) as an epoxy resin, 20.0 g (methyl ethyl ketone solution having a resin solid content of 50% by mass) ) And further adding 0.1 g of 1-cyano-ethyl-2-phenylimidazole (2PZ-CN) and stirring for about 1 hour until the resin is uniform, then 24 hours for defoaming, The resin composition varnish was left standing at room temperature.

(Comparative Example 2)
200 g of NMP solution of polyamideimide resin of Comparative Example 1 (resin solid content 30 mass%) and 120.0 g of YDCN-500 (manufactured by Nippon Steel Chemical Co., Ltd., product name) as an epoxy resin (with a resin solid content of 50 wt%) Dimethylacetamide solution) and 0.1 g of 2-ethyl-4-methylimidazole (2E4MZ) were mixed and stirred for about 1 hour until the resin became homogeneous, and then allowed to stand at room temperature for 24 hours for defoaming. To obtain a resin composition varnish.

(Measurement of acid value)
About 1 g of polyamideimide resin varnish was precisely weighed into a polycup and dissolved in 25 ml of N-methyl-2-pyrrolidone. One drop of phenolphthalein was added as an indicator, and 0.1N-potassium hydroxide in methanol was added until the pinkish yellow color disappeared for 30 seconds or more even when stirred. The amount of potassium hydroxide required to neutralize 1 g of the resin from the amount of 0.1N-potassium hydroxide methanol solution used was calculated using the following formula to obtain the measured acid value.

Measured acid value (mg / g) = {(t−t ₀ ) (mL) × 5.611 (mg / mL)} / (x (g) × NV (%) / 100)

Here, t represents titre (mL), _{t 0} represents the blank drops at (solvent only) Determination (mL), x is varnish collection amount (g), NV solid concentration of varnish (%). 5.611 is an amount of potassium hydroxide equivalent to 0.1 mL of 0.1 N KOH.

(Production of film)
Example 1-6, polyamideimide resin varnish of Comparative Example 1 and resin composition varnishes of Examples 7, 8 and Comparative Example 2 having a thickness of 50 μm, a release-treated polyethylene terephthalate film “Purex A63” (Teijin Tetron Film Co., Ltd.) Product, product name) was coated with a bar coater so that the thickness in the B-stage state after drying was 50 μm, and heated and dried at 140 ° C. for 15 minutes to obtain a film.

(Preparation of elastic modulus, Tg and mechanical property evaluation sample)
One film formed from the varnishes of Examples 1 to 6 and Comparative Example 1 was sandwiched between stainless steel frames, treated in a thermostatic bath at a temperature of 180 ° C. for 60 minutes, and evaluated for elastic modulus, Tg, and mechanical properties. A sample (film) was prepared. The mechanical property evaluation sample (film) does not contain an epoxy resin, but is a sample for evaluating the properties of the polyamideimide resin itself.

  Two of the above films formed from the varnishes of Examples 7 and 8 and Comparative Example 2 were stacked, and an electrolytic copper foil F2-WS-12 (product name, manufactured by Furukawa Circuit Foil Co., Ltd.) having a thickness of 12 μm was roughened on both sides. (Surface roughness; Rz = 2.1 μm) is overlapped with the film, and the molding pressure is 2.0 MPa, the molding temperature is 180 ° C., the molding time is 60 minutes, or the molding pressure is 2.0 MPa, the molding temperature is 230 ° C. After press lamination under the conditions of a molding time of 60 minutes, the copper foil was etched to prepare a sample for elastic modulus, Tg and mechanical property evaluation (C stage film). Here, the sample for mechanical property evaluation (C stage film) is obtained by curing a polyamideimide resin composition containing an epoxy resin.

