JP2008280511A - Polyamide resin and method for producing the same, curable resin composition containing polyamide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin which can form a curable resin composition capable of being cured in mild conditions and capable of facilitating the removal of solvents at low temperature, and to provide a method for producing the same. <P>SOLUTION: The present polyamide resin can be dissolved in methyl ethyl ketone, and has a reactive double bond. The polyamide resin can be produced by a method having a process of reacting a dicarboxylic acid with a diisocyanate, to produce the polyamide resin, wherein the dicarboxylic acid comprises a reactive double bond-having dicarboxylic acid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  As a method for producing a polyamide resin, a method based on a polymerization reaction between a diamine and an activated dicarboxylic acid (an acid halide or a condensing agent) is generally known. However, according to this method, it is necessary to separate a by-product that is produced in an equal amount to the polyamide resin after polymerization.

  On the other hand, a method for producing a polyamide resin by a reaction between a dicarboxylic acid and a diisocyanate is also known (see, for example, Patent Document 1). According to such a method, since the by-product is a gas, an operation for separating the by-product after polymerization is not necessary.

  In recent years, polyamide resins having various structures have been manufactured in order to cope with various uses. For example, as a method for producing a polyamide resin having an unsaturated bond, (1) a method of introducing a reactive double bond into an acid site or a hydroxyl group of a polyamic acid which is a polyimide or polybenzoxazole precursor (see, for example, Patent Document 2) ), (2) a method of polymerizing diamine and maleic anhydride (see, for example, Patent Document 3), and (3) a method of adding a hydrocarbon oligomer having an unsaturated double bond to the polyamide terminal (for example, Patent Document 4). (4) A method in which a reactive double bond is partially introduced into polyaniline and then polymerized with an acid chloride (see, for example, Patent Document 5) is known.

  Moreover, it is known that a polyamide resin is used for various uses as a curable resin composition. For example, the polyamide resin obtained by the method (1) can be cured into a corresponding polyimide or polybenzoxazole by heating after patterning by light irradiation as a photocurable resin composition. it can.

In general, N, N-dimethylformamide, N, N-dimethylacetamide, gamma butyrolactone, N-methyl-2-pyrrolidone, and the like are used in the method for producing a polyamide resin as described above. In addition, it is known that the solubility of the solvent of the polyamide resin becomes worse as the degree of polymerization becomes higher (see, for example, Patent Document 6).
JP-A-6-172516 Japanese Patent No. 2880523 Japanese Patent Laid-Open No. 10-182837 JP 2001-31759 A JP-A-4-132733 JP 2006-28367 A

  The polyamide resin is, for example, a curable resin composition as described above, and is often used after being converted into a protective film or the like by a curing reaction. In this case, the film formation is generally performed by forming a solution in which a polyamide resin is dissolved or dispersed in a solvent or the like, applying the solution, and then removing the solvent. In the formation of such a protective film or the like, it is preferable that the curing reaction can proceed under mild conditions such as a low temperature as much as possible from the viewpoint of reducing the influence on the substrate or the like on which the film is formed. From the same point of view, in the film formation as described above, it is desirable to remove the solvent after applying the solution containing the polyamide resin at the lowest possible temperature.

  However, there are many cases where it is difficult to sufficiently perform such low-temperature curing and solvent removal at a low temperature in the polyamide resin obtained by the conventional production method as described above.

  Therefore, the present invention has been made in view of such circumstances, and forms a curable resin composition that can be cured under mild conditions and can be easily removed at a low temperature. It aims at providing the polyamide resin which can be manufactured. Another object of the present invention is to provide a method for producing such a polyamide resin and a curable resin composition containing the polyamide resin.

  In order to achieve the above object, the polyamide resin of the present invention is soluble in methyl ethyl ketone and has a reactive double bond. Here, “polyamide resin soluble in methyl ethyl ketone” means a resin that is soluble in 1 g or more in 100 g of methyl ethyl ketone at 25 ° C.

  First, since the polyamide resin of the present invention has a reactive double bond in the molecule, when the curing reaction is carried out as a curable resin composition, the reactive double bond favorably causes a crosslinking reaction. As compared with the case where no reactive double bond is present, sufficient curing can be achieved even under low temperature conditions. Conventionally, the polyamide resin having such a reactive double bond tended to be soluble only in a solvent having a high boiling point, but the polyamide resin of the present invention has a relatively low boiling point as compared with the conventional one. It can be dissolved in methyl ethyl ketone. Therefore, the film forming process can be performed at a low temperature, the influence on the substrate and the like can be reduced, and energy saving can be achieved.

