JP4474961B2 - Polyamideimide and resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide-imide exhibiting excellent flame retardancy while keeping the adhesiveness to a metal; and to provide a resin composition containing the polyamide-imide. <P>SOLUTION: The polyamide-imide has a chemically bonded phosphorus atom in the molecular structure regulated so that the content of the phosphorus atom based on the whole mass is 0.5-2.5 mass%. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to a polyamideimide and a resin composition containing the same.

  Polyamideimide is generally synthesized by an acid chloride method in which an aromatic diamine and trimellitic acid chloride are reacted, or an isocyanate method in which trimellitic anhydride and aromatic diisocyanate are reacted.

  However, these polyamideimide production methods have the following problems. For example, in the acid chloride method, HCl is generated as a by-product, and thus there is a problem that a complicated process for removing this is required. In addition, in the isocyanate method, although there are few by-products, there is a problem that the structure of the polyamideimide that can be synthesized is limited because there are few kinds of commercially available aromatic diisocyanates.

  Thus, as a method for producing a polyamideimide for avoiding the above-mentioned problems, a method for obtaining a polyamideimide by reacting a diisocyanate compound with the diimide dicarboxylic acid once has been proposed. For example, a method is known in which an aromatic tricarboxylic acid anhydride and a diamine having an ether bond are reacted in an excess of diamine and then a diisocyanate is reacted (see, for example, Patent Document 1). In addition, as a method for efficiently obtaining diimide dicarboxylic acid, a method of reacting an aromatic diamine and trimellitic anhydride is known (for example, see Patent Document 2).

  According to such a method via diimide dicarboxylic acid, HCl is not generated as a by-product, and moreover, it is possible to use a variety of aromatic diamines compared to aromatic diisocyanates. As a result, polyamideimides having various structures can be easily synthesized.

  In addition, an attempt has been made to obtain a polyamideimide having a higher molecular weight according to the above method, and as such an attempt, a diimide having a high solubility in a solvent by using a diamine having three or more aromatic rings as a diamine. A method for synthesizing a dicarboxylic acid has also been proposed (see, for example, Patent Document 3).

  Furthermore, attempts have been made to improve properties such as elastic modulus, flexibility, and drying efficiency by introducing a siloxane structure into polyamideimide (see, for example, Patent Document 4).

  Polyamideimides produced by these production methods are excellent in heat resistance and chemical resistance, and have the characteristics of high elastic modulus and low dielectric constant, so that films, adhesives, paints, It is practically used as a wiring board material.

  By the way, in recent years, in addition to the above-mentioned characteristics, polyamideimide applied to these applications has excellent flame retardancy in consideration of use under high temperature conditions and safety in a fire. It is required to be. However, most of the conventional polyamideimides do not have sufficient characteristics for such a flame retardant requirement.

  Conventionally, as a method for imparting flame retardancy to a resin material, a halogen compound that captures radicals generated during combustion, a hydrated aluminum filler that releases water molecules with combustion, and the like are added to the resin as a flame retardant. A method or a method of increasing the flame retardancy of the resin itself by increasing the aromatic component in the molecule is known. However, resins that have been improved in flame retardancy by these methods often have inconveniences such as generation of harmful gases during combustion and deterioration of resin properties other than flame retardancy. It was.

In order to solve these problems, recently, the use of phosphorus-containing compounds as flame retardants has been studied. Such phosphorus-containing compounds can be said to be relatively safe because there is little concern that harmful gases are generated by combustion. For example, Patent Document 5 below discloses a resin composition obtained by adding an organic phosphorus compound represented by the following formula (8) or the like as a flame retardant.

[Wherein, X ¹ to X ⁸ are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and A represents a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Represents a dihydroxyphenyl group or a dihydroxynaphthyl group which may be substituted with. ]

Japanese Patent Laid-Open No. 3-181511 JP-A-4-182466 JP-A-9-268214 JP-A-11-130831 JP 2000-336204 A

  In recent years, polyamideimide is expected to be applied as a material for an interlayer insulating layer that bonds and insulates each wiring board in a multilayer printed wiring board. In such applications, polyamide imides are required to be superior in elasticity, flexibility, drying efficiency, and the like as compared to conventional ones. These characteristics are achieved by introducing a siloxane structure into the polyamideimide as described above, but the polyamideimide having the siloxane structure introduced in this way improves the above characteristics, but has a remarkable flame retardancy. Tended to be lower. For this reason, when it was going to improve the flame retardance of a polyamideimide by adding the above phosphorus containing compounds as a flame retardant, it was necessary to use a flame retardant in large quantities.

  However, since phosphorus-containing compounds usually have low solubility in resins and solvents, they are often added as solid fillers to polyamideimide. When applied to the interlayer insulating layer material as described above, polyamideimide is often used as a resin composition mixed with a thermosetting resin or the like, and thus contains a large amount of phosphorus-containing compound as a filler. When the polyamideimide used is used as a resin composition, it tends to significantly reduce the adhesion of the wiring board to the metal conductive layer. For this reason, in a multilayer wiring board in which such a resin composition is applied to an interlayer insulating layer, problems such as separation of the insulating layer and the conductive layer are likely to occur.

  This invention is made | formed in view of such a situation, and provides the polyamideimide which can exhibit the outstanding flame retardance, fully maintaining adhesiveness with a metal, and a resin composition containing this With the goal.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by introducing a phosphorus atom into the molecule rather than including a phosphorus-containing compound as a filler in the polyamideimide, The present invention has been completed.

  That is, the polyamideimide of the present invention has a phosphorus atom in the molecular structure, and the phosphorus atom content relative to the total mass is 0.5 to 2.5% by mass.

  The polyamide having such a structure has phosphorus atoms in a state in which it is chemically bonded to the molecular structure, not as a filler as in the prior art. For this reason, the polyamide-imide itself can exhibit excellent flame retardancy without using a flame retardant as described above. Therefore, when such a polyamideimide is used, the problem of lowering the adhesion to the metal, which has occurred with the conventional polyamideimide, is extremely reduced. In addition, the polyamideimide containing a large amount of filler as in the prior art also has a tendency that the cured product becomes extremely brittle. However, according to the polyamideimide of the present invention, there is very little problem of such strength reduction. Become.

