JP2007302887A - Polyamide-imide resin, method for producing the same and resin composition containing the polyamide-imide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide-imide resin giving a cured film having sufficient heat-resistance and sufficiently curable even at a low temperature. <P>SOLUTION: The polyamide-imide resin is produced by reacting a polyamide-imide used as a raw material with a glycidyl compound having glycidyl group and has at least one reactive organic group on a side chain or a chain terminal. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  As a method for producing a polyamide-imide resin, an acid chloride method and an isocyanate method are known. Specific examples of the acid chloride method include a method of reacting diamine and trimellitic acid chloride (see, for example, Patent Document 1). Specific examples of the isocyanate method include a method in which trimellitic anhydride and diisocyanate are reacted, a method in which aromatic tricarboxylic acid anhydride and diamine having an ether bond are reacted in an acid component excess condition, and then a diisocyanate is reacted ( For example, refer to Patent Document 2) and a method of reacting diamine and diisocyanate and then reacting trimellitic anhydride (for example, refer to Patent Document 3).

Polyamideimide resin is often used as a resin composition combined with other components in order to obtain excellent adhesion to a predetermined substrate or the like. For example, as a thermosetting resin composition containing a polyamideimide resin, a composition containing a polyamideimide resin and a glycidyl compound is known (for example, Patent Document 4).
Japanese Patent Laid-Open No. 11-49858 Japanese Patent No. 2897186 Japanese Patent Laid-Open No. 04-182466 Japanese Patent Laid-Open No. 11-217503

  The cured film of the polyamideimide resin and the resin composition containing the same as described above are often applied to, for example, electronic materials (such as an adhesive layer and a protective film). In such applications, polyamideimide resins and resin compositions are required to have excellent heat resistance. However, if solid impurities, metal impurities, ionic impurities, etc. are mixed in the cured film, it tends to cause deterioration of various characteristics in addition to heat resistance, which is disadvantageous for application to electronic materials. Tend to be.

  Here, the polyamideimide resin obtained by the method of Patent Document 1 may contain ionic impurities by-produced from the raw acid halide, and it is difficult to remove this. Moreover, in the resin composition containing a polyamideimide resin and a glycidyl compound as in Patent Document 4, since the reactivity of the polyamideimide resin and the glycidyl compound is low, an unreacted glycidyl compound remains after the curing reaction, which is an impurity. There was a case.

  In addition, the polyamide-imide resin and the resin composition often become a cured film by being cured after being applied on a predetermined substrate. In this case, in order to minimize the influence on the substrate and the like, It is desirable to be able to cure with However, the above-mentioned conventional polyamideimide resin and resin composition tend to be hard to cause a sufficient curing reaction when subjected to low temperature curing, so that the impurities described above are more likely to remain, and as a result, the properties of the cured film are reduced. Often it was insufficient.

  Therefore, the present invention has been made in view of such circumstances, and an object of the present invention is to provide a polyamideimide resin capable of obtaining a cured film having sufficient heat resistance and capable of sufficiently curing even at a low temperature. To do. Another object of the present invention is to provide a method for producing such a polyamideimide resin and a resin composition containing the polyamideimide resin.

  In order to achieve the above object, the polyamide-imide resin of the present invention is obtained by reacting a raw material polyamide-imide with a glycidyl compound having a glycidyl group, and has at least one reactive organic group at a side chain or terminal. And

  Since the polyamideimide resin of the present invention is the one in which the raw material polyamideimide and the glycidyl compound have already reacted, there is no need to cause these reactions during curing, and when these are contained separately A cured film with less impurities can be formed. Moreover, since the cured film thus obtained contains a polyamideimide resin and a glycidyl compound in addition to excellent heat resistance, the adhesiveness to the substrate is also excellent. Furthermore, this polyamideimide resin has a reactive organic group at the side chain or terminal, but this reactive organic group can contribute to the curing reaction during curing. Therefore, the polyamideimide resin of the present invention and the resin composition containing the same can be sufficiently cured even at a low temperature.

  The polyamideimide resin of the present invention is obtained by a reaction between a raw material polyamideimide having an amide group and an imide group in the molecular chain and an amino group and / or a carboxyl group at the terminal, and a glycidyl compound having a glycidyl group. In addition, a reactive organic group generated by a reaction between the raw material polyamideimide and a glycidyl compound may be included in a side chain or a terminal.

  Furthermore, the polyamideimide resin of the present invention comprises a raw material polyamideimide having an amide group and an imide group in the molecular chain and an amino group and / or a carboxyl group at the terminal, and a glycidyl compound having two or more glycidyl groups. It is obtained by reaction, and the raw material polyamideimide has a structure that is multiplied by bonding with the glycidyl compound, and has two or more reactive organic groups generated by the reaction between the raw material polyamideimide and the glycidyl compound. Also good.

