JP5000074B2 - Method for producing polyamideimide - Google Patents

Description

The present invention relates to the production how polyamideimide.

  As a method for producing polyamideimide, an acid chloride method (for example, see Patent Document 1) using an aromatic diamine as a raw material and an isocyanate method (for example, see Patent Document 2) are known.

  In recent years, attempts have been made to improve properties such as elastic modulus, flexibility, and drying efficiency by introducing a siloxane structure into polyamideimide. Polyamideimide having such a siloxane structure can be obtained by polycondensation of aromatic tricarboxylic acid anhydride, aromatic diisocyanate and diaminosiloxane (for example, see Patent Document 3), aromatic dicarboxylic acid or aromatic tricarboxylic acid and A method of polycondensation with diaminosiloxane (for example, see Patent Document 4) has been studied.

Furthermore, a method for improving the above-described isocyanate method has also been attempted. For example, a method of obtaining a high molecular weight polyamideimide by using a diamine having three or more aromatic rings and a siloxane diamine as a diamine component (for example, Patent Document 5). And a method of introducing an aliphatic chain into polyamide-imide by using an aliphatic diamine as a diamine component (for example, see Patent Document 6).
U.S. Pat. No. 3,920,612 Japanese Patent No. 2897186 JP-A-5-009254 JP-A-6-116517 JP-A-11-130831 Japanese Patent Laid-Open No. 11-263840

  However, according to the method described in Patent Document 1 or 4, the remaining components based on the condensing agent used in the synthesis, oligomers that may be by-produced during the reaction, hydrochloric acid, unreacted monomers, etc. are synthesized. In some cases, the electrical properties such as volume resistance and insulation resistance after moisture absorption of the obtained polyamideimide become insufficient due to mixing in the polyamideimide.

  Further, in the method described in Patent Document 2, a polyamideimide film having a sufficient strength for the purpose of a protective film for a substrate and the like can be obtained, but a high enough strength that a film alone can exhibit a sufficient strength. It was difficult to obtain a molecular weight polyamideimide. Furthermore, the polyamideimide obtained by the method described in Patent Document 3 tends to be inferior in film formability, and has a heat resistance such as a decrease in elastic modulus at a temperature exceeding the glass transition temperature, particularly at a temperature exceeding 200 ° C. Tended to be insufficient.

  On the other hand, the polyamideimide obtained by the method described in Patent Document 5 or 6 has not only film formability, electrical characteristics, strength and heat resistance, but also excellent adhesion to the substrate. It was. However, this polyamideimide tends to have an excessively large linear thermal expansion coefficient. Therefore, when a laminate is formed by applying to a substrate or the like, the linear thermal expansion coefficient between the substrate and the layer made of polyamideimide is low. The difference was large, and the laminate sometimes warped.

  The present invention has been made in view of the above circumstances, and when applied as a layer forming material of a laminate, a method for producing a polyamideimide capable of reducing warpage of the laminate, and a polyamideimide and a polyamide obtained by such a production method An object is to provide an imide varnish.

  As a result of detailed investigations by the present inventors in order to achieve the above object, the polyamideimide obtained can be controlled by controlling the continuity of the predetermined structural units constituting the polyamideimide molecule to be large. The present inventors have found that the linear thermal expansion coefficient can be lowered and completed the present invention.

[式中、Ｒ¹は、オルガノポリシロキサンジアミンからアミノ基を除いてなる、主鎖に芳香環構造を有しない２価の基を示す。] That is, the production method of the polyamide-imide of the present invention includes a first step of obtaining a first dicarboxylic acid Ru Rana or aromatic dicarboxylic acid, the polymer is reacted with first a diisocyanate compound represented by the following general formula A second step of reacting the second dicarboxylic acid composed of the dicarboxylic acid represented by (1) , the second diisocyanate compound, and the polymer to obtain a polyamideimide is provided. In addition, in the following general formula (1), “the main chain does not have an aromatic ring structure” means that the main chain constituting the group is constituted mainly by bonds between structures having an aromatic ring. This means that the group may have an aromatic ring structure in the side chain or terminal portion.

[Wherein, R ¹ represents a divalent group having no aromatic ring structure in the main chain, which is obtained by removing an amino group from an organopolysiloxane diamine . ]

  The polyamideimide obtained by the production method of the present invention has a structural unit based on an aromatic dicarboxylic acid in the molecule. Thus, it is considered that the polyamideimide having an aromatic ring structure in the molecule is likely to produce a stacking effect based on the action of the aromatic rings within the molecule or between the molecules. For this reason, the polyamideimide produced by the above-described method is limited in molecular deformation due to this stacking effect, and has a small linear thermal expansion coefficient.

In this production method, a polymer of aromatic dicarboxylic acid and diisocyanate is once formed in the first step, and then the reaction of this polymer with another dicarboxylic acid and diisocyanate is performed in the second step. We are carrying out. For this reason, the structural unit based on the polymer produced in the first step is incorporated into the obtained polyamideimide as it is.

  If it becomes like this, in the obtained polyamideimide, each structural unit which comprises a molecule | numerator will come to have a bigger continuity compared with the past. As a result, the action of the aromatic rings described above, and hence the stacking effect based thereon, is more likely to occur, and thereby the linear thermal expansion coefficient of polyamideimide is further reduced. However, the action is not limited to these. In addition, continuity shall mean the degree of repetition of the predetermined structural unit which comprises the polyamideimide.

  In the first step of the above method, it is particularly preferable to use an aromatic dicarboxylic acid as the first dicarboxylic acid. In this case, since the continuity of the structural unit containing the aromatic ring becomes extremely large, the above-described stacking effect is more likely to occur, and the linear thermal expansion coefficient of the polyamideimide tends to be significantly reduced.

  The first and second steps are preferably performed in the presence of a basic catalyst. By doing so, each reaction is likely to occur, and a polyamideimide having a larger molecular weight can be produced.