  The said polyamideimide contains 0.5-2.5 mass% phosphorus atom with respect to the total mass. When the phosphorus atom content is 0.5% by mass or less with respect to the total mass, the flame retardancy of the polyamideimide is significantly reduced. On the other hand, when the synthesis of polyamideimide is attempted so that the content of phosphorus atoms exceeds 2.5% by mass, all of the phosphorus atoms cannot be present in the molecular structure, and excess phosphorus atoms or compounds containing this are It remains in the polyamide imide, and this reduces the adhesion and strength of the polyamide imide. That is, the polyamideimide of the present invention contains 0.5 to 2.5% by mass of phosphorus atoms, so that the properties such as flame retardancy and adhesiveness are remarkably excellent.

Moreover, it is more preferable that the polyamideimide has a functional group represented by the following chemical formula (1) in the molecular structure. Here, the phosphorus atom in the polyamideimide is more preferably contained mainly in the form of this functional group. A functional group containing a phosphorus atom having such a structure (hereinafter referred to as “phosphorus-containing functional group”) can impart excellent flame retardancy to polyamideimide.

  The polyamideimide of the present invention further has a silicon atom in the molecular structure, and the silicon atom content relative to the total mass is preferably 1.0 to 25.0 mass%.

  Since such a polyamideimide has a silicon atom in its molecular structure, it has excellent elasticity, flexibility, drying efficiency when drying the solvent, and the like. As described above, conventionally, a polyamideimide having a silicon atom introduced into a molecule has a tendency to significantly reduce flame retardancy. On the other hand, since the polyamideimide of the present invention has a phosphorus atom in the molecular structure, the above properties are improved while maintaining excellent heat resistance.

  Moreover, the polyamideimide of the said structure has 1.0-25.0 mass% silicon atom with respect to the total mass. When the silicon atom content is less than 1.0% by mass, for example, when processing polyamideimide into a film, it becomes difficult to volatilize the solvent mixed with polyamideimide, and workability during processing Tend to get worse. On the other hand, when it exceeds 25% by mass, the flame retardancy of polyamideimide is remarkably lowered, and the adhesiveness and strength when the film is formed tend to be lowered. That is, the polyamideimide having a silicon atom content in the above range has sufficient flame retardancy and the like, and has excellent workability during processing.

  In addition, the polyamideimide preferably has an organosiloxane structure in the molecular structure. In particular, it is preferable that the silicon atom in the polyamideimide is mainly contained as the organosiloxane structure. When the polyamideimide has such an organosiloxane structure, the above-described characteristics such as the elastic modulus, flexibility, and drying efficiency are further improved.

Furthermore, the polyamideimide of the present invention is obtained by reacting a phosphorus-containing diisocyanate compound obtained by reacting a phosphorus-containing compound represented by the following chemical formula (2) with a diisocyanate compound and a dicarboxylic acid having an imide group. It is preferable that the structure is included.

  The reaction between the phosphorus-containing compound and the diisocyanate compound and the reaction between the phosphorus-containing diisocyanate thus obtained and the dicarboxylic acid are reactions that can be easily controlled and can occur efficiently. For this reason, according to these reactions, the phosphorus-containing functional group represented by the chemical formula (1) can be easily introduced into the molecular structure of polyamideimide.

More specifically, the dicarboxylic acid contains a diimide dicarboxylic acid mixture including a diimide dicarboxylic acid represented by the following general formula (3) and a diimide dicarboxylic acid represented by the following general formula (4). And preferred.


[Wherein R ³ is a divalent group having one or more aromatic rings, R ⁴¹ is an alkyl group, a phenyl group or a substituted phenyl group, R ⁴² is a divalent organic group, and n is an integer of 1 to 15. Each is shown. A plurality of R ⁴¹ and R ⁴² may be the same or different. ]

  Polyamideimides having structural units composed of these diimidedicarboxylic acids have the property of being excellent in heat resistance and adhesion to metals. For this reason, the polyamideimide having such a structural unit is extremely suitable as an insulating layer forming material in a multilayer wiring board.

Here, the diimide dicarboxylic acid mixture is obtained by a reaction between a diamine mixture containing an aromatic diamine and a siloxane diamine and trimellitic anhydride. In this reaction, an aromatic diamine, a siloxane diamine, and It is more preferable to adjust the blending amount of trimellitic anhydride so as to satisfy the following formula (5).
2.05 ≦ W ₃ / (W ₁ + W ₂ ) ≦ 2.20 (5)
[Wherein, W ₁ represents the number of moles of aromatic diamine, W ₂ represents the number of moles of siloxane diamine, and W ₃ represents the number of moles of trimellitic anhydride. ]

  In the synthesis of the diimide dicarboxylic acid mixture, each of the two amino groups of each diamine reacts with trimellitic anhydride by adjusting the blending amount of each component to the above-described range. As a result, a structure having a carboxyl group derived from trimellitic anhydride at both ends, that is, a diimide dicarboxylic acid having a structure represented by the above general formulas (3) and (4) can be obtained efficiently.

Furthermore, the polyamide-imide of the present invention contains a structural unit obtained by reaction of a phosphorus-containing diisocyanate compound and the above-mentioned diimide dicarboxylic acid mixture (a mixture obtained by the reaction of a diamine mixture and trimellitic anhydride). In this reaction, it is more preferable to adjust the blending amounts of the phosphorus-containing compound, diisocyanate compound, aromatic diamine and siloxane diamine so as to satisfy the following formulas (6) and (7).
1.0 ≦ W ₄ / (W ₁ + W ₂ ) ≦ 1.3 (6)
1.0 ≦ W ₅ / (W ₁ + W ₂ ) ≦ 1.3 (7)
[Wherein W ₁ represents the number of moles of aromatic diamine, W ₂ represents the number of moles of siloxane diamine, W ₄ represents the number of moles of phosphorus-containing compound, and W ₅ represents the number of moles of the diisocyanate compound. ]

  The structural unit synthesized so as to satisfy the above conditions includes a unit containing a diimide dicarboxylic acid represented by the general formula (3) or (4) and a unit containing a phosphorus-containing diisocyanate almost alternately. Become. Polyamideimide having such a structural unit has extremely excellent flame retardancy, and also has excellent characteristics in terms of heat resistance and adhesion to metal.