  Since such a polyamide-imide resin is obtained by reacting a raw material polyamide-imide and a glycidyl compound in advance, impurities are hardly generated during curing, and a cured film having excellent heat resistance can be formed. In addition, since the raw material polyamideimide has been increased in quantity, this further increases the heat resistance. Furthermore, since it contains at least two reactive organic groups, it can be cured extremely well even under low temperature conditions.

  More specifically, the polyamideimide resin of the present invention is obtained by a reaction between an amino group and / or a carboxyl group in a raw material polyamideimide and a glycidyl group in a glycidyl compound, and a reactive organic group generated by this reaction. It is more preferable that it has. In such a reaction, no by-product is theoretically generated, so that the obtained polyamide-imide resin has a very low impurity content. As a result, this polyamide-imide resin and a resin composition containing the same can form a cured film having further excellent heat resistance.

  As a result of the above-described reaction, a hydroxyl group is generated as a reactive organic group, and the polyamideimide resin has this hydroxyl group as the reactive organic group at the side chain or terminal. Thus, the polyamide-imide resin having a hydroxyl group as a reactive organic group can cause a curing reaction particularly well and can be sufficiently cured even at a low temperature.

  Moreover, it is preferable that the polyamideimide resin of this invention has at least one of a hydroxyl group or a carboxyl group, and an amino group at the terminal. Thereby, the polyamide-imide resin is more likely to cause a curing reaction.

  Specifically, the raw material polyamideimide for obtaining the polyamideimide resin is preferably obtained by reacting diimide dicarboxylic acid obtained by reacting diamine and tricarboxylic acid monoanhydride with diisocyanate.

  In addition, the method for producing a polyamide-imide resin of the present invention includes a raw material polyamide-imide having an amide group and an imide group in a molecular chain and an amino group and / or a carboxyl group at a terminal, and a glycidyl group having two or more glycidyl groups. A compound is reacted with each other to obtain a polyamideimide resin having a structure in which a plurality of raw material polyamideimides are multimerized by bonding with a glycidyl compound. According to such a production method, the polyamideimide resin having a structure in which the raw material polyamideimide is multimerized via the glycidyl compound and having a reactive organic group generated by these reactions can be obtained favorably. .

  More specifically, in the production method of the present invention, it is preferable to react the amino group and / or carboxyl group in the raw material polyamideimide with the glycidyl group in the glycidyl compound. As a result, it is possible to obtain a polyamideimide resin with less impurities by suppressing the formation of by-products, and the obtained polyamideimide resin has a hydroxyl group generated by the above reaction as a reactive organic group. Become.

  The present invention also provides a resin composition comprising the polyamideimide resin of the present invention. For example, if a curable resin composition is contained in combination with a curable component, it can be formed by low-temperature curing, and a cured film having excellent heat resistance can be formed.

  According to the present invention, a cured film having sufficient heat resistance can be obtained, and a polyamide-imide resin that can be sufficiently cured even at a low temperature can be provided. Moreover, it becomes possible to provide the manufacturing method of such a polyamide imide resin, and the resin composition containing this polyamide imide resin and suitable for an electronic material use.

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

  First, a method for producing a polyamideimide resin according to a preferred embodiment will be described.

  The polyamideimide resin is obtained by a reaction between a raw material polyamideimide and a glycidyl compound. The raw material polyamideimide is a compound having an amide group and an imide group in the molecular chain and an amino group and / or a carboxyl group at the terminal. As such a raw material polyamideimide, those obtained by methods such as acid chloride method and isocyanate method can be applied without limitation. In the case of synthesizing a raw material polyamideimide used for preparation of a polyamideimide resin used for an electronic material, one obtained by an isocyanate method is more preferable.

  As the raw material polyamideimide obtained by the isocyanate method, for example, those obtained by the production method shown below are suitable. That is, the raw material polyamideimide is preferably obtained by reacting diimide dicarboxylic acid obtained by reacting diamine and tricarboxylic acid monoanhydride with diisocyanate.

  The diamine for obtaining diimidedicarboxylic acid is a compound having two amino groups in the molecule, and is composed of an aromatic diamine containing an aromatic ring between the two amino groups and an aliphatic group between the two amino groups. An aliphatic diamine, a siloxane diamine having a structural unit containing a siloxane bond between two amino groups, and the like can be applied.

  Aromatic diamines include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4-aminophenoxy) phenyl]. Sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-aminophenoxy) biphenyl, Bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-amino) Phenoxy) benzene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis (trifluoromethyl) biphenyl- , 4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonyl-biphenyl-4,4′-diamine, ( 4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, Examples include (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, and the like.