  The polyamide resin of the present invention preferably has 2 to 30 mol% of a structural unit derived from an epoxy (meth) acrylate compound, and more preferably 5 to 10 mol%. When the proportion of the structural unit derived from the epoxy (meth) acrylate compound is less than 2 mol%, it is difficult to cause good crosslinking due to the reactive double bond, and it is difficult to dissolve in methyl ethyl ketone depending on the combination with other dicarboxylic acids. There is a risk. On the other hand, when it is larger than 30 mol%, the molecular weight of the resulting polyamide resin tends to be small, and it may be difficult to obtain a good film.

  The polyamide resin of the present invention described above is preferably manufactured by the following manufacturing method. That is, the method for producing a polyamide resin of the present invention includes a step of producing a polyamide resin by reacting a dicarboxylic acid and a diisocyanate in the method for producing a polyamide resin having a reactive double bond. And a dicarboxylic acid having a reactive double bond.

  Here, the conventional method for producing a polyamide resin as described above has the following problems. That is, when using a resin for electronic material applications, solid impurities, metal impurities, ionic impurities, etc. cause poor appearance and reduced performance. desirable. However, in the methods described in Patent Documents 2 and 5, since an acid halide, a metal catalyst, or the like is used, a by-product is generated, and a step of separating these is necessary to prevent contamination of impurities. Therefore, the manufacturing method of the polyamide resin has become complicated.

  Further, in the method described in Patent Document 3, the ratio of the repeating unit of the structure as a polyamide tends to be reduced due to the formation of an imide ring by diamine and maleic anhydride, so that the heat resistance of the obtained film or the like is lowered. Or the self-supporting film cannot be formed. Furthermore, in the method of Patent Document 5, since the raw material contains many branches, gelation is likely to occur, and in order to suppress this, it tends to be difficult to increase the repeating structure of the polyamide resin.

  Furthermore, in the method of adding a hydrocarbon oligomer having a double bond at the end of polyamide as described in Patent Document 4, a double bond is introduced only at the end, so that three-dimensional There was also a problem that crosslinking did not occur efficiently.

  On the other hand, according to the method for producing a polyamide resin of the present invention, since a raw material that allows easy selection of a compound having excellent solubility in methyl ethyl ketone is used, as a result, it is soluble in methyl ethyl ketone as in the present invention. It becomes easy to produce a polyamide resin.

  Moreover, in this invention, since the polyamide resin is manufactured by reaction of dicarboxylic acid and diisocyanate, a by-product mainly becomes gas. Therefore, it is possible to obtain a polyamide resin with less contamination of impurities, and it is possible to omit a process of separating impurities. Furthermore, since both the raw material dicarboxylic acid and diisocyanate form a polyamide resin repeating structure, the resulting polyamide resin has a large repeating structure, and has a high heat resistance and excellent self-supporting film. It becomes possible to form.

  Furthermore, in the production method of the present invention, since the dicarboxylic acid has a reactive double bond, the polyamide resin obtained as a result of the reaction with the diisocyanate is not only reactive at the terminal but also within the molecule. It can have a double bond. As a result, the obtained polyamide resin can satisfactorily cause three-dimensional crosslinking upon curing.

  In the method for producing a polyamide resin of the present invention, the dicarboxylic acid having a reactive double bond is preferably soluble in methyl ethyl ketone. By using a dicarboxylic acid that is soluble in methyl ethyl ketone, as a result, the polyamide resin of the present invention that is soluble in methyl ethyl ketone is more easily obtained.

  More specifically, the dicarboxylic acid having a reactive double bond includes a functional group capable of generating a carboxyl group by reaction with a carboxylic anhydride group, and a (meth) acrylate compound having a (meth) acryloyl group. , And preferably obtained by reaction with a carboxylic acid anhydride.

  The dicarboxylic acid thus obtained has, as a reactive double bond, a (meth) acryloyl group that easily undergoes a crosslinking reaction during curing. Therefore, the polyamide resin obtained by reacting it with diisocyanate. Also, the three-dimensional crosslinking can be satisfactorily formed by curing.

  Here, in this specification, the notation of “(meth) acryloyl” collectively represents acryloyl and methacryloyl, and includes all cases of one or both of acrylic and methacrylic. Similarly, “(meth) acryl” indicates acryl and / or methacryl, and “(meth) acrylate” indicates acrylate and / or methacrylate.

  Moreover, it is preferable that the functional group which can produce | generate a carboxyl group by reaction with a carboxylic anhydride group is a hydroxyl group. Since a hydroxyl group can react with a carboxylic acid anhydride group to form a carboxyl group satisfactorily, the resulting carboxylic acid has a good carboxyl group for reaction with an isocyanate. As a result, in the present invention, the reaction between the carboxylic acid and the diisocyanate occurs efficiently, which makes it easier to obtain a polyamide resin.