  The present invention also provides a resin composition containing the polyamideimide of the present invention and a thermosetting resin. The thermosetting resin in such a resin composition preferably has a functional group that reacts with the amide group of the polyamideimide.

  Since such a resin composition contains the polyamideimide of the present invention, it has excellent flame retardancy, heat resistance and adhesion to metal. For this reason, for example, it is suitable as a material for forming an interlayer insulating layer in a multilayer wiring board. A multilayer wiring board provided with such an interlayer insulating layer is excellent in flame retardancy, heat resistance and adhesion to metal. In this multilayer wiring board, there is very little inconvenience that the wiring boards of the respective layers are separated from each other.

  According to the present invention, it is possible to provide a polyamideimide having excellent flame retardancy and sufficient characteristics in terms of adhesion to metal.

  Hereinafter, preferred embodiments of the present invention will be described.

  The polyamideimide of the present invention has a structure containing phosphorus atoms chemically bonded in the molecule. In the polyamideimide having such a structure, the phosphorus atom content is 0.5 to 2.5% by mass, preferably 1.0 to 2.3% by mass, based on the total mass. If the content of phosphorus atoms in the polyamideimide is less than 0.5% by mass, the flame retardancy of the polyamideimide becomes insufficient. On the other hand, when trying to synthesize a polyamideimide exceeding 2.5% by mass, the raw material compound to which phosphorus atoms are to be supplied to the polyamideimide does not sufficiently react, so that the raw material compound remains in the polyamideimide. As a result, the adhesion and strength of the polyamideimide become insufficient.

In such a polyamideimide, the phosphorus atom is preferably introduced into the molecule mainly in the form of a phosphorus-containing functional group represented by the following chemical formula (1).

  Moreover, when suitable, the polyamide-imide of this invention further has a silicon atom in molecular structure. In this case, the content of silicon atoms in the total mass is preferably 1.0 to 25.0 mass%, and more preferably 4.0 to 14.0 mass%. When the silicon atom content is less than 1.0 mass, the flexibility of the polyamideimide is lowered, and for example, when a film or the like is formed, it tends to be brittle. On the other hand, if it exceeds 25.0% by mass, the flame retardancy of polyamideimide is lowered, and the strength and adhesiveness tend to be lowered when a film is formed. The silicon atom in such polyamideimide is preferably contained mainly in the form of an organosiloxane structure.

  Hereinafter, the suitable manufacturing method of the polyamideimide of this invention is demonstrated.

The polyamideimide of the present invention can be obtained by reacting a phosphorus-containing diisocyanate compound obtained by reacting a diisocyanate compound with a phosphorus-containing compound represented by the following chemical formula (2) and a dicarboxylic acid having an imide group. it can. By such a reaction, a polyamideimide having a phosphorus-containing functional group represented by the chemical formula (1) in the molecule is generated.

(Phosphorus-containing diisocyanate)
First, phosphorus-containing diisocyanate will be described. As phosphorus containing diisocyanate, what is obtained by making the phosphorus containing compound represented by the said Chemical formula (2) and a diisocyanate compound react is preferable.

  The phosphorus-containing compound represented by the chemical formula (2) is 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and HCA-HQ It is commercially available as (trade name, manufactured by Sanko Co., Ltd.).

Moreover, as a diisocyanate compound, the compound represented by following General formula (9) can be illustrated.

In the formula, R ⁹¹ is a divalent organic group having one or more aromatic rings or a divalent aliphatic hydrocarbon group. Examples of such divalent _{groups, -C 6 H 4 -CH 2 -C} 6 H 4 - , a group represented by tolylene group, a naphthylene group, a hexamethylene group, 2,2,4-trimethylhexamethylene group And at least one group selected from isophorone groups is preferred.

  Examples of the diisocyanate compound represented by the general formula (9) include aliphatic diisocyanates and aromatic diisocyanates, and these can be used alone or in combination.

  Examples of aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and 2,4-tolylene dimer. It can be illustrated. On the other hand, examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  Among these diisocyanate compounds, aromatic diisocyanates are preferable, and MDI is particularly preferable. By using MDI as the diisocyanate compound, the flexibility of the resulting polyamideimide can be improved and the crystallinity can be reduced. Thereby, the film-formability of polyamideimide is improved.

  The reaction of the phosphorus-containing compound represented by the chemical formula (2) and the diisocyanate compound represented by the general formula (9) can be performed in a solvent capable of dissolving both. As such a solvent, it is preferable to select a solvent that can dissolve a phosphorus-containing compound having a particularly low solubility in the solvent. For example, N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”), dimethylacetamide, dimethylformamide, dimethylsulfoxide and the like can be mentioned. Especially, NMP which is excellent in the solubility of a phosphorus containing compound is preferable.

  In this reaction, it is preferable to react 1.9 to 2.5 times the molar amount of the diisocyanate compound with respect to the phosphorus-containing compound represented by the chemical formula (2). By carrying out like this, two phenolic hydroxyl groups in a phosphorus containing compound come to react with a diisocyanate compound, respectively, and, thereby, a phosphorus containing diisocyanate compound can be obtained efficiently.

  The above reaction is preferably caused to occur at a reaction temperature of 40 to 100 ° C, more preferably 50 to 80 ° C. When this reaction temperature is less than 40 ° C., the progress of the reaction is remarkably slow, and it may be difficult to sufficiently generate a phosphorus-containing diisocyanate compound. On the other hand, when reaction temperature exceeds 100 degreeC, reaction will come to occur rapidly and phosphorus containing diisocyanate compounds may superpose | polymerize and an oligomer body and a polymer body may be produced. As a result, the production amount of the desired phosphorus-containing diisocyanate compound tends to decrease.