  Furthermore, aromatic diisocyanate is preferable as the first and second diisocyanate compounds used in the above production method. By using the aromatic diisocyanate, the above-described stacking effect is more strongly generated, and the linear thermal expansion coefficient of the polyamideimide can be further reduced.

［式中、Ｒ^２１は、水素原子、水酸基、メトキシ基、メチル基又はハロゲン化メチル基、Ｒ^２２は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基、単結合、又は、下記一般式（３ａ）若しくは（３ｂ）で表される２価の基、Ｒ^２３は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基又はカルボニル基を示す。なお、複数存在するＲ^２１は、それぞれ同一でも異なっていてもよい。

但し、Ｒ^３１は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基又は単結合を示す。］ As the aromatic dicarboxylic acid, a dicarboxylic acid obtained by reacting a diamine having an aromatic ring structure in the main chain with trimellitic anhydride, a dicarboxylic acid represented by the following general formula (2a), Of the dicarboxylic acids represented by 2b), the dicarboxylic acids represented by the following general formula (2c), and the dicarboxylic acids represented by the following general formula (2d), at least one dicarboxylic acid is preferred.

[Wherein R ²¹ represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group, R ²² represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a divalent group having 1 to 3 carbon atoms. A halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, a single bond, or a divalent group represented by the following general formula (3a) or (3b), R ²³ has 1 to 3 carbon atoms A divalent aliphatic hydrocarbon group, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group or a carbonyl group. A plurality of R ²¹ may be the same or different.

However, R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group or a single bond . ]

  By using these components as the aromatic dicarboxylic acid, the stacking effect in the polyamideimide molecule can be increased, and the linear thermal expansion coefficient can be further reduced.

［式中、Ｒ^４１は水素原子、水酸基、メトキシ基、メチル基又はハロゲン化メチル基、Ｒ^４２は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基、単結合又は下記一般式（５ａ）若しくは（５ｂ）で表される２価の基、Ｒ^４３は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基又はカルボニル基を示す。なお、複数存在するＲ^４１は、それぞれ同一でも異なっていてもよい。

但し、Ｒ^５１は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基又は単結合を示す。] Of the above-mentioned aromatic dicarboxylic acids, dicarboxylic acids obtained by reacting a diamine having an aromatic ring structure in the main chain with trimellitic anhydride are particularly preferred. When this is used, the content of imide groups in the molecule tends to increase and the heat resistance of the polyamideimide tends to further improve. In this case, the diamine having an aromatic ring structure in the main chain is preferably a diamine represented by the following general formula (4a) or a diamine represented by the following general formula (4b).

[Wherein, R ⁴¹ is a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group, R ⁴² is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a divalent aliphatic group having 1 to 3 carbon atoms. A halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, a single bond, or a divalent group represented by the following general formula (5a) or (5b), R ⁴³ is a divalent group having 1 to 3 carbon atoms An aliphatic hydrocarbon group, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group or a carbonyl group. A plurality of R ⁴¹ may be the same or different.

However, ^R51 shows a C1-C3 bivalent aliphatic hydrocarbon group, a C1-C3 bivalent halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond. . ]

  Moreover, as dicarboxylic acid represented by the said General formula (1), what is obtained by making diamine which does not have an aromatic ring structure in a principal chain, and trimellitic anhydride react is preferable. In this case, as the diamine having no aromatic ring, organopolysiloxane diamine and / or aliphatic diamine is preferable. By introducing structural units derived from these compounds into polyamideimide, the flexibility and film formability of the resulting polyamideimide are improved.

  The present invention also provides a polyamideimide obtained by the production method of the present invention. Since this polyamideimide is obtained by the production method of the present invention, the coefficient of linear thermal expansion is low, and even when a laminated body is formed by laminating metal foil or the like, it is difficult to cause warping of the laminated body. Therefore, it is extremely effective as a substrate material such as a printed wiring board.

  Furthermore, this invention provides the polyamideimide varnish containing the solvent and the polyamideimide obtained by the manufacturing method of the said this invention melt | dissolved or disperse | distributed to this solvent.

  According to the method for producing a polyamideimide of the present invention, a polyamideimide having not only excellent properties such as film formability, electrical properties, strength, heat resistance, and adhesion to a substrate but also a very low linear thermal expansion coefficient can be obtained. Be able to. Polyamideimide having such characteristics can greatly reduce the occurrence of warpage of the laminate when applied as a layer forming material of the laminate.

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

  In the method for producing a polyamideimide of the present invention, first, in the first step, the aromatic carboxylic acid and the dicarboxylic acid represented by the general formula (1) are any kind of group. A polymer is obtained by causing a polymerization reaction between 1 dicarboxylic acid and the first diisocyanate compound. Next, in the second step, the polymer obtained in the first step is reacted with the second dicarboxylic acid and the second diisocyanate compound, which are different from the first dicarboxylic acid in the group described above. To obtain a polyamideimide. Hereinafter, after explaining each component used in the manufacturing method of a polyamideimide, reaction implemented at each step is demonstrated.

(Aromatic dicarboxylic acid)
Examples of the aromatic dicarboxylic acid include dicarboxylic acids having one or two or more aromatic rings, and two carboxyl groups bonded to the aromatic rings. When the dicarboxylic acid has two or more aromatic rings, these aromatic rings may be directly bonded to form a condensed ring or may be bonded via a divalent group.

  As such an aromatic dicarboxylic acid, a dicarboxylic acid obtained by reacting a diamine having an aromatic ring structure in the main chain with trimellitic anhydride (hereinafter referred to as “aromatic diimide dicarboxylic acid”), the above general formula ( The dicarboxylic acid represented by 2a), the dicarboxylic acid represented by the above general formula (2b), the dicarboxylic acid represented by the above general formula (2c), or the dicarboxylic acid represented by the above general formula (2d) Can be mentioned.