  Further, the (meth) acrylate compound is more preferably obtained by a reaction between a bifunctional epoxy compound and (meth) acrylic acid. By using a dicarboxylic acid obtained by using such a (meth) acrylate compound as a raw material, a polyamide resin containing a structure derived from a polyfunctional epoxy compound having excellent solubility in methyl ethyl ketone as a repeating unit can be obtained. . Therefore, it becomes possible to more easily produce a polyamide resin soluble in methyl ethyl ketone.

  The present invention also provides a polyamide resin obtained by the production method of the present invention. As described above, such a polyamide resin has a low impurity content and can be soluble in methyl ethyl ketone.

  Furthermore, this invention provides the curable resin composition which contains the polyamide resin of the said invention, Preferably it hardens | cures with a heat | fever or light. Since such a curable resin composition contains the polyamide resin of the present invention, three-dimensional crosslinking is satisfactorily generated at the time of curing and not only can be cured at low temperature, but methyl ethyl ketone can be used as a solvent. Therefore, solvent removal and the like can be performed at a lower temperature than in the past. As a result, it is possible to satisfactorily form a film having excellent heat resistance while minimizing damage to the substrate and the like.

  According to the present invention, it is possible to provide a polyamide resin capable of forming a curable resin composition that can be cured at a low temperature and can be easily removed at a low temperature. Moreover, it becomes possible to provide the manufacturing method of such a polyamide resin, and the curable resin composition containing this polyamide resin.

Hereinafter, preferred embodiments of the present invention will be described.
[Production method of polyamide resin]

  First, a preferred embodiment of a production method for obtaining the polyamide resin of the present invention will be described.

  A method for producing a polyamide resin according to a preferred embodiment includes a step of reacting a dicarboxylic acid and a diisocyanate to form a polyamide resin, and the dicarboxylic acid that is a raw material is a dicarboxylic acid having a reactive double bond. Including. In this reaction, these compounds are polymerized by a reaction between a carboxyl group in the dicarboxylic acid as a raw material and an isocyanate group in the diisocyanate to produce a polyamide resin.

  The polymerization reaction between the raw material dicarboxylic acid and diisocyanate is preferably carried out at 100 ° C. or more, more preferably 140 to 180 ° C. from the viewpoint of obtaining a good reaction rate. In this polymerization reaction, a tertiary amine such as imidazole or trialkylamine may be used as a catalyst. By using such a catalyst, the polymerization reaction can be carried out at a lower temperature.

  In this polymerization reaction, the diisocyanate is preferably used in an amount of 0.7 to 1.3 equivalents, more preferably 1.0 to 1.2 equivalents, based on the total amount of the raw dicarboxylic acid. When the amount of diisocyanate used is less than 1 equivalent with respect to the carboxylic acid of the raw material, unreacted carboxylic acid remains. On the other hand, when it exceeds 1.3 equivalents, side reactions occur due to unreacted diisocyanate, and it becomes difficult to obtain a high molecular weight polyamide resin, and the by-product may reduce the properties such as heat resistance of the polyamide resin. is there.

  Hereinafter, the raw material dicarboxylic acid and diisocyanate will be described.

  First, examples of the diisocyanate include methylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, and the like. As the diisocyanate, only a single compound may be used, or a plurality of types may be used in combination.

  Next, the carboxylic acid as a raw material includes a dicarboxylic acid having a reactive double bond. This dicarboxylic acid has two carboxyl groups in the molecule to enable a polymerization reaction with diisocyanate. Hereinafter, a suitable dicarboxylic acid will be described in detail.

  The dicarboxylic acid as a raw material contains a dicarboxylic acid having a reactive double bond as described above, and the dicarboxylic acid having a reactive double bond has one or more reactive double bonds, A dicarboxylic acid having two carboxyl groups is preferred. As the reactive double bond, a (meth) acryloyl group is preferable because it can cause a good crosslinking reaction in the polyamide resin. In addition, it is particularly preferable that the dicarboxylic acid is soluble in methyl ethyl ketone because the obtained polyamide resin is likely to be soluble in methyl ethyl ketone.

  As the dicarboxylic acid having a (meth) acryloyl group as a reactive double bond, a functional group capable of generating a carboxyl group by reaction with a carboxylic anhydride group (hereinafter referred to as “carboxyl-forming group”), and (meta ) What was obtained by reaction with the (meth) acrylate compound which has an acryloyl group, and carboxylic anhydride (dicarboxylic anhydride) is preferable. Since the former (meth) acrylate compound has two carboxyl-generating groups, a reaction with a carboxylic acid anhydride occurs at two locations of the (meth) acrylate compound, thereby obtaining a dicarboxylic acid. From the viewpoint of suppressing gelation due to branching in the above reaction, the (meth) acrylate compound preferably has 2.0 to 2.5 carboxyl-generating groups on average.