  More specifically, the above reaction is preferably carried out by mixing the phosphorus-containing compound and the diisocyanate compound at room temperature and then gradually raising the temperature within the above-mentioned temperature range. In this case, since the phosphorus-containing compound that is a solid substance gradually dissolves in the solvent as the reaction proceeds, the progress of the reaction can be easily confirmed.

By reacting the phosphorus-containing compound represented by the chemical formula (2) and the diisocyanate compound represented by the general formula (9) in this way, for example, the phosphorus-containing compound represented by the following general formula (10) A diisocyanate compound is formed. In the formula, R ⁹¹ has the same meaning as described above.

(Dicarboxylic acid having an imide group)
Examples of the dicarboxylic acid having an imide group include a diimide dicarboxylic acid mixture containing a diimide dicarboxylic acid represented by the following general formula (3) and a diimide dicarboxylic acid represented by the following general formula (4).

In the general formula (3), R ³ represents a divalent group having one or more aromatic rings. In the general formula (4), R ⁴¹ represents an alkyl group, a phenyl group or a substituted phenyl group, and R ⁴² represents A divalent organic group is shown respectively. Here, a plurality of R ⁴¹ and R ⁴² may be the same or different.

  The diimide dicarboxylic acid mixture containing the diimide dicarboxylic acid represented by the general formula (3) and the diimide dicarboxylic acid represented by the general formula (4) is a diamine mixture containing an aromatic diamine and a siloxane diamine (hereinafter referred to as “diamine”). It is preferable that it is obtained by the reaction of "mixture") and trimellitic anhydride. In such a reaction, the reaction between the aromatic diamine and trimellitic anhydride produces the diimide dicarboxylic acid represented by the above general formula (3), and the reaction between the siloxane diamine and trimellitic anhydride causes the above general formula ( The diimide dicarboxylic acid represented by 4) is produced.

Examples of the aromatic diamine for obtaining the diimide dicarboxylic acid represented by the general formula (3) include aromatic diamines having one or more aromatic rings. Such aromatic diamines can be classified into monocyclic aromatic diamines having one aromatic ring, bicyclic aromatic diamines having two aromatic rings, and aromatic diamines having three or more aromatic rings. . As a result of such a reaction, the diimide dicarboxylic acid represented by the general formula (3) has a divalent group obtained by removing an amino group from these aromatic diamines as the group represented by R ^3. It becomes like this.

  For example, examples of the monocyclic aromatic diamine include paraphenylene diamine and metaphenylene diamine. Examples of the bicyclic aromatic diamine include 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ', 6'-tetramethyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyl-biphenyl-4,4'-diamine, 4,4'-diaminobiphenylsulfone, 4,4 Examples include '-diaminobiphenyl ether, 4,4'-diaminobiphenylmethane, 4,4'-diaminobiphenyl ketone, and the like.

Examples of the diamine having three or more aromatic rings include diamines represented by the following general formula (11).

In the formula, R ¹¹ is a divalent group having one or more aromatic rings, and preferably a divalent group represented by the following formula (12a) or (12b). In the following formula (12a), R ¹² represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, or a single bond. Indicates.

  Examples of the aromatic diamine having three or more aromatic rings include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as “BAPP”), bis [4- (3-amino Phenoxy) phenyl] sulfone, 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- Examples thereof include bis (4-aminophenoxy) benzene and 1,4-bis (aminophenoxy) benzene. These can be used alone or in combination of two or more.

  Among the aromatic diamines described above, aromatic diamines having three or more aromatic rings are preferable, and the preferred number of aromatic rings is 3 to 6. Such an aromatic diamine can improve properties such as heat resistance and strength of the obtained polyamideimide. Among these, BAPP is particularly preferable because it is particularly excellent in these characteristics and is easily available.

On the other hand, the siloxane diamine for obtaining the diimide dicarboxylic acid represented by the general formula (4) is a diamine represented by the following general formula (13). In the formula, R ⁴¹ and R ⁴² are as defined above.

More specifically, R ⁴¹ is preferably a C 1-3 alkyl group, a C 1-3 alkyl group, or a phenyl group optionally substituted with a halogen atom. As the R ^42, or an alkylene group having 1 to 6 carbon atoms, an alkyl group or an optionally substituted phenylene group with a halogen atom having 1 to 3 carbon atoms, an alkyl group or a halogen atom having 1 to 3 carbon atoms An optionally substituted naphthalene group is preferred.

  Examples of such siloxane diamines include X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), and X-22-161B (amine equivalent 1500) which are amino-modified silicone oils (above. Manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-853 (amine equivalent 650), BY-16-853B (amine equivalent 2200) (above, manufactured by Toray Dow Corning Silicone), X-22-9409 (amine equivalent 680), X -226-1660B (amine equivalent 2260, above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. These can be used alone or in combination of two or more.

  In producing the polyamideimide of the present invention, the diamine mixture may contain other diamine compounds in addition to the aromatic diamine and siloxane diamine described above. Examples of such other diamine compounds include aliphatic diamines, and the blending amount thereof is desirably about 0 to 50 mol% in the total amount of the diamine mixture.

  The reaction of the diamine mixture and trimellitic anhydride to obtain the diimide dicarboxylic acid mixture can be performed as follows, for example. That is, first, the diamine mixture and trimellitic anhydride are dissolved or dispersed in a solvent and stirred at 50 to 90 ° C. for reaction. In this reaction, a reaction between an amino group in each diamine and a carboxyl group in trimellitic anhydride mainly occurs, and as a result, an amide group and a carboxyl group resulting from both reactions are generated. In addition, it is preferable to adjust suitably the ratio of the aromatic diamine and siloxane diamine in a diamine mixture according to the desired characteristic in the range from which the content of the silicon atom in a polyamideimide becomes the suitable value mentioned above.