  Among the dicarboxylic acids described above, first, aromatic diimide dicarboxylic acid will be described. The diamine having an aromatic ring structure in the main chain, which is a raw material for aromatic diimide dicarboxylic acid, has one or two or more aromatic rings, and two diamine groups bonded to the same or different aromatic rings. Is preferred. When such a diamine has two or more aromatic rings, these aromatic rings may be directly bonded to form a condensed ring, or may be bonded via a divalent group. .

As such a diamine having an aromatic ring structure in the main chain, a diamine represented by the above general formula (4a) or (4b) is preferable. In the diamine represented by the general formula (4a), R ⁴² in the formula is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms. As the diamine which is a sulfonyl group, an ether group, a carbonyl group or a single bond, for example, 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, 3, 3′-dihydroxybiphenyl-4,4′-diamine, 4,4′-diaminobiphenyl sulfone, 4,4′-diaminobiphenyl ether, 3,3′-diaminobiphenyl ether, 4,4′-diaminobiphenylmethane, 4 , 4'- Aminobiphenyl ketone, 3,3'-biphenyl ketone.

Moreover, in the diamine represented by the general formula (4a), R ⁴² in the formula is a divalent group represented by the general formula (5a) or (5b). [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) 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-amino Phenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (a Nofenokishi) benzene and the like.

  Furthermore, examples of the diamine represented by the general formula (4b) include 2,7-fluorenediamine, 2,2'-sulfonylbiphenyl-4,4'-diamine, and the like.

  The aromatic diimide dicarboxylic acid is obtained by reacting a diamine represented by the above general formula (4a) or (4b) with trimellitic anhydride as follows. That is, first, a diamine having an aromatic ring and trimellitic anhydride are dissolved or dispersed in a solvent, and stirred and reacted at 50 to 90 ° C. In this reaction, 2.0 to 2.2 equivalents of trimellitic anhydride is used with respect to 1 equivalent of diamine having an aromatic ring, each of the two amino groups of the diamine and trimellitic anhydride. It is preferable to cause a reaction with the anhydrous carboxyl group possessed by.

  Examples of the solvent used at this time include aprotic polar solvents such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone (NMP), 4-butyrolactone, and sulfolane. Among them, NMP is preferable.

  Next, an aromatic hydrocarbon that can be azeotroped with water is added to the solution after the reaction, the mixture is further stirred at 120 to 180 ° C., and the amide group generated by the reaction between the amino group and the anhydrous carboxyl group described above An aromatic diimide dicarboxylic acid is obtained by causing a dehydration ring-closing reaction with a carboxyl group. Examples of the aromatic hydrocarbon that can be azeotroped with water include toluene, benzene, xylene, ethylbenzene, and the like, and toluene is preferable. By adding 10 to 50% by weight of these aromatic hydrocarbons with respect to the solvent, the dehydration ring closure reaction can be efficiently generated. 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.

Examples of the aromatic diimide dicarboxylic acid thus obtained include compounds represented by the following general formula (6). In addition, R ⁶¹ in the following general formula (6) is a divalent group obtained by removing an amino group from a diamine having an aromatic ring, and from the diamine represented by the above general formula (4a) or (4b) to amino A divalent group excluding the group is preferred.

  As the aromatic dicarboxylic acid, in addition to the aromatic diimide dicarboxylic acid thus obtained, aromatic dicarboxylic acids represented by the above general formulas (2a) to (2d) can be used. Specifically, for example, examples of the dicarboxylic acid represented by the general formula (2a) include terephthalic acid and isophthalic acid, and examples of the dicarboxylic acid represented by the general formula (2b) include 1,4. -A naphthalene dicarboxylic acid, 2, 6- naphthalene dicarboxylic acid etc. can be illustrated.

  Examples of the dicarboxylic acid represented by the general formula (2c) include (4,4′-dicarboxy) diphenyl ether, (4,4′-dicarboxy) diphenylsulfone, and (4,4′-dicarboxy) diphenyl. Ketone, (3,3′-dicarboxy) diphenylketone, and the like. Examples of the dicarboxylic acid represented by the general formula (2d) include 2,7-fluorenedicarboxylic acid, 2,2′-sulfonylbiphenyl-4. 4,4'-dicarboxylic acid. In the method for producing polyamideimide of the present invention, the above-mentioned aromatic dicarboxylic acids may be used alone or in combination.

(Dicarboxylic acid represented by general formula (1))
As shown in the formula, the dicarboxylic acid represented by the general formula (1) is a divalent phthalimide molecule in which two carboxyl groups are bonded to an aromatic ring, and the main chain does not have an aromatic ring structure. A dicarboxylic acid formed by bonding nitrogen atoms of an imide group through a group (this dicarboxylic acid is hereinafter referred to as “non-aromatic dicarboxylic acid”). Such a non-aromatic dicarboxylic acid can be obtained by reacting a diamine having no aromatic ring structure in the main chain with trimellitic anhydride. Examples of the diamine used in this case include organopolysiloxane diamine and aliphatic diamine. By using these diamines, the flexibility of the resulting polyamideimide can be improved. The non-aromatic dicarboxylic acid thus obtained is obtained by removing an amino group from an organopolysiloxane diamine or an aliphatic diamine as a divalent organic group represented by R ¹ in the above general formula (1), if preferred. It has a divalent group.

Examples of the organopolysiloxane diamine for forming the non-aromatic dicarboxylic acid include compounds represented by the following general formula (7).

In the formula, R ⁷¹ includes a divalent organic group, R ⁷² includes an alkyl group, a phenyl group, or a substituted phenyl group, and n and m are preferably integers of 1 to 15. A plurality of R ⁷¹ and R ⁷² may be the same or different. More specifically, as R ⁷¹ , an alkylene group having 1 to 6 carbon atoms, a phenylene group which may be substituted with an alkyl group having 1 to 3 carbon atoms or a halogen atom, an alkyl group having 1 to 3 carbon atoms, Or the naphthalene group which may be substituted by the halogen atom is preferable. As the R ^72, an alkyl group having 1 to 3 carbon atoms, a phenyl group which may be substituted with an alkyl group or a halogen atom having 1 to 3 carbon atoms preferably.