As the dicarboxylic acid having such a reactive double bond, in particular, a reaction between an epoxy acrylate represented by the following formula (1a) and a carboxylic acid anhydride represented by the following formula (1b) (Dicarboxylic acid represented by the following formula (1c)) is preferred. Here, the epoxy acrylate is a compound obtained by reacting acrylic acid with an epoxy group of a polyfunctional epoxy compound. This epoxy acrylate has a hydroxyl group generated by the above reaction as a carboxyl-forming group. This reaction is represented by the following chemical formula (1), for example. In the following formula (1a), A is a structural unit derived from an epoxy compound in the epoxy acrylate, and B in the following formula (1b) is a structural unit other than the acid anhydride group in the carboxylic acid anhydride.

  Here, the carboxylic acid anhydride is not particularly limited, and examples thereof include the following. That is, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic acid and the like can be exemplified. These may be used alone or in combination of two or more.

On the other hand, as the epoxy acrylate, a polyfunctional epoxy compound represented by the following formula (2a), particularly a bisepoxy compound obtained by a reaction of acrylic acid represented by the following formula (2b) Is preferred. Such a reaction is represented by the following chemical formula (2), for example. A in the formula (2a) represents a main structure that does not contribute to the reaction of the polyfunctional epoxy compound (in the formula (2a), a structural unit excluding a glycidyl group), and A in the chemical formula (1) is formed as it is.

  The polyfunctional epoxy compound that is a raw material for the epoxy acrylate production reaction may contain a bisepoxy compound and other polyfunctional epoxy compounds, but in order to prevent excessive branching of the resulting polyamide resin, the average is overall. The number of epoxy groups per molecule is particularly preferably 2 or more and 2.5 or less.

  Examples of the bisepoxy compound include a bisphenol A type epoxy compound (for example, Epicoat 825 manufactured by Japan Epoxy Resin), a bisphenol F type epoxy compound (for example, Epicoat 806 manufactured by Japan Epoxy Resin), and a biphenyl type epoxy compound (for example, Japan Epoxy Resin Co., Ltd.). (Epicoat YX4000H) and the like can be exemplified.

  In addition, as an epoxy acrylate, you may apply commercially available epoxy acrylate as it is besides what is obtained by said reaction. Examples of commercially available epoxy acrylates include EA-1020 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl group equivalent 270), EMA-1020 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl group equivalent 280), EA- 5520 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl group equivalent 173), EA-5421 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl group equivalent 230), and the like. The hydroxy group in one molecule of these epoxy acrylates is 2 or more and 2.5 or less.

  Generally, polyurethane is produced by the reaction of diol and diisocyanate, but gelation may proceed by the reaction of epoxy acrylate and diisocyanate. Therefore, in the present embodiment, such gelation can be suppressed by reliably reacting the hydroxyl group in the epoxy acrylate with the carboxylic acid anhydride.

  The reaction between the epoxy acrylate and the carboxylic acid anhydride for obtaining the raw material dicarboxylic acid can be carried out at room temperature (25 ° C.). However, from the viewpoint of reaction rate, 30 ° C. to 150 ° C. is preferable, 120 ° C. is more preferable. In this reaction, it is theoretically possible to react the carboxylic anhydride with the hydroxyl group equivalent of the epoxy acrylate 100%, but from the viewpoint of obtaining a good reaction rate, the carboxylic anhydride used in the reaction The amount is preferably 0.80 to 1.10 and more preferably 0.90 to 1.05 with respect to the equivalent of the hydroxyl group. When the amount of the carboxylic acid anhydride is less than 0.8 equivalent, unreacted hydroxyl groups remain and gelation tends to occur. On the other hand, when it exceeds 1.10 equivalent, a side reaction due to the unreacted carboxylic acid anhydride is caused, and the molecular weight of the resin to be produced is lowered, and physical properties such as heat resistance may be lowered.

  As described above, the dicarboxylic acid having a reactive double bond has been described as the raw material dicarboxylic acid. In the reaction of dicarboxylic acid and diisocyanate to obtain a polyamide resin, in addition to the dicarboxylic acid having a reactive double bond, Other dicarboxylic acids can also be used in combination. By appropriately selecting other dicarboxylic acids, the resin skeleton can be changed. For example, excessive three-dimensional crosslinking due to reactive double bonds can be suppressed, and heat resistance can be improved. However, from the viewpoint of reliably obtaining the low-temperature curability of the polyamide resin, it is more preferable that the dicarboxylic acid having a reactive double bond is 10 mol% or more of all the raw dicarboxylic acids.

  Specific examples of other dicarboxylic acids are not particularly limited, and examples thereof include isophthalic acid, terephthalic acid, adipic acid, sebacic acid and imidodicarboxylic acid. These dicarboxylic acids are also preferably soluble in methyl ethyl ketone. By using these together as the dicarboxylic acid, excessive three-dimensional crosslinking due to the reactive double bond can be suppressed, or the heat resistance of the resulting polyamide resin can be improved. Here, imidodicarboxylic acid is derived from the reaction of diamine and 2 equivalents of trimellitic acid. These other dicarboxylic acids can be used alone or in combination of two or more.