In this reaction, for example, when the diamine mixture is composed of an aromatic diamine and a siloxane diamine, the blending amounts of the aromatic diamine, the siloxane diamine, and trimellitic anhydride are adjusted so as to be represented by the following formula (5). It is preferable.
2.05 ≦ W ₃ / (W ₁ + W ₂ ) ≦ 2.20 (5)

In the above formula, W ₁ represents the number of moles of aromatic diamine, W ₂ represents the number of moles of siloxane diamine, and W ₃ represents the number of moles of trimellitic anhydride. By setting each component to such a blending amount, each of the two amino groups at the ends of the aromatic diamine and siloxane diamine will react with the anhydrous carboxyl group in trimellitic anhydride.

  Examples of the solvent used in the above reaction include aprotic polar solvents such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone (NMP), 4-butyrolactone, and sulfolane. Among these, NMP is preferable.

  Following such a reaction, an aromatic hydrocarbon capable of azeotroping with water is added to the solution after the reaction to a temperature of 120 to 180 ° C., whereby the amide group and the carboxyl group generated by the above-described reaction can be reduced. Cause a dehydration ring closure reaction. By this dehydration ring closure reaction, an imide group is generated from the amide group and the carboxyl group, and as a result, diimide dicarboxylic acid corresponding to each diamine in the diamine mixture is generated.

  Examples of aromatic hydrocarbons that can be azeotroped with water used in the dehydration ring closure reaction include toluene, benzene, xylene, and ethylbenzene. Of these, toluene is preferable. When these aromatic hydrocarbons are added in an amount of 10 to 50% by mass based on the solvent, the dehydration ring closure reaction tends to occur efficiently. In addition, after completion | finish of a spin-drying | dehydration ring-closing reaction, it is preferable to remove the aromatic hydrocarbon azeotropic with water by further heating and stirring the solution after reaction to about 190 degreeC.

(Synthesis of polyamideimide)
As described above, the polyamideimide of the present invention is obtained by treating the phosphorus-containing diisocyanate compound and the dicarboxylic acid having an imide group in a solvent at 100 to 180 ° C. for about 2 to 4 hours. be able to.

  The aprotic polar solvent used in this reaction is preferably one that does not have reactivity with a dicarboxylic acid having an imide group or a phosphorus-containing diisocyanate compound and that can be used at the reaction temperature described above. . As such a solvent, the aprotic polar solvent used at the time of manufacture of the diimide dicarboxylic acid mixture mentioned above is preferable, and NMP that can be used under higher temperature conditions is particularly preferable.

  Further, the compounding amount of the dicarboxylic acid having an imide group and the phosphorus-containing diisocyanate compound in this reaction is preferably adjusted according to the amount of phosphorus atoms to be contained in the polyamideimide, but the phosphorus atom content is as described above. As long as it becomes the range, it is preferable that each compounding quantity shall be a substantially equimolar amount. If it carries out like this, a polyamideimide will have the structural unit based on these compounds uniformly (preferably alternately), and the flame retardance of a polyamideimide will improve further by this.

For example, when a diimide dicarboxylic acid mixture as described above is used as the dicarboxylic acid having an imide group, the reaction is carried out using the amount of phosphorus-containing compound and diisocyanate compound as the aromatic diamine used when preparing the diimide dicarboxylic acid mixture. It is preferable to adjust so that the relationship represented by the following formulas (6) and (7) is satisfied with respect to the blending amount of siloxane diamine and siloxane diamine. In the following formula, W ₁ represents the number of moles of aromatic diamine, W ₂ represents the number of moles of siloxane diamine, W ₄ represents the number of moles of phosphorus-containing compound, and W ₅ represents the number of moles of the diisocyanate compound.
1.0 ≦ W ₄ / (W ₁ + W ₂ ) ≦ 1.3 (6)
1.0 ≦ W ₅ / (W ₁ + W ₂ ) ≦ 1.3 (7)

  In such a reaction, the isocyanate group in the phosphorus-containing diisocyanate compound reacts with the carboxyl group of the dicarboxylic acid having an imide group to produce an amide group, and thereby a polyamideimide having a phosphorus atom in the molecular structure. Produces.

For example, the phosphorus-containing diisocyanate compound is a compound represented by the above general formula (10), and the dicarboxylic acid having an imide group includes a diimide dicarboxylic acid represented by the above general formulas (3) and (4). In the case of a dicarboxylic acid mixture, a polyamideimide having a structural unit represented by the following general formula (14a) and a structural unit represented by the following general formula (14b) is often mainly produced. In addition, all the symbols in a following formula are synonymous with the above.

  In addition, the reaction may not necessarily include only the above-described phosphorus-containing diisocyanate compound and dicarboxylic acid containing an imide group, and other reactions may be included in the reaction as long as the properties of the obtained polyamideimide can be maintained. You may mix an ingredient. For example, a part of the phosphorus-containing diisocyanate compound can be replaced with a diisocyanate having no phosphorus atom. Examples of the diisocyanate that does not contain a phosphorus atom include diisocyanate compounds that can be used when the above-described phosphorus-containing diisocyanate compound is synthesized. By doing so, the properties of the polyamideimide can be controlled, and the content of the phosphorus atom in the polyamideimide can be adjusted so as not to exceed 2.5% by mass. However, when the polyamideimide is synthesized by the above-described method, in most cases, the phosphorus atom content is 2.5% by mass or less, so that such replacement for the latter purpose is hardly required.

  From the same viewpoint, the dicarboxylic acid containing an imide group can be partially replaced with a dicarboxylic acid having no imide group. By carrying out like this, content of the imide group in a polyamideimide can also be adjusted. Examples of the dicarboxylic acid having no imide group include aromatic dicarboxylic acids and aliphatic dicarboxylic acids that can be used when the above-described diimide dicarboxylic acid is synthesized.

(Resin composition)
The polyamideimide of the present invention as described above can be applied to various uses such as adhesives and wiring board materials in the form of a resin composition combined with a thermosetting resin. Examples of such thermosetting resins include epoxy resins, polyimide resins, unsaturated polyester resins, polyurethane resins, bismaleimide resins, triazine-bismaleimide resins, and phenol resins.