  Examples of the aliphatic diamine include (4,4′-diamino) dicyclohexylmethane, polypropylene oxide diamine (trade name Jeffamine), and the like. Furthermore, as siloxane diamine, polydimethylsiloxane diamine (silicone oil X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500), X-22 -9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200), KF-8010 (amine equivalent 415) (above, manufactured by Shin-Etsu Chemical Co., Ltd.)) and the like. As the diamine, those described above can be used alone or in combination of two or more.

  Examples of the tricarboxylic acid monoanhydride to be reacted with diamine include trimellitic acid and hydrogenated trimellitic acid. Diimide dicarboxylic acid is obtained by reacting the two amino groups in the diamine described above with an acid anhydride group in tricarboxylic acid monoanhydride, and then dehydrating the reaction portion to produce an imide group. The diimide dicarboxylic acid thus obtained has a carboxyl group derived from trimellitic acid at both ends.

  In such a reaction, the ratio of tricarboxylic acid monoanhydride to diamine (tricarboxylic acid / diamine; molar ratio) is preferably 1.0 to 1.3, and more preferably 1.05 to 1.2. When the ratio is smaller than this range, unreacted diamine tends to remain, and when the ratio is large, gelation tends to occur.

  The diisocyanate to be reacted with diimide dicarboxylic acid in the production of the raw material polyamideimide is a compound having two isocyanato groups in the molecule. Examples of such diisocyanates include methylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, and the like. As a diisocyanate, a single thing may be used and you may use in combination of multiple types.

  The reaction of diimide dicarboxylic acid and diisocyanate occurs between the carboxyl group in diimide dicarboxylic acid and the isocyanato group in diisocyanate. By repeating this reaction, a raw material polyamideimide having a plurality of structural units derived from diimide dicarboxylic acid and structural units derived from diisocyanate is obtained. In this reaction, in addition to diimide dicarboxylic acid and diisocyanate, diamine or dicarboxylic acid may be further used in combination. If it carries out like this, the structural unit derived from this diamine will be contained in raw material polyamideimide, and raw material polyamideimide can be adjusted to a desired characteristic.

  In this reaction, diisocyanate is preferably used in an amount of 0.5 to 1.3 equivalents based on the total amount of diimide dicarboxylic acid, or when diamine or dicarboxylic acid is used in combination. It is more preferable to use -1.2 equivalent. If the amount of diisocyanate is less than 0.5 equivalent, the raw material polyamideimide may not be obtained sufficiently. On the other hand, when it exceeds 1.3 equivalents, a side reaction due to unreacted diisocyanate is caused, and physical properties of the obtained raw material polyamideimide may be lowered.

  The glycidyl compound which is the other component for obtaining the polyamideimide resin is a compound having at least one glycidyl group in the molecule, and is preferably a compound having two or more glycidyl groups. Examples of such glycidyl compounds include epoxy resins having two or more glycidyl groups, and specific examples include bisphenol A type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, and bisphenol F type epoxy resins. , Phosphorus-containing epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, diglycidyl etherified product of bisphenol Examples include diglycidyl etherified products of naphthalene diol, diglycidyl etherified products of phenols, diglycidyl etherified products of alcohols, alkyl substituted products, halides or hydrogenated products thereof. Kill. These epoxy resins can be used alone or in combination of two or more.

The reaction between the raw material polyamideimide and the glycidyl compound occurs between the terminal amino group and / or carboxyl group in the raw material polyamideimide and the glycidyl group in the glycidyl compound, if appropriate. These reactions are represented by the following chemical formula (1) or (2), for example.

  As a result of the reaction as described above, the structural unit derived from the raw material polyamideimide and the structural unit derived from the glycidyl compound are bonded via a predetermined structure, and the polyamideimide having a hydroxyl group generated by the above reaction at this bonded portion A resin is obtained. Such a hydroxyl group becomes a reactive organic group in the polyamide-imide resin. And according to the polyamideimide resin obtained in this way, the effect that low temperature hardening is attained comes to be acquired.

In addition, when a compound having two or more glycidyl groups is used as the glycidyl compound, one glycidyl group and the raw material polyamideimide cause the reaction as described above, and another unreacted glycidyl group and the raw material polyamide. Reaction with imides can also occur. As a result, the raw material polyamideimide can be increased in quantity. Such a reaction is represented, for example, by the following chemical formula (3).

  In the above formula (3), the reaction in which a polyamideimide resin in which two molecules of raw material polyamideimide are bonded via one molecule of glycidyl compound is exemplified, but the polyamide in the case of using a glycidyl compound having a plurality of glycidyl groups The production reaction of the imide resin is not necessarily limited to this. For example, the raw material polyamideimide can further react with other unreacted glycidyl groups possessed by the glycidyl compound. In addition, when the raw material polyamideimide has functional groups (amino group, carboxyl group, etc.) capable of reacting with glycidyl groups at a plurality of terminals, the raw material polyamideimide and the glycidyl compound have a structure that is alternately and repeatedly bonded. Polyamideimide resins can also be produced.