  In particular, when an imidodicarboxylic acid is used in combination as a dicarboxylic acid, the resulting polyamide resin also contains an imide group in addition to an amide group, and includes a structure as a so-called polyamideimide resin, and has characteristics such as high heat resistance and high strength. Can be provided. As described above, imidodicarboxylic acid is obtained by the reaction of diamine and trimellitic acid. The diamine is not particularly limited, and examples thereof include the following.

  That is, for example, as aromatic diamine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 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-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis ( 4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) B) Biphenyl-4,4′-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, (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. These may be used alone or in combination of two or more.

It is particularly preferable that these diamines are soluble in methyl ethyl ketone because imidodicarboxylic acid, and thus polyamide resin, are likely to be soluble in methyl ethyl ketone. From this viewpoint, it is particularly preferable to use polypropylene oxide diamine as the diamine.
[Polyamide resin]

  Although the polyamide resin can be favorably obtained by the production method as described above, the polyamide resin of a preferred embodiment is soluble in methyl ethyl ketone and has a reactive double bond.

  The polyamide resin of the present embodiment preferably has a reactive double bond at the end of the molecule constituting the resin and also in the molecule. More preferably, it is contained in the repeating structure of the polyamide resin. By having a reactive double bond in this way, good low-temperature curability can be obtained.

  The reactive double bond that the polyamide resin has is preferably a (meth) acryloyl group. Such a reactive double bond can be introduced by using a (meth) acrylate compound as a raw material in the production method described above.

  Moreover, it is preferable that a polyamide resin contains the structural unit derived from an epoxy (meth) acrylate. The structural unit derived from epoxy (meth) acrylate means a structural unit remaining without reacting in the production process of polyamide among the epoxy (meth) acrylate used as a raw material. It is particularly preferable that the epoxy (meth) acrylate forming the structural unit is soluble in methyl ethyl ketone.

  In this case, the structural unit derived from the epoxy (meth) acrylate is preferably contained in the polyamide resin in an amount of 2 to 30 mol%, more preferably 5 to 10 mol%. Thus, when the structural unit derived from epoxy (meth) acrylate is contained, the obtained polyamide resin tends to be soluble in methyl ethyl ketone. In this case, the structural unit derived from epoxy (meth) acrylate has the (meth) acryloyl group which is a reactive double bond.

As in the production method described above, the polyamide resin is more preferably obtained by reaction of carboxylic acid obtained by reaction of epoxy (meth) acrylate and carboxylic acid anhydride with diisocyanate. In this case, the polyamide resin mainly has a structure in which the structural unit of dicarboxylic acid including the structural unit derived from the epoxy (meth) acrylate described above and the structural unit of diisocyanate are alternately and repeatedly bonded. In this case, it is particularly preferable that the diisocyanate used as a raw material is also soluble in methyl ethyl ketone.
[Curable resin composition]

  The polyamide resin having a reactive double bond described above can be applied as a curable resin composition by combining a curing accelerator, a diluent, a crosslinking agent, particles, a flame retardant, and a sensitizer as necessary. In addition, since the polyamide resin itself can be cured by a reactive double bond, it can be applied alone as a curable resin composition.

  A curable resin composition containing a polyamide resin and a curing accelerator is preferable because it can efficiently cause cross-linking and has an excellent low-temperature curability. The curing accelerator is not particularly limited as long as it accelerates the reaction between reactive double bonds of the polyamide resin, and can be appropriately selected according to conditions such as the curing temperature used and the wavelength of irradiation light. . Examples of the curing accelerator include peroxide, radical, and cationic compounds, and a plurality of these may be combined.

  Specific examples of the curing accelerator include peroxides such as 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, and the like, α, α′-di (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-bis (t-butyl) Peroxy) -3-hexane, di-t-hexyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, and other dialkyl peroxides, and ketone peroxides such as methyl ethyl ketone peroxide Compound, t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoyl peroxide) And peroxyester compounds such as xy) hexane. Examples of the radical system include benzophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzophenone compounds such as 4,4′-bis (dimethylamino) benzophenone, 2-isopropylthioxanthone, etc. Thioxanthone compounds, metal complexes such as titanocene, phosphinic acid compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-hydroxy-1,2-diphenylethanone, 2-isopropyl-1,2-diphenylethane Non, 2,2-dimethoxy-1,2-diphenylethanone, benzoin compounds such as 1-hydroxycyclohexyl phenyl ketone, amine compounds such as methyldiethanolamine, and ester compounds such as ethyl 4- (dimethylamino) benzoate Et That. Examples of the cationic system include onium salts such as bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluorophosphate, diphenyliodonium-hexafluorophosphate, and (cyclopentadienyl) (isopropylbenzene) iron (II ) And the like.