As such an organopolysiloxane diamine, compounds represented by the following chemical formulas (8) to (11) are suitable. In addition, x and y in a formula show the integer of 1-50 each independently.

  Specifically, as the organopolysiloxane diamine represented by the above general formula (8), amino modified silicone oils X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X -22-161B (amine equivalent 1500) (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) it can. Examples of the organopolysiloxane diamine represented by the general formula (11) include X-22-9409 (amine equivalent 680) and X-22-1660B (amine equivalent 2260, manufactured by Shin-Etsu Chemical Co., Ltd.). .

On the other hand, examples of the aliphatic diamine for forming the non-aromatic dicarboxylic acid include compounds represented by the following general formula (12).

In the formula, examples of R ¹²¹ include a hydrogen atom, an alkyl group, a phenyl group, and a substituted phenyl group, and a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a halogen atom are substituted. A phenyl group or the like which may be present as a group is preferred. Examples of R ¹²² include a methylene group, a sulfonyl group, an ether group, a carbonyl group, and a single bond, and an ether group is preferable. Furthermore, Z is preferably an integer of 1 to 50. A plurality of R ¹²¹ may be the same or different. Examples of such aliphatic diamines include Jeffamine D-400 (amine equivalent 400) and Jeffamine D-2000 (amine equivalent 2000).

  The reaction between the diamine having no aromatic ring structure in the main chain and trimellitic anhydride in the formation of the non-aromatic dicarboxylic acid is the above except that a diamine having no aromatic ring structure is used instead of the aromatic diamine. It can carry out on the same conditions as the synthesis method of the aromatic diimide dicarboxylic acid made. In addition, as diamine which does not have an aromatic ring structure, it is not necessary to use a single kind of diamine, for example, the above-mentioned organopolysiloxane diamine and aliphatic diamine can also be used in combination. Thus, when both are used together, there exists a tendency for the flexibility of the polyamideimide obtained to improve further.

Thus, the non-aromatic dicarboxylic acid mainly represented by the general formula (1) is obtained by the reaction of diamine having no aromatic ring structure in the main chain and trimellitic anhydride. In the non-aromatic dicarboxylic acid thus obtained, when preferred, R ¹ in the general formula (1) is a divalent group obtained by removing the amino group from the diamine represented by the general formula (7). Alternatively, a divalent group is obtained by removing the amino group from the diamine represented by the general formula (12).

(First and second diisocyanate compounds)
Examples of the first and second diisocyanate compounds include compounds represented by the following general formula (13). In addition, in the manufacturing method of the polyamideimide of this invention, as a 1st diisocyanate compound and a 2nd diisocyanate compound, the same compound may respectively be used and a different compound may be used. These may be appropriately selected according to the desired physical properties of the polyamideimide.

In the formula, R ¹³¹ is a divalent organic group having at least one aromatic ring or a divalent aliphatic hydrocarbon group, and represented by —C ₆ H ₄ —CH ₂ —C ₆ H ₄ —. It is preferably at least one group among a group, a tolylene group, a naphthylene group, a hexamethylene group, a 2,2,4-trimethylhexamethylene group and an isophorone group.

  Examples of the diisocyanate represented by the general formula (13) include aliphatic diisocyanates and aromatic diisocyanates. Of these, aromatic diisocyanates are preferable, and it is more preferable to use both in combination.

  Aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, and the like. As an example, it is particularly preferable to use MDI. By using MDI as the aromatic diisocyanate, the flexibility of the polyamideimide obtained can be improved, the crystallinity can be reduced, and the film-formability of the polyamideimide can be improved.

  Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  When the aromatic diisocyanate and the aliphatic diisocyanate are used in combination, it is preferable to add the aliphatic diisocyanate to about 5 to 10 mol% with respect to the aromatic diisocyanate. By using both in combination, the heat resistance of the resulting polyamideimide can be further improved.

(Production method of polyamideimide)
As described above, in the method for producing polyamideimide of the present invention, the first step and the second step are sequentially performed. Hereinafter, reactions occurring in each step will be described.

  First, in the first step, polymerization of one of the aromatic dicarboxylic acid and the non-aromatic dicarboxylic acid (first dicarboxylic acid) with a diisocyanate compound (first diisocyanate compound). Cause a reaction.

  The reaction between the first dicarboxylic acid and the first diisocyanate compound is preferably 1 to 1.5 equivalents, more preferably 1-1.1, of the first diisocyanate compound with respect to 1 equivalent of the first dicarboxylic acid. Add 3 equivalents to react. When the molar ratio during the reaction is set in this way, it is possible to produce a polyamideimide having a higher molecular weight and excellent film forming property.

  At this time, the reaction between the first dicarboxylic acid and the first diisocyanate compound is preferably carried out in an aprotic polar solvent. As the aprotic polar solvent, the same solvents as those used for the synthesis of the aromatic diimide dicarboxylic acid described above can be used. At this time, the aprotic polar solvent is used in such an amount that the solid content weight is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, based on the total weight of the solution. When the solid content in the solution is less than 10% by weight, the amount of the solvent used is excessive and tends to be disadvantageous in terms of cost. On the other hand, when it exceeds 70% by weight, the amount of dicarboxylic acid or the like dissolved becomes insufficient, and it tends to be difficult to cause a sufficient reaction.

  The reaction temperature of such a reaction is preferably in the range of 130 to 200 ° C. If the reaction temperature is less than 130 ° C., the reaction does not occur sufficiently and the amount of polymer produced tends to decrease. On the other hand, when it exceeds 200 degreeC, side reactions, such as reaction of diisocyanate, may advance so that it cannot be disregarded.