  The reactivity and reaction amount of such a raw material polyamideimide and a glycidyl compound can be determined by introducing a hydroxyl group capable of reacting with a glycidyl group into the raw material polyamideimide, or by arbitrarily selecting the number of terminal carboxyl groups, amino groups, and hydroxyl groups. It can be controlled by increasing or decreasing the value.

  The reaction between the raw material polyamideimide and the glycidyl compound can be carried out at a temperature around room temperature (25 ° C.), but from the viewpoint of obtaining a good reaction rate, it is preferably carried out at 50 to 180 ° C., and 80 to 160 ° C. It is more preferable to carry out with. In this reaction, a compound such as a tertiary amine such as imidazole or trialkylamine may be added as a catalyst. This also makes it possible to lower the reaction temperature.

  Next, the polyamideimide resin of a preferred embodiment will be described.

  The polyamideimide resin is obtained by the reaction between the raw material polyamide and the glycidyl compound as described above. Such a polyamideimide resin includes a structural unit derived from a raw material polyamideimide and a structural unit derived from a glycidyl compound, and has at least one reactive organic group at a side chain or a terminal.

  The structural unit derived from the raw material polyamideimide is, for example, a portion obtained by removing a functional group capable of causing a reaction with the glycidyl compound from the raw material polyamideimide. The structural unit derived from the glycidyl compound is, for example, a portion obtained by removing a functional group capable of causing a reaction with the raw material polyamideimide from the glycidyl compound. And the polyamideimide resin has a bonded structure (for example, a structural unit derived from the raw material polyamideimide and a structural unit derived from the glycidyl compound resulting from the reaction between the functional groups of these compounds. The structures are bonded via a structure generated by the reaction of the above formulas (1) and (2).

  Moreover, the polyamide-imide resin has a reactive organic group in the side chain or terminal of the polyamide-imide resin. Here, a side chain means the structural unit couple | bonded with the said principal chain when the molecular chain containing the structural unit derived from the raw material polyamideimide in a polyamideimide resin is made into a principal chain. For example, when the polyamideimide resin has a branched structure, all the molecular chains including the structural unit derived from the raw material polyamideimide correspond to the main chain. When the polyamideimide resin has a reactive organic group in the side chain, the reactive organic group may be directly bonded to the main chain or may be contained in a structural unit constituting the side chain. The term “terminal” refers to the terminal portion of the molecular chain constituting the main chain.

  The reactive organic groups possessed by the polyamideimide resin include those produced by the reaction between the raw material polyamideimide and the glycidyl compound, those originally possessed by the raw material polyamideimide and the glycidyl compound, and after the reaction between the raw material polyamideimide and the glycidyl compound. Some have been introduced. Here, the reactive organic group is a functional group that can form a bond by reacting with another reactive organic group between the same or different molecules constituting the polyamide-imide resin. Group, carboxyl group, isocyanate group, amino group, imino group and the like.

  The polyamideimide resin preferably contains at least a reactive organic group that has been introduced into the polyamideimide resin as a result of the reaction between the raw material polyamideimide and the glycidyl compound. Such a reactive organic group is included in the above-described bonding structure formed by the above reaction, and as a result, it is formed at a position corresponding to a side chain in the polyamideimide resin. Examples of such a reactive organic group include a hydroxyl group generated as a result of a reaction between an amino group or a carboxyl group in a raw material polyamideimide as described above and a glycidyl group in a glycidyl compound, or an epoxy group derived from a glycidyl compound. Can be mentioned.

  In particular, the polyamideimide resin preferably contains only the reactive organic group introduced into the structure of the polyamideimide resin by the reaction of the raw material polyamideimide and the glycidyl compound as described above. Since such a polyamideimide resin has a reactive organic group only in a side chain at a specific position, it tends to have appropriate curability.

  Moreover, it is preferable that a polyamideimide resin has at least one of a hydroxyl group or a carboxyl group, and an amino group at the terminal. This terminal hydroxyl group is preferably derived from the reaction of the hydroxyl group or amino group in the polyamideimide resin with the monoepoxy compound, and the carboxyl group or amino group was at the terminal of the raw material polyamideimide It is preferable that it is. The polyamideimide resin having these functional groups at the ends has further excellent curability.