  The blending amount of the curing accelerator is not particularly limited, but is preferably 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin in order to maintain the properties of the polyamide resin. More preferably. In addition, as a hardening accelerator, one type of compound may be used among the things mentioned above, and multiple types may be mixed and used.

  Moreover, the curable resin composition can be in a state in which other components are dissolved or dispersed by including a diluent, and tends to be advantageous in terms of work. The diluent is not particularly limited as long as it can dissolve or disperse other components such as polyamide resin. 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., and one or more of these can be used.

  When the curable resin composition further contains a cross-linking agent, three-dimensional cross-linking is more easily formed and curing can be efficiently caused, and physical properties such as thermal expansion coefficient, adhesiveness, and chemical resistance of the cured product can be obtained. There is a tendency to improve. The crosslinking agent is not limited as long as it is a compound containing a plurality of functional groups capable of reacting with the reactive double bond of the polyamide resin.

  Examples of such compounds include bismaleimide compounds, bisnadic acid compounds, and di (meth) acrylates. When the crosslinking agent is included, the blending amount 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 polyamide resin. When the blending amount is less than 1 part by weight, the effect of the crosslinking agent tends not to be sufficiently exhibited. When the blending amount is more than 90 parts by weight, the properties of the crosslinking agent become dominant and the properties of the polyamide resin are lost. There is a tendency to be.

  Furthermore, the curable resin composition tends to improve the expansion coefficient and electrical characteristics of the cured product by including predetermined particles. Examples of the particles include particles made of silica, alumina, titania, zirconia and the like. The maximum particle size of these particles is preferably 500 nm or less. If the particle diameter is larger than 500 nm, it is not preferable because the possibility of causing defects when a cured film is formed is increased. When the particles are included, the blending amount is preferably 1 to 90 parts by weight with respect to 100 parts by weight of the curable resin composition. If the blending amount is less than 1 part by weight, the effect of the particles tends to decrease, and if it exceeds 90 parts by weight, the reliability may be lowered due to the occurrence of defects or the like, which is not preferable.

  The flame retardant is a component that can impart flame retardancy to the curable resin composition. As this flame retardant, any additive type flame retardant generally used can be applied without any particular limitation. When a flame retardant is included, the blending amount is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the curable resin composition. If the blending amount is less than 0.1 part by weight, the effect of the flame retardant tends to decrease, and if it exceeds 50 parts by weight, the physical properties of the resin may be lowered, which is not preferable.

  Furthermore, the curable resin composition contains a sensitizer, so that light absorption is efficiently generated, and the curability by light is improved. As the sensitizer, a known sensitizer may be appropriately selected and used according to the wavelength of light to be irradiated. The blending amount of the sensitizer is not particularly limited. However, in order to satisfactorily form an image by light irradiation while maintaining the properties of the polyamide resin, it is 0.01 to the solid content of the curable resin composition. It is preferably 20% by weight, and more preferably 0.1 to 10 parts by weight.

Furthermore, the curable resin composition may further contain a rubber-based elastomer, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent, etc., if necessary.
[Adhesive layer]

  The curable resin composition described above can form, for example, an adhesive layer for bonding a predetermined base to another substrate (printed wiring board or the like). The adhesive layer can be formed by, for example, a method of directly applying the curable resin composition onto the substrate on which the adhesive layer is to be formed, a method using a film (adhesive film) made of the curable resin composition, or the like. .

  In the case of the method of directly applying the curable resin composition, for example, first, a solution obtained by dissolving the curable resin composition in an organic solvent or the like is used. Next, this solution is applied onto a substrate using a spin coater, a multi coater or the like, and then dried by heating or the like, thereby forming a curable resin composition layer. This functions as an adhesive layer.

  In the latter method using an adhesive film, a material in which a curable resin composition layer (adhesive film) is formed on a predetermined support is prepared in advance, and this adhesive film is bonded to a substrate. In this case, the adhesive film can be obtained by applying a solution obtained by dissolving the curable resin composition in a solvent to the support, volatilizing the solvent by heating or hot air blowing, and drying. After adhesion of the adhesive film, an adhesive layer composed of a curable resin composition layer can be formed on the substrate by further performing drying by heating or the like as necessary. The support may be removed from the adhesive film before adhesion to the substrate or may be removed after adhesion.

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

  Examples of the method for storing the adhesive film include a method in which the adhesive film is cut into a predetermined length and stored in a sheet form, and a method in which the adhesive film is further wound 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 of the adhesive film, and wind and store it in a roll shape. In this case, examples of the protective film include polyethylene, polyvinyl chloride, polyethylene terephthalate, and release paper. The protective film may be subjected to mat treatment, embossing, and mold release treatment.