[Evaluation results]
(Evaluation of elastic modulus and Tg)
Using the above-mentioned sample for evaluating mechanical properties, the elastic modulus and Tg were evaluated. Specifically, dynamic viscoelasticity from 30 ° C. to 350 ° C. at a temperature rising rate of 5 ° C./min using a dynamic viscoelasticity measuring device REO-GEL E-4000 (product name, manufactured by UBM Co., Ltd.). It was measured. The temperature at which tan δ had a maximum was taken as Tg. The evaluation results of the mechanical property evaluation samples prepared from the varnishes of Examples 1 to 6 and Comparative Example 1 are shown in Table 1, and the evaluation results of the mechanical property evaluation samples prepared from the varnishes of Examples 7 and 8 and Comparative Example 2 are shown in Table 1. It shows in Table 2.

(Evaluation of 5% thermal weight loss temperature)
Using the above-mentioned sample for evaluating mechanical properties, a 5% thermogravimetric decrease temperature was evaluated. Specifically, 5% thermogravimetric decrease temperature was measured using TG-DTA (Bruker Co., Ltd.). The measurement conditions were a heating rate of 10 ° C./min and under air. The evaluation results of the mechanical property evaluation samples prepared from the varnishes of Examples 1 to 6 and Comparative Example 1 are shown in Table 1, and the evaluation results of the mechanical property evaluation samples prepared from the varnishes of Examples 7 and 8 and Comparative Example 2 are shown in Table 1. It shows in Table 2.

(Evaluation of mechanical properties (breaking strength, breaking elongation))
Using the samples for evaluating mechanical properties described above and the B stage films of Examples 7 and 8 and Comparative Example 2, the breaking strength and breaking elongation as mechanical properties were measured. The breaking strength and elongation were measured using a rheometer (EZ-Test, manufactured by Shimadzu Corporation) on a test piece obtained by processing a film for evaluation into a width of 10 mm and a length of 80 mm under the conditions of a distance between chucks of 60 mm and a pulling speed of 5 mm / min. It was measured. The evaluation results of the mechanical property evaluation samples prepared from the varnishes of Examples 1 to 6 and Comparative Example 1 are shown in Table 1, and the evaluation results of the mechanical property evaluation samples prepared from the varnishes of Examples 7 and 8 and Comparative Example 2 are shown in Table 1. It shows in Table 2.

  As described above, the polyamideimide of the example has mechanical strength and thermal decomposition temperature equal to or higher than those of the comparative example of polyamideimide. When an epoxy resin is blended, the cured polyimide machine is cured even at 180 ° C. It was confirmed that the strength was high.

Claims (6)

A polyamideimide resin comprising a structure represented by the following formula (1) and an organopolysiloxane structure .

[In the formula (1), Ar represents an aromatic ring which may have a substituent other than a carboxyl group, and n represents an integer of 1 or more. ] The polyamide-imide resin according to claim 1, comprising a structure represented by the following formula (2).

A dicarboxylic acid compound, an aromatic polybasic acid that does not undergo dehydration and ring closure in the molecule represented by the following formula (3), and a diisocyanate compound, the aromatic polybasic acid relative to the total number of moles of the dicarboxylic acid compound 0.01-1.0-fold mole and the diisocyanate compound is reacted at a ratio of 1.01-1.45-fold mole with respect to the total mole number of the dicarboxylic acid compound and the aromatic polybasic acid. A method for producing an imide resin ,
A method for producing a polyamideimide resin, wherein the dicarboxylic acid compound has an organopolysiloxane imide structure .

[In the formula (3), Ar represents an aromatic ring which may have a substituent other than a carboxyl group, and m represents an integer of 3 or more. ] An imide obtained by reacting the dicarboxylic acid compound with diamine and trimellitic anhydride at a ratio of 2.0 to 2.3 moles of the trimellitic anhydride with respect to the total number of moles of the diamine. The manufacturing method of the polyamide-imide resin of Claim 3 which is a dicarboxylic acid compound. The method for producing a polyamide-imide resin according to claim 3 or 4 , wherein the aromatic polybasic acid is 1,3,5-tricarboxybenzene. It claims 3-5 polyamideimide resin obtained by the production process of the polyamide-imide resin according to any one of.