  These resin compositions preferably contain 1 to 200 parts by mass of thermosetting resin with respect to 100 parts by mass of polyamideimide, more preferably 3 to 100 parts by mass, and more preferably 5 to 80 parts by mass. More preferably, it is contained in part. When the content of the thermosetting resin is less than 1 part by mass, the solvent resistance after curing deteriorates, and the durability of the cured product tends to decrease. On the other hand, when it exceeds 200 mass parts, the glass transition temperature of hardened | cured material will become low and it exists in the tendency for heat resistance to fall.

  As the thermosetting resin to be combined with the polyamideimide of the present invention, a thermosetting resin having a functional group that reacts with the amide group in the polyamideimide (hereinafter referred to as “amide reactive compound”) is preferable. The functional group that reacts with the amide group is preferably an epoxy group, particularly a glycidyl group. As the amide-reactive compound, a polyfunctional epoxy compound (epoxy resin) having two or more of these functional groups is preferable. When such a polyfunctional epoxy compound is used as the amide-reactive compound, the cured product of the resin composition is excellent in heat resistance, mechanical properties, and electrical properties. Of the polyfunctional epoxy compounds, polyfunctional epoxy compounds having 3 or more epoxy groups are preferred.

  Examples of polyfunctional epoxy compounds having two or more epoxy groups include epoxy resins obtained by reacting polychlorophenols such as bisphenol A, novolac type phenol resins, orthocresol novolac type phenol resins and epichlorohydrin; 1,4-butane An epoxy resin obtained by reacting a polyhydric alcohol such as a diol with epichlorohydrin; a polyglycidyl ester obtained by reacting a polybasic acid such as phthalic acid or hexahydrophthalic acid with epichlorohydrin; an amine, an amide or a heterocyclic type Examples thereof include N-glycidyl derivatives of compounds having a nitrogen base; alicyclic epoxy resins and the like.

  In addition, as polyfunctional epoxy compounds having three or more glycidyl groups, ZX-15548-2 (manufactured by Tohto Kasei Co., Ltd.), DER-331L (bisphenol A type epoxy resin manufactured by Dow Chemical Company), YDCN-195 (Tohto) Examples thereof include a cresol novolac type epoxy resin manufactured by Kasei Corporation.

  Thus, when using a polyfunctional epoxy compound as an amide-reactive compound, it is preferable to further add the hardening | curing agent and hardening accelerator of a polyfunctional epoxy compound in curable resin. Known curing agents and curing accelerators can be used. For example, as the curing agent, amines such as dicyandiamide, diaminodiphenylmethane, guanylurea; imidazoles; hydroquinone, resorcinol, bisphenol A and their halides, polyfunctional phenols such as novolac-type phenol resin, resole-type phenol resin; Examples thereof include acid anhydrides such as phthalic anhydride, benzophenone tetracarboxylic dianhydride, and methyl hymic acid. Examples of the curing accelerator include imidazoles such as alkyl group-substituted imidazole and benzimidazole.

  When adding a hardening | curing agent, the compounding quantity can be determined according to the epoxy equivalent in a polyfunctional epoxy compound. For example, when an amine compound is added as a curing agent, the compound is blended so that the active hydrogen equivalent of the amine is equal to the epoxy equivalent of the polyfunctional epoxy compound. When the curing agent is a polyfunctional phenol or acid anhydride, the compounding amount is 0.6 to 1.2 equivalent of phenolic hydroxyl group or carboxyl group with respect to 1 equivalent of polyfunctional epoxy compound. It is preferable that Furthermore, when adding a hardening accelerator, it is preferable that the compounding quantity shall be 0.001-10 weight part with respect to 100 weight part of polyfunctional epoxy compounds.

  When the blending amount of these curing agents or curing accelerators is less than the above range, the polyfunctional epoxy compound is insufficiently cured, and the glass transition temperature after curing of the resin composition tends to be low and the heat resistance tends to decrease. . On the other hand, when the amount is larger than the above range, the electrical characteristics after curing of the resin composition tend to be lowered by the remaining curing agent or curing accelerator.

  Since the resin composition thus configured contains the polyamideimide of the present invention in the composition, the resin composition has extremely excellent flame retardancy and excellent adhesion to metals and the like. . Therefore, it can be suitably used as an insulating adhesive layer between wiring boards in a multilayer printed wiring board.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Synthesis of Polyamideimide]

Example 1
Reactive silicone oil KF8010 (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430) 215 as a siloxane diamine was added to a 25-mL water quantitative receiver with a cock connected to a reflux condenser, a thermometer and a stirrer. 0.0 g (0.25 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 102.5 g (0.25 mol) as an aromatic diamine, trimellitic anhydride (TMA) 201. 6 g (1.05 mol) and 519 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes.

  After completion of the stirring, 200 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 2 hours. When it is confirmed that water has accumulated in the moisture determination receiver about 18 mL or more and water is no longer being distilled, the distillate in the moisture determination receiver is removed, and the temperature is further increased to 190 ° C. Toluene in the reaction solution was removed. Thereafter, the solution was lowered to room temperature to obtain a solution containing a diimide dicarboxylic acid mixture.

  In parallel with this, in another 5 L separable flask equipped with a 25 mL water quantitative receiver with a cock connected to a reflux condenser, a thermometer and a stirrer, NMP 1363 mL, HCA-HQ as a phosphorus-containing compound (manufactured by Sanko Co., Ltd., (Phosphorus-containing compound represented by the above chemical formula (2)) 194.4 g (0.6 mol), 4,4′-diphenylmethane diisocyanate (MDI) 300 g (1.2 mol) was added as a diisocyanate compound, and 2 at 60 ° C. Reacted for hours.

  In this 5 L separable flask, the whole amount of the solution containing the above-mentioned diimide dicarboxylic acid mixture was added, and the temperature was raised to 160 ° C. and reacted for 2 hours. After the reaction, the solution was cooled to room temperature to obtain an NMP solution of polyamideimide having a phosphorus atom in the molecule. The content of polyamideimide in the obtained solution was 35% by mass, and the content of phosphorus atoms in the polyamideimide was 1.89% by mass.