  As the polyamideimide resin, those having a structure in which a plurality of raw material polyamideimides are quantified through a glycidyl compound are preferable. Examples of such polyamideimide resins include those obtained by bonding a plurality of molecules of raw material polyamideimide to a single molecule of glycidyl compound, and those obtained by alternately bonding raw material polyamideimide and glycidyl compound. Can be mentioned. Such a polyamide-imide resin includes a reactive organic group in all the parts where the raw material polyamide-imide and the glycidyl compound are reacted, and has at least two reactive organic groups.

  Among them, as the polyamide-imide resin, a product obtained by binding a plurality of raw material polyamide-imides to a single molecule of glycidyl compound as in the former is easier to cure at low temperatures when used as a resin composition. This is preferable. In this case, a compound having two or more glycidyl groups is used as the glycidyl compound for forming the polyamideimide resin. The polyamideimide resin thus obtained can have a terminal derived from the raw material polyamideimide, that is, a carboxyl group or an amino group.

  Next, the resin composition according to a preferred embodiment will be described.

  The resin composition of the present embodiment includes at least the polyamideimide resin as described above, and further includes components for adjusting the characteristics of the resin composition. Such a resin composition is preferably a curable resin composition that can be cured by a predetermined treatment such as heating. From the viewpoint of obtaining such curability satisfactorily, the resin composition preferably includes a curing agent or a curing accelerator that accelerates the curing of the polyamideimide resin. Moreover, the resin composition can contain a diluent, a crosslinking agent, particles, a flame retardant, and the like as necessary.

A resin composition comes to produce a crosslinking reaction efficiently by including a hardening accelerator, and the outstanding curability comes to be obtained. Curing accelerators include imidazole, 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2. -Phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazoline, naphthimidazole, pyrazole, triazole , Tetrazole, indazole, pyridine, pyrazine, pyridazine, pyrimidine, benzotriazole, purine, imidazoline, pyrazoline, quinoline, isoquinoline, dipyridyl, di Noryl, phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, benzoquinoline, benzoisoquinoline, benzocinnoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, carboline, perimidine, triazine, tetrazine, pteridine, Oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazole, thiadiazole, pyrroledione, isoindoledione, pyrrolidinedione, benzoisoquinolinedione, triethylenediamine, hexamethylenetetramine And nitrogen-containing compounds such as aminosilane and phenylaminosilane Becomes promoter can be exemplified. In addition, a hardening accelerator is not necessarily limited to these. Moreover, it is preferable to select a hardening accelerator suitably according to use temperature.

  The blending amount of the curing accelerator in the resin composition is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyamideimide resin from the viewpoint of sufficiently maintaining the characteristics of the polyamideimide resin. It is more preferable that it is -10 weight part. In addition, as a hardening accelerator, only 1 type may be used among the things mentioned above, and you may use in combination of multiple types.

  Moreover, the resin composition can be adjusted so as to have appropriate properties such as viscosity by including a diluent, which is advantageous when a coating film is formed on a predetermined substrate. As the diluent, those capable of satisfactorily dissolving or dispersing other components of the resin composition are preferable. For example, acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, methanol, ethanol, N, N-dimethylformamide, N, N-dimethylacetamide, gamma butyrolactone, N-methyl-2-pyrrolidone Etc. can be illustrated. As the diluent, one or more of these can be used.

  Furthermore, since the resin composition contains a crosslinking agent, curing is more likely to occur, and characteristics such as thermal expansion coefficient, adhesiveness, and chemical resistance may be improved. Examples of the crosslinking agent include phenol-based, amine-based, acid anhydride-based, and epoxy-based crosslinking agents. The amount of the crosslinking agent is preferably 1 to 90 parts by weight and more preferably 5 to 70 parts by weight with respect to 100 parts by weight of the polyamideimide resin. When the amount of the crosslinking agent is less than 1 part by weight, the effect of the crosslinking agent tends to be insufficient. On the other hand, if the amount is more than 90 parts by weight, the properties of the cross-linking agent become dominant and the properties of the polyamideimide resin may be lost.

  Moreover, the resin composition tends to obtain a good expansion coefficient and electrical characteristics by including particles. Examples of the particles include silica, alumina, titania, zirconia and the like. It is preferable that the maximum particle size of the particles contained in the resin composition is 500 nm or less. If the particle diameter is larger than 500 nm, there is a tendency that defects are likely to occur when a cured film is formed. Moreover, it is preferable that the compounding quantity of particle | grains shall be 1-90 weight part among 100 weight part of total amounts of a resin composition. When the blending amount of the particles is less than 1 part by weight, the effect tends to be hardly obtained by the particles. On the other hand, when the amount exceeds 90 parts by weight, there is a risk that the reliability may be lowered due to the fact that defects are likely to occur.