  Examples of the substrate on which the adhesive layer is formed include copper, aluminum, polyimide, ceramic, and glass, but applicable substrates are not necessarily limited thereto.

  The adhesive layer formed on the substrate can be cured by being fully or partially polymerized by, for example, heating or irradiating light after bonding to another substrate or the like. it can. Thereby, a base | substrate can be strongly adhere | attached with respect to another board | substrate.

  In the case of curing by heating, the heating can be performed using a hot plate, an oven or the like. In this case, the curing temperature varies depending on the presence and type of the curing accelerator, but is preferably 130 to 230 ° C. from the viewpoint of work.

  In addition, when curing by light irradiation, the light source is not particularly limited, for example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, black light lamp, A lamp light source such as a metal halide lamp or a laser light source such as an argon ion laser, an excimer laser, a nitrogen laser, or a YAG laser can be applied. Moreover, when using a specific wavelength, you may utilize an optical filter as needed. In the case of curing by light irradiation, the curing can be completed by performing post-heating with a hot plate or an oven after the light irradiation.

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

Example 1
In a 300 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 37 mmol of epoxy acrylate EA-1020 (trade name, hydroxyl group equivalent 270, manufactured by Shin-Nakamura Chemical Co., Ltd.), cis as dicarboxylic anhydride -4-Cyclohexene-1, 2-dicarboxylic anhydride 78 mmol, N-methyl-2-pyrrolidone 85 g as an aprotic polar solvent was added, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours.

  After cooling the solution in the flask to room temperature (25 ° C.), 26 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, the temperature was raised to 150 ° C. and reacted for 2 hours, and an NMP solution of the polyamide resin of Example 1 Got.

(Example 2)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 36 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound and KF-8010 (as siloxane diamine). Shin-Etsu Chemical Co., Ltd. trade name, amine equivalent 415) 2 mmol, cyclohexanetricarboxylic anhydride (Mitsubishi Gas Chemical Co., Ltd. trade name) 79 mmol, 157 g of N-methyl-2-pyrrolidone as an aprotic polar solvent, and the temperature The mixture was heated to 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 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. Thereby, a solution containing imidodicarboxylic acid was obtained.

  After cooling the solution in this flask to room temperature (25 ° C.), EA-1020 (trade name, hydroxyl group equivalent 270, manufactured by Shin-Nakamura Chemical Co., Ltd.) as an epoxy acrylate, 38 mmol, cis-4-cyclohexene-1, 2-dicarboxylic acid 79 mmol of acid water was added, and the temperature was raised to 100 ° C. to react for 2 hours. After cooling the solution in the flask to room temperature (25 ° C.) again, 52 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, the temperature was raised to 150 ° C., and the mixture was reacted for 2 hours. NMP of the polyamide resin of Example 2 A solution was obtained.

(Example 3)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 53 mmol of polypropylene oxide diamine (trade name Jeffamine D-400 manufactured by Mitsui Chemicals Fine Co., Ltd.) as a diamine compound, 110 mmol of trimellitic anhydride, 236 g of N-methyl-2-pyrrolidone was added as an aprotic polar solvent, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 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. Thereby, a solution containing imidodicarboxylic acid was obtained.

  After cooling the solution in this flask to room temperature (25 ° C.), EA-5520 (trade name, hydroxyl group equivalent 173, manufactured by Shin-Nakamura Chemical Co., Ltd.) as an epoxy acrylate, 123 mmol, cis-4-cyclohexene-1, 2-dicarboxylic acid 245 mmol of acid water was added, the temperature was raised to 100 ° C., and the reaction was carried out for 2 hours. After the flask solution was cooled again to room temperature (25 ° C.), 9 mmol of acrylic acid and 193 mmol of 4,4′-diphenylmethane diisocyanate were added as diisocyanate, the temperature was raised to 150 ° C., and the reaction was performed for 2 hours. An NMP solution of polyamide resin was obtained.

Example 4
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 47 mmol of polypropylene oxide diamine (trade name Jeffamine D-400, manufactured by Mitsui Chemicals Fine Co., Ltd.) as a diamine compound, 98 mmol of trimellitic anhydride, 254 g of N-methyl-2-pyrrolidone was added as an aprotic polar solvent, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 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. Thereby, a solution containing imidodicarboxylic acid was obtained.

  After cooling the solution in this flask to room temperature (25 ° C.), EA-1020 (trade name, hydroxyl group equivalent 270, manufactured by Shin-Nakamura Chemical Co., Ltd.) as an epoxy acrylate, 109 mmol, cis-4-cyclohexene-1,2-dicarboxylic acid 217 mmol of acid water was added, the temperature was raised to 100 ° C., and the reaction was carried out for 2 hours. After the flask solution was cooled again to room temperature (25 ° C.), 8 mmol of acrylic acid and 171 mmol of 4,4′-diphenylmethane diisocyanate were added as diisocyanate, and the temperature was raised to 150 ° C. and reacted for 2 hours. An NMP solution of polyamide resin was obtained.