  In order to enable the reaction at a lower temperature, the reaction of the first dicarboxylic acid and the first diisocyanate compound is preferably carried out in the presence of a basic catalyst. In this case, the reaction temperature is preferably 70 to 180 ° C, more preferably 120 to 150 ° C. In this way, the progress of the side reaction as described above is suppressed, and a polymer having a larger molecular weight is generated.

  The basic catalyst used at this time is preferably a basic catalyst suitable for promoting the polymerization reaction and easily removed after the reaction. For example, a tertiary amine or the like can be preferably used. Examples of such tertiary amines include trimethylamine, triethylamine, tripropylamine, tri (2-ethylhexyl) amine, trioctylamine, and the like, among which triethylamine is preferable.

The reaction of the first dicarboxylic acid and the first diisocyanate compound in the first step is a polyaddition reaction mainly occurring between the carboxyl group of the dicarboxylic acid and the isocyanate group of the diisocyanate compound. By this reaction, a polymer having a repeating unit represented mainly by the following general formula (14) is produced.

In the formula, R ¹⁴¹ represents a divalent group formed by removing a carboxyl group from a first dicarboxylic acid, that is, a divalent group formed by removing a carboxyl group from an aromatic dicarboxylic acid or a non-aromatic dicarboxylic acid. Show. R ¹⁴² represents a divalent group formed by removing an isocyanate group from the first diisocyanate compound. In a preferred case, the compound represented by the general formula (14) is a divalent group obtained by removing a carboxyl group from the dicarboxylic acid represented by the general formula (6) as R ¹⁴¹ , or the above It has a divalent group formed by removing a carboxyl group from the dicarboxylic acid represented by the general formula (1), and R ¹⁴² is represented by —R ¹³¹ — in the general formula (13). It has a divalent group.

  The weight average molecular weight of the polymer thus obtained is preferably 10,000 to 300,000, more preferably 20,000 to 200,000, and further preferably 30,000 to 180,000. When the weight average molecular weight of the polymer is within such a range, in the obtained polyamideimide, the continuity of structural units derived from this polymer is sufficiently increased, and the linear thermal expansion coefficient of the polyamideimide is further reduced. . Here, the weight average molecular weight indicates a value obtained by measurement by gel permeation chromatography (GPC) and conversion using a calibration curve prepared using standard polystyrene.

  Next, in the second step, the polymer obtained in the first step and the dicarboxylic acid of the type not used in the first step among the aromatic dicarboxylic acid and non-aromatic dicarboxylic acid (second dicarboxylic acid). Acid) and a second diisocyanate compound. As described above, the second diisocyanate compound may be the same as or different from the first diisocyanate compound, but from the viewpoint of making the continuity of each structural unit in the polyamideimide uniform, the same compound is used for both. It is preferable to use it.

  When performing the said reaction, it is preferable to add 2nd dicarboxylic acid and 2nd diisocyanate compound so that a diisocyanate compound may be 1-1.5 equivalent with respect to 1 equivalent of dicarboxylic acid, It is more preferable to add so that it may become 3 equivalent.

  Such a reaction is preferably caused to occur in an aprotic polar solvent in the presence of a basic catalyst. If it carries out like this, reaction under a low temperature condition will be attained, and a side reaction will be suppressed and a high molecular weight polyamideimide will be obtained. As the aprotic polar solvent and the basic catalyst, the same ones used in the first step can be used. The reaction temperature at this time is preferably set to the same temperature as that in the first step described above.

  In the reaction of the second step, after the first step is performed, the solution after the reaction (solution containing the polymer) is cooled, and the second dicarboxylic acid and the second diisocyanate are added to the solution, and the reaction is resumed. It can be generated by warming. Further, for example, the reaction may be caused by dropping a mixture containing the second dicarboxylic acid and the second diisocyanate into the solution after the reaction obtained in the first step. When the reaction of the second step is caused by dropping like the latter, the second step can be carried out continuously without lowering the temperature of the solution after the completion of the first step, and the polyamideimide can be more efficiently performed. Can be manufactured. In this case, more specifically, a mixture containing the second dicarboxylic acid and the second diisocyanate is dissolved or dispersed in the aprotic polar solvent in the solution after the reaction in the first step, and a basic catalyst is further added. It is preferable to cause the reaction of the second step by dropping the added solution.

In the second step, the polymerization mainly takes place between the carboxyl group at the terminal of the polymer obtained in the first step and the carboxyl group of the second dicarboxylic acid and the isocyanate group of the diisocyanate compound. An addition reaction occurs. As a result, a polyamideimide having a repeating unit represented by the following general formula (15) is mainly produced.

In the formula, R ¹⁵¹ is a divalent group obtained by removing the carboxyl group from the first dicarboxylic acid, and R ¹⁵² is a divalent group obtained by removing the isocyanate group from the diisocyanate compound used in the first step. Show. R ¹⁵³ represents a divalent group obtained by removing a carboxy group from the second dicarboxylic acid, and R ¹⁵⁴ represents a divalent group obtained by removing an isocyanate group from the diisocyanate compound used in the second step. . Furthermore, n is preferably an integer of 2 to 400, and m is preferably an integer of 1 to 400. The weight average molecular weight of the polyamide thus obtained is preferably 20,000 to 400,000, more preferably 30,000 to 300,000, still more preferably 40,000 to 200,000.

In the production of the polyamideimide of the present invention, it is particularly preferred to use an aromatic diimide dicarboxylic acid as the first dicarboxylic acid and to use the same diisocyanate compound in the first and second steps. According to this production method, a polyamideimide represented by the following general formula (16) can be obtained. In the formula, R ¹ , R ⁶¹ , R ¹³¹ , n and m are as defined above. The polyamideimide obtained in this way has excellent properties such as electrical properties, strength and heat resistance in addition to the properties of low linear thermal expansion coefficient.

  The polyamideimide thus obtained can be used as a varnish dissolved or dispersed in a predetermined solvent. By making the polyamide imide into a varnish shape, it becomes possible to easily apply on the substrate, and it becomes possible to easily form the polyamide imide layer when manufacturing the laminate. Examples of the solvent used for the varnish include dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 4-butyrolactone, sulfolane and the like.