(Example 2)
In a 3 L separable flask equipped with a 25 mL water meter with a cock connected to a reflux condenser, a thermometer and a stirrer, 205.0 g (0.50 mol) of BAPP as an aromatic diamine and 201.6 g of TMA (1.05 mol), 407 g of NMP was charged as an aprotic polar solvent and stirred at 80 ° C. for 30 minutes.

  After completion of the stirring, 150 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 2 hours. When it is confirmed that water has accumulated in the moisture determination receiver about 18 mL or more and water is no longer being distilled, the distillate in the moisture determination receiver is removed, and the temperature is further increased to 190 ° C. Toluene in the reaction solution was removed. Thereafter, the solution was lowered to room temperature to obtain a solution containing a diimide dicarboxylic acid mixture.

  In parallel with this, in another 5 L separable flask equipped with a 25 mL water quantitative receiver with a cock connected to a reflux condenser, a thermometer and a stirrer, NMP 1267 mL, 194.4 g of HCA-HQ as a phosphorus-containing compound ( 0.6 mol), 300 g (1.2 mol) of MDI was added as an aromatic diisocyanate, and the mixture was reacted at 60 ° C. for 2 hours.

  In this 5 L separable flask, the whole amount of the solution containing the above-mentioned diimide dicarboxylic acid mixture was added, and the temperature was raised to 160 ° C. and reacted for 2 hours. After the reaction, the solution was cooled to room temperature to obtain an NMP solution of polyamideimide having a phosphorus atom in the molecule. The content of the polyamideimide in the obtained solution was 35% by mass, and the content of phosphorus atoms in the polyamideimide was 2.13% by mass.

(Example 3)
43.0 g (0.05 mol) of reactive silicone oil KF8010 as a siloxane diamine in a 3 L separable flask equipped with a 25 mL moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer, aromatic 184.5 g (0.45 mol) of BAPP as a diamine, 201.6 g (1.05 mol) of TMA, and 546 g of NMP as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes.

  After completion of the stirring, 150 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 2 hours. When it is confirmed that water has accumulated in the moisture determination receiver about 18 mL or more and water is no longer being distilled, the distillate in the moisture determination receiver is removed, and the temperature is further increased to 190 ° C. Toluene in the reaction solution was removed. Thereafter, the solution was lowered to room temperature to obtain a solution containing a diimide dicarboxylic acid mixture.

  In parallel with this, in a separate 5 L separable flask equipped with a 25 mL water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer, 194.4 g (0. 6 mol), 300 g (1.2 mol) of MDI was added as an aromatic diisocyanate and reacted at 60 ° C. for 2 hours.

  In this 5 L separable flask, the whole amount of the solution containing the diimide dicarboxylic acid mixture described above was further added, the temperature was raised to 160 ° C., and the reaction was performed for 2 hours. After the reaction, the solution was cooled to room temperature to obtain an NMP solution of polyamideimide having a phosphorus atom in the molecule. The content of polyamideimide in the obtained solution was 35% by mass, and the content of phosphorus atoms in the polyamideimide was 1.79% by mass.

(Comparative Example 1)
Into a 3 L separable flask equipped with a 25 mL moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer, 84.2 g of reactive silicone oil KF8010 as a siloxane diamine and 41 of BAPP as an aromatic diamine 0.1 g, 80.7 g of TMA, and 494 g of NMP as an aprotic polar solvent were added and stirred at 80 ° C. for 30 minutes.

  After completion of stirring, 100 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 2 hours. After confirming that water has accumulated in the moisture determination receiver about 7.2 mL or more and that water is no longer being distilled, remove the distillate in the moisture determination receiver and further raise the temperature to 190 ° C. Then, toluene in the reaction solution was removed.

After this solution was cooled to room temperature, 60.1 g of MDI as an aromatic diisocyanate was charged into the flask and reacted at 160 ° C. for 2 hours. Thereafter, the solution was cooled to room temperature to obtain a polyamideimide NMP solution containing no phosphorus atom in the molecule.
[Preparation of resin composition]

Example 4
In the NMP solution of polyamideimide of Example 1, 1 part by mass of DER331L (Dow Chemical Co., bisphenol A type epoxy resin) and 0.01 parts by mass of 9 parts by mass of polyamideimide 2-Ethyl-4-methylimidazole was added to obtain a resin composition.

(Example 5)
A resin composition was obtained in the same manner as in Example 4 except that the NMP solution of polyamideimide in Example 2 was used instead of the NMP solution in polyamideimide of Example 1.

(Example 6)
A resin composition was obtained in the same manner as in Example 4 except that the NMP solution of polyamideimide in Example 3 was used instead of the NMP solution in polyamideimide of Example 1.

(Example 7)
A resin composition was obtained in the same manner as in Example 4 except that ZX1548-2 (manufactured by Tohto Kasei Co., Ltd., phosphorus-containing polyfunctional epoxy resin) was used instead of DER331L which is an epoxy resin.

(Example 8)
A resin composition was obtained in the same manner as in Example 5 except that ZX1548-2 (manufactured by Toto Kasei Co., Ltd., phosphorus-containing polyfunctional epoxy resin) was used instead of DER331L, which was an epoxy resin.

(Comparative Example 2)
A resin composition was obtained in the same manner as in Example 4 except that the NMP solution of polyamideimide of Comparative Example 1 was used instead of the NMP solution of polyamideimide of Example 1.
[Flame retardance evaluation]

  The adhesive compositions of Examples 4 to 8 and Comparative Example 2 were applied on a polyethylene terephthalate (PET) film that had been subjected to a release treatment and dried at 140 ° C. for 20 minutes. After the dried coating film was peeled off from the PET film, this was put on a stainless steel frame, and the film of the resin composition was cured by treatment at 200 ° C. for 1 hour to obtain a resin film.