  When the resin composition further contains a flame retardant, the flame retardancy of the cured film can be improved, and as a result, the resin composition is further suitable for use as an electronic material. As the flame retardant, commonly used additive type flame retardants can be applied. The blending amount of the flame retardant is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyamideimide resin. When the blending amount of the flame retardant is less than 0.1 parts by weight, the flame retardancy tends not to be sufficiently improved. On the other hand, when it exceeds 50 parts by weight, the physical properties of the resin composition and its cured film tend to be lowered.

  The resin composition may further contain a rubber-based elastomer, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent and the like in addition to the components described above.

  Such a resin composition can be applied as an adhesive layer as it is or by being cured. When applied to an electronic component or the like, this adhesive layer can function as a layer for bonding substrates together and as an insulating layer for ensuring insulation between the substrates.

  Examples of the method for forming the adhesive layer include a method in which the adhesive layer is directly applied to the substrate on which the adhesive layer is to be formed, and a method in which the film is adhered to the substrate after the film is formed. In the method of direct application, for example, the resin composition dissolved in an organic solvent such as a diluent as described above is applied by a spin coater, multi-coater, etc., and then the organic solvent is volatilized by heating or hot air blowing. The adhesive layer is formed by removing them.

  On the other hand, in the case of a method using a film, a film made of a resin composition is formed on a predetermined support, and then the obtained film is adhered to a substrate. The film can be formed by applying a resin composition dissolved in an organic solvent on a support and then removing the solvent. And after laminating | stacking this film on a base | substrate, an adhesive layer is formed on a base | substrate by performing a heating and drying as needed. Peeling of the support from the film may be performed before or after lamination to the substrate.

  Examples of the support used for forming the film include polyethylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, tetrafluoroethylene film, release paper, and metal foil such as copper foil and aluminum foil. The thickness of the support is preferably 10 to 150 μm. This support may be subjected to mud treatment, corona treatment, mold release treatment, and the like.

  The film thus obtained can be stored by various methods. For example, the film is cut into a certain length and stored in a sheet form, or the film is wound and stored in a roll form. The method of doing is mentioned. From the viewpoints of storage stability, productivity, and workability, it is preferable that a protective film is further laminated on the surface of the film opposite to the support, and this is wound into a roll and stored. Examples of the protective film include polyethylene, polyvinyl chloride, polyethylene terephthalate, and release paper. This protective film may also be subjected to mat treatment, embossing, and mold release treatment.

  The substrate on which the adhesive layer is formed is not particularly limited, and examples thereof include copper, aluminum, polyimide, ceramic, and glass. When the adhesive layer is formed of a cured film of the resin composition, the adhesive layer formed on the substrate as described above is further heated to cause thermosetting. Examples of the heating method include a method using a hot plate or an oven. A suitable curing temperature varies depending on the presence and type of a curing accelerator contained in the resin composition, but is preferably set to 130 to 230 ° C, for example.

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

(Synthesis Example 1)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 171 mmol of bis (3-hydroxy-4-aminophenyl) as a diamine compound and X-22-161-B (Shin-Etsu Chemical) as a siloxane diamine 9 mmol of trade name manufactured by Kogyo Co., Ltd., amine equivalent 1600), 378 mmol of trimellitic anhydride, and 424.7 g of N-methyl-2-pyrrolidone as an aprotic polar solvent were added, and the temperature was raised to 80 ° C. Stir 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 4 hours. After confirming that the theoretical amount of water has accumulated in the moisture determination receiver and that no water has flowed out, remove the water and toluene in the moisture determination receiver, and raise the temperature to 180 ° C in the reaction solution. Of toluene was removed. After cooling the solution in the flask to room temperature, 198 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, and the temperature was raised to 150 ° C. and reacted for 2 hours. This obtained the NMP solution of the raw material polyamideimide of Synthesis Example 1.

(Synthesis Example 2)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 142.5 mmol of bis (3-hydroxy-4-aminophenyl) as a diamine compound and X-22-161-B as a siloxane diamine ( Shin-Etsu Chemical Co., Ltd. trade name, amine equivalent 1600) is 7.5 mmol, trimellitic anhydride is 315 mmol, N-methyl-2-pyrrolidone is added as an aprotic polar solvent, 346.3 g, and the temperature is increased to 80 ° C. The mixture was warmed and stirred 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 4 hours. After confirming that the theoretical amount of water has accumulated in the moisture determination receiver and that no water has flowed out, remove the water and toluene in the moisture determination receiver, and raise the temperature to 180 ° C in the reaction solution. Of toluene was removed. After cooling the solution in the flask to room temperature, 150.8 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, and the temperature was raised to 150 ° C. and reacted for 2 hours. Thereby, the NMP solution of the raw material polyamideimide of Synthesis Example 2 was obtained.
[Production of polyamide-imide resin]

Example 1
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 250 g of NMP solution of the raw material polyamideimide obtained in Synthesis Example 1 and NC3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as the glycidyl compound (3.8 functional) 22.7 g was added, the temperature was raised to 120 ° C., and the mixture was stirred for 5 hours. Thereby, the polyamide-imide resin of Example 1 was obtained.