(Thermosetting resin composition)
When the polyamideimide obtained by the above-described production method is combined with a compound having a functional group that reacts with the amide group of the polyamideimide by applying heat or the like (hereinafter referred to as “amide-reactive compound”). Furthermore, it comes to have characteristics as a thermosetting resin composition that can be cured by heat. Such a thermosetting resin composition is useful as a layer-forming material for metal-clad laminates used in the production of printed wiring boards and the like, as will be described later.

  Examples of the amide-reactive compound combined with the polyamideimide include a polyfunctional epoxy compound and an oxetane compound, and it is preferable to use a polyfunctional epoxy compound.

  Examples of the polyfunctional epoxy compound include bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, and the like, one or more of these Can be used.

  When preparing a thermosetting resin composition, it is preferable that the compounding quantity of an amide reactive compound is 10-40 weight part with respect to 100 weight part of polyamideimides, and it is more preferable that it is 15-25 weight part. preferable. If the amount of the amide-reactive compound is less than 10 parts by weight, the thermosetting property of the resulting thermosetting resin composition tends to decrease, and if it exceeds 40 parts by weight, the cured thermosetting resin composition There is a tendency that the bridging structure of the product becomes dense and the brittleness of the resin decreases.

  In addition, when the thermosetting resin composition further contains a curing accelerator, a curing reaction occurs more easily, and the thermosetting resin composition becomes more convenient. Here, a hardening accelerator is a component which accelerates | stimulates hardening of the mixture of a polyamideimide and an amide reactive compound, and it is preferable that it is especially a component which accelerates | stimulates hardening of an amide reactive compound. Examples of the curing accelerator include amines and imidazoles, and one or more of these can be used.

  Examples of amines include dicyandiamide, diaminodiphenylethane, and guanylurea. Examples of imidazoles include alkyl-substituted imidazoles such as 2-ethyl-4-methylimidazole and benzimidazoles.

  When the curing accelerator is contained, the blending amount of the curing accelerator can be determined according to the type of the amide reactive compound. For example, a polyfunctional epoxy compound is used as the amide reactive compound, and an amine is used as the curing accelerator. When using an amine, it is preferable to add an amount of the amine so that the epoxy equivalent in the polyfunctional epoxy compound and the equivalent of the active hydrogen of the amino group of the amine are almost equal. When a polyfunctional epoxy compound is used as the amide-reactive compound and an imidazole is used as the curing accelerator, 0.1 to 2.0 parts by weight of the imidazole is preferably added to 100 parts by weight of the polyfunctional epoxy compound. . When the addition amount of the curing accelerator is insufficient, the uncured amide reactive compound remains in the thermosetting resin composition, and the heat resistance after curing of the thermosetting resin composition tends to decrease. If the amount is too large, the curing accelerator remains in the thermosetting resin composition, and the insulation property of the thermosetting resin composition after curing tends to decrease.

  When the thermosetting resin composition is cured, the curing reaction is preferably performed at about 100 to 250 ° C. When the curing reaction is performed at less than 100 ° C., the curing time tends to be long, and when it exceeds 250 ° C., the reaction between the amide reactive compounds is observed, and the thermosetting resin composition is insufficiently cured. There is a tendency.

  Further, in the thermosetting resin composition, if necessary, in addition to the above-described components, a rubber elastomer, a phosphorus compound as a flame retardant, an inorganic filler, a coupling agent, a pigment, a leveling agent, an antifoaming agent, An ion trapping agent or the like can also be blended.

  As described above, this thermosetting resin composition can be used as a layer forming material in a metal-clad laminate. Specifically, it can be applied as an adhesive layer for bonding a substrate and a conductive layer made of metal or the like. As such a metal-clad laminate, for example, a substrate material made of polyimide film or the like, an adhesive layer made of a cured product of the above-mentioned thermosetting resin composition formed on the substrate material, and formed on the adhesive layer What has a structure provided with the made metal foil is mentioned as a suitable example. The metal-clad laminate having such a configuration can be preferably used as a substrate material for a flexible printed wiring board.

  Examples of a method for forming an adhesive layer when manufacturing this metal-clad laminate include a method of directly applying a thermosetting resin composition on a substrate material, a method of using an adhesive film described later, and the like. .

  An adhesive film consists of a support film and the thermosetting resin composition mentioned above, and is provided with the contact bonding layer provided on the support film. A protective film for protecting the adhesive layer may be further provided on the adhesive layer. Formation of the adhesive layer on the substrate material using the adhesive film can be performed by laminating the adhesive film on the substrate material so that the adhesive layer is in contact, and then heating and / or drying as necessary. it can. In addition, peeling of the support body from an adhesive film may be performed before lamination | stacking, and may be performed after lamination | stacking.

  The adhesive film can be formed, for example, by applying a thermosetting resin composition dissolved or dispersed in an organic solvent on a support film and then drying the organic solvent by heating or hot air blowing. Examples of the support film include polyethylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, tetrafluoroethylene film, release paper, metal foil such as copper foil and aluminum foil, and the thickness is 10 to 150 μm. preferable. The support film may be subjected to mud treatment, corona treatment, mold release treatment, and the like.

  Examples of the organic solvent capable of dissolving the thermosetting resin composition include ketones such as acetone, methyl ethyl ketone, and cyclohequinone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Two or more kinds can be used.

  The thickness of the adhesive layer in the adhesive film is preferably 5 to 50 μm, and more preferably 10 to 40 μm. The produced adhesive film can be stored in the form of a sheet obtained by cutting the adhesive film into a certain length, or the sheet-like adhesive film can be wound up and stored in a roll form. From the viewpoints of storage stability, productivity, and workability, it is preferable to further laminate a protective film on the adhesive layer in the adhesive film, and wind and store it in a roll shape. Examples of the protective film include polyethylene, polyvinyl chloride, polyethylene terephthalate, and release paper. The thickness is preferably 10 to 100 μm, and may be subjected to mat treatment, embossing, and release treatment.