  The obtained resin film was cut into a strip shape having a width of 13 mm and a length of 130 mm to obtain a sample for a combustion test. Using this sample for combustion test, a combustion test based on UL94 was conducted. That is, first, after applying a methane / air mixed flame to the 1 cm lower end of the sample for 10 seconds, the flame was released, and the time until the flame disappeared from the sample (burning time) was measured. Next, after the flame was again applied to the same part of the same sample for 10 seconds, the flame was released, and the time until the flame disappeared from the sample (burning time) was measured.

Five samples obtained from each adhesive composition were prepared, and the above test was conducted for all of them, and the average burning time and the maximum burning time for each sample were determined. A sample having an average burning time of 5 seconds or less and a maximum burning time of 10 seconds or less was recognized as V-0, and the other samples were judged to be easy to burn. The obtained results are shown in Table 1.
[Evaluation of adhesion to polyimide film]

  The resin compositions of Examples 4 to 8 and Comparative Example 2 were applied to one side of a polyimide film (Kapton (registered trademark), manufactured by Toray DuPont, thickness 50 μm) so that the thickness after drying was 20 μm. . This was dried at 120 ° C. for 15 minutes in a hot air circulating dryer, and further treated at 180 ° C. for 2 hours to cure the resin composition, thereby obtaining a laminated film. The cured film of the resin composition in this laminated film was adhered to an epoxy resin plate using an epoxy adhesive (Araldite, manufactured by Ciba Geigy) to obtain a laminated body.

Thereafter, the polyimide film in the obtained laminate was peeled from the cured film of the resin composition at a rate of 1 cm width at a rate of 5 cm / min, whereby the adhesive strength A between the cured film of the resin composition and the polyimide film ( kN / m). The obtained results are shown in Table 1.
[Evaluation of adhesion to copper foil]

  The resin compositions of Examples 4 to 8 and Comparative Example 2 were applied to the roughened surface of copper foil (SLP-18, manufactured by Nippon Electrolytic Copper Foil Co., Ltd.) so that the thickness after drying was 20 μm. It dried at 120 degreeC and 15 minute (s) in the warm air circulation type dryer, and obtained copper foil with resin. The roughened surface of the same copper foil as above is laminated to the layer of the resin composition in this laminated film, and the resin composition is cured by thermocompression bonding under conditions of 180 ° C. and 2 MPa for 1 hour. Obtained.

  The copper foil in the resin film with double-sided copper foil is peeled from the layer of the resin composition at a rate of 1 cm width at a rate of 5 cm / min, and thereby the adhesion between the cured film of the resin composition and the roughened surface of the copper foil The strength B (kN / m) was measured. The obtained results are shown in Table 1.

  From Table 1, the resin compositions (Examples 4 to 8) containing the polyamideimide (Examples 1 to 3) of the present invention having 0.5 to 2.5% by mass of phosphorus atoms in the molecular structure are as follows. All the films made of the cured product were able to achieve V-0 in the UL94 test and were found to have excellent flame retardancy. Moreover, it was confirmed that the adhesiveness to a polyimide film or copper foil is also high. On the other hand, the resin composition (Comparative Example 2) containing the polyamideimide (Comparative Example 1) that does not have a phosphorus atom is excellent in adhesiveness to a polyimide film or a copper foil, but in the form of a film. It turned out to be easy to burn.

Claims (8)

It includes a structural unit obtained by reacting a phosphorus-containing diisocyanate compound obtained by reacting a phosphorus-containing compound represented by the following chemical formula (2) with a diisocyanate compound and a dicarboxylic acid having an imide group. you Lupo Riamidoimido.
The dicarboxylic acid mixture containing a diimide dicarboxylic acid represented by the following general formula (3) and a diimide dicarboxylic acid represented by the following general formula (4) as the dicarboxylic acid: 1. Polyamideimide according to 1 .
[Wherein R ³ is a divalent group having one or more aromatic rings, R ⁴¹ is an alkyl group, a phenyl group or a substituted phenyl group, R ⁴² is a divalent organic group, and n is an integer of 1 to 15. Each is shown. A plurality of R ⁴¹ and R ⁴² may be the same or different. ] The diimide dicarboxylic acid mixture is obtained by reacting a diamine mixture containing an aromatic diamine and a siloxane diamine with trimellitic anhydride,
3. The polyamide according to claim 2 , wherein in the reaction, the blending amounts of the aromatic diamine, the siloxane diamine, and the trimellitic anhydride are adjusted so as to satisfy the relationship represented by the following formula (5). Imide.
2.05 ≦ W ₃ / (W ₁ + W ₂ ) ≦ 2.20 (5)
[Wherein, W ₁ represents the number of moles of aromatic diamine, W ₂ represents the number of moles of siloxane diamine, and W ₃ represents the number of moles of trimellitic anhydride. ] Including a structural unit obtained by the reaction of the phosphorus-containing diisocyanate compound, the diimide dicarboxylic acid mixture obtained by the reaction of the diamine mixture and the trimellitic anhydride,
In the reaction, the amount of the phosphorus-containing compound, the diisocyanate compound, the aromatic diamine, and the siloxane diamine is adjusted so as to satisfy the relationship represented by the following formulas (6) and (7). The polyamideimide according to claim 3 .
1.0 ≦ W ₄ / (W ₁ + W ₂ ) ≦ 1.3 (6)
1.0 ≦ W ₅ / (W ₁ + W ₂ ) ≦ 1.3 (7)
[Wherein W ₁ represents the number of moles of aromatic diamine, W ₂ represents the number of moles of siloxane diamine, W ₄ represents the number of moles of phosphorus-containing compound, and W ₅ represents the number of moles of the diisocyanate compound. ] It has a phosphorus atom in molecular structure, Content of the said phosphorus atom with respect to the total mass is 0.5-2.5 mass%, It is any one of Claims 1-4 characterized by the above-mentioned. The polyamideimide described. The polyamideimide according to any one of claims 1 to 5, wherein the molecular structure has an organosiloxane structure. A resin composition comprising the polyamideimide according to any one of claims 1 to 6 and a thermosetting resin. The resin composition according to claim 7 , wherein the thermosetting resin has a functional group that reacts with an amide group of the polyamideimide.