(Example 2)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 250 g of NMP solution of the raw material polyamideimide obtained in Synthesis Example 1 and EPON 1031 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) as the glycidyl compound (Tetrafunctional) 17.3 g was added, the temperature was raised to 120 ° C., and the mixture was stirred for 5 hours. Thereby, the polyamideimide resin of Example 2 was obtained.

(Example 3)
In a 300 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 100 g of the NMP solution of the raw material polyamideimide obtained in Synthesis Example 2, and NC3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as the glycidyl compound (3.8 functional) 0.9 g was added, the temperature was raised to 120 ° C., and the mixture was stirred for 5 hours. Thereby, the polyamideimide resin of Example 3 was obtained.

Example 4
In a 300 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 100 g of the NMP solution of the raw material polyamideimide obtained in Synthesis Example 2, and NC3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as the glycidyl compound (3.8 functional) 1.45 g was added, the temperature was raised to 120 ° C., and the mixture was stirred for 5 hours. Thereby, the polyamide-imide resin of Example 4 was obtained.

(Example 5)
In a 300 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 100 g of the NMP solution of the raw material polyamideimide obtained in Synthesis Example 2, and NC3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as the glycidyl compound (3.8 functional) 5.78 g was added, the temperature was raised to 120 ° C., and the mixture was stirred for 5 hours. Thereby, the polyamideimide resin of Example 5 was obtained.

(Comparative Example 1)
In a 300 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, 200 g of the polyamideimide resin NMP solution obtained in Synthesis Example 1 was heated to 120 ° C. and stirred for 5 hours. Thereby, the polyamideimide resin of Comparative Example 1 was obtained.

(Comparative Example 2)
In a 300 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 60 g of bis (3-hydroxy-4-aminophenyl) as a diamine compound and EPON 1031 (product of Japan Epoxy Resin Co., Ltd.) as a glycidyl compound Name, tetrafunctional) 62 g, N-methyl-2-pyrrolidone 250 g as an aprotic polar solvent was added, the temperature was raised to 120 ° C. and stirring was started. Resin was not obtained.

(Comparative Example 3)
22.7 g of NC3000H (trade name, manufactured by Nippon Kayaku Co., Ltd., 3.8 functional) as a glycidyl compound is added to 250 g of the NMP solution of the raw material polyamideimide of Synthesis Example 1, and N, N-dimethyl is added so as to obtain an appropriate viscosity. Dilution with acetamide gave a resin composition.
[Evaluation of raw material polyamideimide and polyamideimide resin]

(Measurement of weight average molecular weight)
As a result of measuring the weight average molecular weight (Mw; styrene conversion) of the raw material polyamideimide or the polyamideimide resin of Synthesis Examples 1-2, Examples 1-5, and Comparative Examples 1-2, the results shown in Table 1 were obtained. It was. As described above, in Comparative Example 2, gelation occurred and a polyamideimide resin could not be obtained, so the weight average molecular weight could not be measured. In Table 1, for the polyamideimide resin, the addition amount of the glycidyl compound reacted with the raw material polyamideimide was shown in mol% with respect to the raw material polyamideimide.

［樹脂組成物の調製］ (Measurement of epoxy equivalent)
The epoxy equivalents of the raw material polyamideimide, polyamideimide resin or resin composition of Synthesis Examples 1-2, Examples 1-5 and Comparative Examples 1-3 were measured by the dioxane hydrochloride method. The obtained results are shown in Table 2. In Comparative Example 2, gelation occurred and the epoxy equivalent could not be measured. Table 2 shows the amount of glycidyl compound added as in Table 1. In Table 2, when there is no description of an epoxy equivalent, it means that the compound did not have an epoxy group.

[Preparation of resin composition]

(Example 6)
In the NMP solution of the polyamideimide resin of Example 3, EXB-9829 (Dainippon Ink Chemical Co., Ltd.) as a curing agent was 1.5% by weight with respect to the solid content of the polyamideimide resin, and 2-ethyl as a curing accelerator. The resin of Example 6 was prepared by blending -4-imidazole to 0.03% by weight of the total solid content of the polyamideimide resin and diluting with N, N-dimethylacetamide to obtain an appropriate viscosity. A composition was prepared.

(Example 7)
In the NMP solution of the polyamideimide resin of Example 4, EXB-9829 (Dainippon Ink Chemical Co., Ltd.) as a curing agent was 2.5% by weight based on the solid content of the polyamideimide resin, and 2-ethyl-as a curing accelerator. The resin composition of Example 7 was prepared by blending 4-imidazole to 0.04% by weight of the total solid content of the polyamideimide resin and diluting with N, N-dimethylacetamide to obtain an appropriate viscosity. Was made.