  Then, a metal-clad laminate can be obtained by laminating a metal foil usually used for a metal-clad laminate such as copper foil and aluminum foil on the adhesive layer laminated on the substrate material as described above. it can. Since the metal-clad laminate thus obtained uses the thermosetting resin composition containing the polyamideimide of the present invention as an adhesive layer, it has excellent heat resistance and further has a characteristic that warpage is extremely small. Become.

(Synthesis Example 1: Synthesis of aromatic dicarboxylic acid)
In a separable flask equipped with a Dean-Stark reflux condenser, thermometer and stirrer, aromatic diamine 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 140 mmol, trimellitic anhydride (TMA) 294 mmol and aprotic polar solvent N-methyl 2-pyrrolidone (NMP) 160 g were added and stirred at 80 ° C. for 30 minutes. After completion of stirring, 60 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 was confirmed that the theoretical amount of water accumulated in the moisture determination receiver and no water was distilled, water and toluene in the moisture determination receiver were removed. Thereafter, the temperature of the solution was raised to 190 ° C. to remove toluene in the solution, thereby obtaining an aromatic dicarboxylic acid.

(Synthesis Example 2: Synthesis of non-aromatic dicarboxylic acid)
In a separable flask equipped with a Dean-Stark reflux condenser, thermometer and stirrer, 60 mmol of reactive silicone oil KF-8010 (amine equivalent 430, manufactured by Shin-Etsu Chemical Co., Ltd.) which is a diamine having no aromatic ring, 126 mmol of TMA , 109 g of NMP was added and stirred at 80 ° C. for 30 minutes. After completion of the stirring, 50 mL of toluene which is an aromatic hydrocarbon azeotropic with water was added, and the temperature was raised to 160 ° C. and refluxed for 2 hours. When it was confirmed that the theoretical amount of water accumulated in the moisture determination receiver and no water was distilled, water and toluene in the moisture determination receiver were removed. Thereafter, the temperature of the solution was raised to 190 ° C. to remove toluene in the solution, thereby obtaining a non-aromatic dicarboxylic acid.

[Synthesis of Polyamideimide]
Example 1
In a 1 L separable flask equipped with a dropping funnel, a thermometer and a stirrer, 140 mmol of the aromatic dicarboxylic acid obtained in Synthesis Example 1, 168 mmol of 4,4′-diphenylmethane diisocyanate (MDI), which is an aromatic diisocyanate, 196 g of NMP and 21 mmol of triethylamine as a catalyst were added, and polyaddition reaction was performed at 130 ° C. for 1.5 hours. Next, 60 mmol of the non-aromatic dicarboxylic acid obtained in Synthesis Example 2, 72 mmol of MDI, and 9 mmol of triethylamine were put into the dropping funnel, and this mixed solution was dropped into the solution in the flask over 20 minutes. After completion of the dropping, the obtained solution was heated at 130 ° C. for 2 hours to obtain an NMP solution of polyamideimide.

( Reference Example 1 )
A 1 L separable flask equipped with a dropping funnel, a thermometer and a stirrer was charged with 60 mmol of the non-aromatic dicarboxylic acid obtained in Synthesis Example 2, 72 mmol of MDI, 196 g of NMP, and 9 mmol of triethylamine at 130 ° C. The polyaddition reaction was carried out for 2.5 hours. Next, 140 mmol of the aromatic dicarboxylic acid obtained in Synthesis Example 1, 168 mmol of MDI, and 21 mmol of triethylamine were put into the dropping funnel, and this mixed solution was dropped into the solution in the flask over 1 hour. After completion of the dropping, the obtained solution was heated at 130 ° C. for 2 hours to obtain an NMP solution of polyamideimide.

(Reference Example 2 )
In a 1 L separable flask equipped with a dropping funnel, a thermometer and a stirrer, 95 g of NMP was placed and heated to 130 ° C. Next, 140 mmol of the aromatic dicarboxylic acid obtained in Synthesis Example 1, 60 mmol of the non-aromatic dicarboxylic acid obtained in Synthesis Example 2, 240 mmol of MDI, 14 g of NMP, and 30 mmol of triethylamine were placed in the dropping funnel. The mixture was added dropwise to the solution in the flask at 130 ° C. over 4.5 hours. After completion of the dropping, the obtained solution was heated at 130 ° C. for 2 hours to obtain an NMP solution of polyamideimide.

(Comparative Example 1)
In a 1 L separable flask equipped with a thermometer and a stirrer, 140 mmol of the aromatic dicarboxylic acid obtained in Synthesis Example 1, 60 mmol of the non-aromatic dicarboxylic acid obtained in Synthesis Example 2, 240 mmol of MDI, NMP 196 g and 30 mmol of triethylamine were added, and polyaddition reaction was performed at 130 ° C. for 4 hours to obtain an NMP solution of polyamideimide.

[Measurement of physical properties of polyamideimide]
Example 1, using an NMP solution of the obtained polyamide-imide in ginseng Reference Example 21 to and Comparative Example 1, the weight average molecular weight of the polyamide-imide by the following method, glass transition temperature (Tg), coefficient of linear thermal expansion In addition, the measurement of the elastic modulus and the continuity of the structural unit containing an aromatic ring in polyamide-imide and the degree of dispersion of the continuity were performed. The obtained results are summarized in Table 1.

(Measurement of weight average molecular weight)
The weight average molecular weight of the polyamideimide was calculated by conversion based on a calibration curve using standard polystyrene by GPC.