(Example 8)
In the NMP solution of the polyamideimide resin of Example 5, EXB-9829 (Dainippon Ink & Chemicals, Inc.) as a curing agent was 8.6% by weight with respect to the solid content of the polyamideimide resin, and 2-ethyl- The resin composition of Example 8 was prepared by blending 4-imidazole to 0.17% by weight of the total solid content weight of the polyamideimide resin and diluting with N, N-dimethylacetamide to obtain an appropriate viscosity. Was made.
[Production of film]

The resin composition solutions prepared in Examples 6, 7, and 8 were uniformly applied onto PET, and dried at 100 ° C. for 15 minutes. Next, the film was peeled off from the PET and cured at 160 ° C. for 1 hour, thereby obtaining a film made of a cured product of each resin composition. Separately, the resin composition solutions prepared in Examples 6, 7, and 8 were uniformly applied onto PET and dried at 100 ° C. for 15 minutes. Subsequently, what peeled the film from PET was hardened at 250 degreeC for 1 hour, and, thereby, the film which consists of hardened | cured material of each resin composition was obtained.
[Evaluation of film]

(Measurement of elastic modulus and glass transition temperature by dynamic viscoelasticity)
Using each of the two types of films (films obtained at a curing temperature of 160 ° C. or 250 ° C.) for each resin composition obtained from the resin compositions of Examples 6, 7 and 8, these dynamic viscoelasticities were obtained. It was measured. The dynamic viscoelasticity is measured by using a wide area dynamic viscoelasticity measuring device E-4000 manufactured by UBM Co., Ltd., a temperature rising rate of 5 ° C./min, a distance between chucks of 20 mm, a frequency of 10 Hz, an amplitude of 3 μm, an automatic static load, and a tension method. It measured on condition of this. And from the obtained result, the elasticity modulus in 50 degreeC and the maximum value (glass transition temperature; Tg) of tan-delta were calculated | required. The obtained results are shown in Table 3.

  From Table 3, it was confirmed that the resin compositions of Examples 6 to 8 can form a sufficiently low elastic modulus and high Tg film (cured film) even at a low temperature. From this result, it was found that the polyamideimide resin obtained by the reaction between the raw material polyamideimide and the glycidyl compound can be cured at low temperature and can form a cured film having excellent heat resistance.

Claims (11)

  A polyamide-imide resin obtained by a reaction between a raw material polyamide-imide and a glycidyl compound having a glycidyl group, and having at least one reactive organic group at a side chain or a terminal.   A raw material polyamideimide having an amide group and an imide group in the molecular chain and having an amino group and / or a carboxyl group at the end, and a glycidyl compound having a glycidyl group, are obtained by the reaction between the raw material polyamideimide and the glycidyl compound, A polyamide-imide resin having a reactive organic group produced by the reaction in the side chain or terminal.   A raw material polyamideimide having an amide group and an imide group in the molecular chain and having an amino group and / or a carboxyl group at the terminal and a glycidyl compound having two or more glycidyl groups, is obtained Polyamideimide resin, characterized by having a structure multiplied by bonding with the glycidyl compound and having two or more reactive organic groups generated by the reaction of the raw material polyamideimide and the glycidyl compound. .   The amino acid and / or carboxyl group in the raw material polyamideimide and the glycidyl group in the glycidyl compound are obtained by the reaction and have the reactive organic group generated by the reaction. Polyamideimide resin according to 2 or 3.   The polyamideimide resin according to any one of claims 1 to 4, wherein the reactive organic group is a hydroxyl group.   It has at least one of a hydroxyl group or a carboxyl group, and an amino group at the terminal, The polyamideimide resin as described in any one of Claims 1-5 characterized by the above-mentioned.   7. The raw material polyamideimide is obtained by reacting diimide dicarboxylic acid obtained by reacting diamine and tricarboxylic acid monoanhydride with diisocyanate. Polyamideimide resin as described in any one.   A raw material polyamideimide having an amide group and an imide group in the molecular chain and having an amino group and / or a carboxyl group at the terminal and a glycidyl compound having two or more glycidyl groups are reacted to produce a plurality of the raw material polyamideimides A process for producing a polyamide-imide resin, characterized in that a polyamide-imide resin having a structure that has been quantified by bonding with the glycidyl compound is obtained.   The method for producing a polyamideimide resin according to claim 8, wherein the amino group and / or carboxyl group in the raw material polyamideimide and the glycidyl group in the glycidyl compound are reacted.   A resin composition comprising the polyamideimide resin according to any one of claims 1 to 7.   The resin composition according to claim 10, which is curable.