(Measurement of Tg, linear thermal expansion coefficient and elastic modulus)
First, Example 1, a NMP solution of the polyamideimide obtained in ginseng Reference Example 21 to and Comparative Example 1 was uniformly applied to a polyethylene terephthalate (PET) film, dried for 15 minutes at 130 ° C., The PET film was peeled from the applied polyamideimide and further dried at 230 ° C. for 1 hour to prepare a polyamideimide film. Using the obtained polyamideimide film, the glass transition temperature (Tg), the linear thermal expansion coefficient, and the elastic modulus were measured with a wide area viscoelasticity measuring device (DVE) or a thermomechanical analyzer (TMA). Tg is the temperature at which tan δ is maximized as measured by DVE, the linear thermal expansion coefficient is the value in the temperature range of 100 to 200 ° C. by TMA, and the elastic modulus is the value shown by DVE at 50 ° C.

(Continuity of structural units containing aromatic rings and dispersity of continuity)
Example 1, a polyamide-imide obtained in ginseng Reference Example 21 to and Comparative Example 1 were chemically cleaved at sites that do not contain aromatic rings, nuclear magnetic resonance residues containing an aromatic ring after the cutting (NMR ) The spectrum was measured, and the continuity of the component containing the aromatic ring was calculated from the peak intensity of the methyl group of BAPP in the obtained spectrum.

From Table 1, the polyamideimide obtained in Example 1 or Reference Example 1 has a greater continuity of components including a weight average molecular weight and an aromatic ring than the polyamideimide obtained in Reference Example 2 or Comparative Example 1, It was also found that the coefficient of linear thermal expansion was low. On the contrary, in Reference Example 2 where the continuity was small, the thermal expansion coefficient was large. In any polyamideimide, no significant difference was observed in Tg and elastic modulus, and it was found that all had high heat resistance.

[Evaluation of curable resin film]
(Preparation of curable resin composition and production of curable resin film)
In the polyamideimide obtained in Example 1, an epoxy resin (YDCN500-10, manufactured by Tohto Kasei Co., Ltd.), which is a thermosetting resin, is blended so as to be 10% of the total solid content weight, and further with a curing accelerator. A certain amount of 2-ethyl-4-methylimidazole was added at 1% by weight of the solid content of the epoxy resin, and diluted with dimethylacetamide to obtain an appropriate viscosity to obtain a varnish of a curable resin composition. The obtained varnish was applied onto a PET film and dried at 130 ° C. for 15 minutes to obtain a curable resin film having a thickness of 20 μm.

(Measurement of adhesive strength)
After peeling the PET film from the obtained curable resin film, the film sandwiched between two electrolytic copper foils was pressed at 230 ° C., 2 MPa, 1 hour with a vacuum press device to obtain a laminated film with double-sided copper foil. Obtained. A sample obtained by cutting the laminated film into a width of 10 mm was used as a sample for measuring adhesive strength, and a 90 ° peel test with a width of 1 cm was performed (90 ° peel strength, conforming to JIS C 6481). The adhesive strength (MPa) was measured. As the copper foil, those having a surface roughness of Rz = 5.5 and Rz = 2.0 were used. As a result, the adhesive strength is 1.3 kN / m for a copper foil with Rz = 5.5, and 0.8 kN / m for a copper foil with Rz = 2.0. It has been found that high adhesive strength is exhibited also to the foil.

Claims (6)

First and dicarboxylic acids Ru Rana or aromatic dicarboxylic acids, a first diisocyanate compound, a first step of obtaining a polymer by reacting,
A second step of obtaining a polyamideimide by reacting a second dicarboxylic acid composed of a dicarboxylic acid represented by the following general formula (1), a second diisocyanate compound, and the polymer;
A process for producing a polyamideimide, comprising:

[In the formula, R ^1, obtained by removing an amino group from the organopolysiloxane diamine, a divalent group having no aromatic ring in the main chain. ] Wherein the first and second steps, the production method of the polyamide-imide of claim 1, wherein the in the presence of a basic catalyst. The method for producing a polyamideimide according to claim 1 or 2 , wherein the first and second diisocyanate compounds are aromatic diisocyanates. The aromatic dicarboxylic acid is a dicarboxylic acid obtained by reacting a diamine having an aromatic ring structure in the main chain with trimellitic anhydride, a dicarboxylic acid represented by the following general formula (2a), or a general formula (2b) And at least one dicarboxylic acid selected from the group consisting of a dicarboxylic acid represented by the following general formula (2c) and a dicarboxylic acid represented by the following general formula (2d). The manufacturing method of the polyamideimide as described in any one of Claims 1-3 characterized by the above-mentioned.

[Wherein R ²¹ represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group, R ²² represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a divalent group having 1 to 3 carbon atoms. A halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, a single bond, or a divalent group represented by the following general formula (3a) or (3b), R ²³ has 1 to 3 carbon atoms A divalent aliphatic hydrocarbon group, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group or a carbonyl group. A plurality of R ²¹ may be the same or different.

However, R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group or a single bond . ] The aromatic dicarboxylic acid is obtained by reacting trimellitic anhydride with at least one diamine selected from the group consisting of a diamine represented by the following general formula (4a) and a diamine represented by the following general formula (4b). The method for producing a polyamideimide according to any one of claims 1 to 4 , wherein the polyamideimide is obtained.

[Wherein, R ⁴¹ is a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group, R ⁴² is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a divalent hydrocarbon group having 1 to 3 carbon atoms. A halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, a single bond, or a divalent group represented by the following general formula (5a) or (5b), R ⁴³ has 1 to 3 carbon atoms A divalent aliphatic hydrocarbon group, a C1-C3 divalent halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group or a carbonyl group is shown. A plurality of R ⁴¹ may be the same or different.

However, ^R51 shows a C1-C3 bivalent aliphatic hydrocarbon group, a C1-C3 bivalent halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond. . ] The dicarboxylic acid represented by the general formula (1) is any one of claims 1 to 5, characterized in that a dicarboxylic acid obtained by reacting an organopolysiloxane diamine with trimellitic anhydride The manufacturing method of the polyamideimide as described in any one of.