(Comparative Example 1)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 171 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound and KF-8010 (Shin-Etsu) as a siloxane diamine Chemical Industry Co., Ltd. trade name, amine equivalent 415) 9 mmol, trimellitic anhydride 378 mmol, 425 g of N-methyl-2-pyrrolidone as an aprotic polar solvent were added, the temperature was raised to 80 ° C., and the mixture was 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. Thereby, a solution containing imidodicarboxylic acid was obtained.

  After cooling the solution in the flask to room temperature (25 ° C.), 50 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, the temperature was raised to 150 ° C. and reacted for 2 hours, and an NMP solution of the polyamide resin of Comparative Example 1 Got.

(Comparative Example 2)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 80 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound and KF-8010 as a siloxane diamine ( Shin-Etsu Chemical Co., Ltd. trade name, amine equivalent 415) 4 mmol, trimellitic anhydride 176 mmol, N-methyl-2-pyrrolidone 349 g as an aprotic polar solvent was added, the temperature was raised to 80 ° C. 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. Thereby, a solution containing imidodicarboxylic acid was obtained.

  After cooling the solution of this flask to room temperature (25 degreeC), as an epoxy acrylate, EA-1020 (Shin-Nakamura Chemical Co., Ltd. brand name, hydroxyl group equivalent 270) 84 mmol, cis-4-cyclohexene-1, 2-dicarboxylic acid 176 mmol of acid water was added, the temperature was raised to 100 ° C., and the mixture was reacted for 2 hours. After the flask solution was cooled again to room temperature (25 ° C.), 117 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, the temperature was raised to 150 ° C., and the reaction was performed for 2 hours. A solution was obtained.

(Comparative Example 3)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 43 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound and KF-8010 (as siloxane diamine). Shin-Etsu Chemical Co., Ltd. trade name, amine equivalent 415) 2 mmol, cyclohexanetricarboxylic anhydride (Mitsubishi Gas Chemical Co., Ltd. trade name) 95 mmol, 140 g of N-methyl-2-pyrrolidone as an aprotic polar solvent, The mixture was heated to 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 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. Thereby, a solution containing imidodicarboxylic acid was obtained.

After cooling the solution in the flask to room temperature (25 ° C.), EA-1020 (trade name, hydroxyl group equivalent 270, manufactured by Shin-Nakamura Chemical Co., Ltd.) as an epoxy acrylate, 15 mmol, cis-4-cyclohexene-1, 2-dicarboxylic acid 32 mmol of water was added, the temperature was raised to 100 ° C., and the reaction was carried out for 2 hours. After the flask solution was cooled again to room temperature (25 ° C.), 69 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, the temperature was raised to 150 ° C., and the mixture was reacted for 2 hours. NMP of the polyamide resin of Comparative Example 3 A solution was obtained.
[Preparation of curable resin composition]

(Example 5)
In the NMP solution of the polyamide resin obtained in Example 1, α, α′-di (t-butylperoxy) diisopropylbenzene (Nippon Yushi Co., Ltd., Perbutyl P) as a curing accelerator was added to 1% by weight of the total solid weight. It was added to become. Furthermore, it diluted with N, N- dimethylacetamide to the appropriate viscosity, and the solution of the curable resin composition was obtained.

(Example 6)
In the NMP solution of the polyamide resin obtained in Example 2, α, α′-di (t-butylperoxy) diisopropylbenzene (Nippon Yushi Co., Ltd., Perbutyl P) as a curing accelerator is 1% by weight of the total solid weight. It was added to become. Furthermore, it diluted with N, N- dimethylacetamide to the appropriate viscosity, and the solution of the curable resin composition was obtained.

(Example 7)
In the NMP solution of the polyamide resin obtained in Example 3, α, α′-di (t-butylperoxy) diisopropylbenzene (Nippon Yushi Co., Ltd., Perbutyl P) as a curing accelerator was added to 1% by weight of the total solid weight. It was added to become. Furthermore, it diluted with N, N- dimethylacetamide to the appropriate viscosity, and the solution of the curable resin composition was obtained.

(Example 8)
In the NMP solution of the polyamide resin obtained in Example 4, α, α′-di (t-butylperoxy) diisopropylbenzene (Nippon Yushi Co., Ltd., Perbutyl P) as a curing accelerator was added to 1% by weight of the total solid weight. It was added to become. Furthermore, it diluted with N, N- dimethylacetamide to the appropriate viscosity, and the solution of the curable resin composition was obtained.

(Comparative Example 4)
In the NMP solution of the polyamide resin obtained in Comparative Example 1, α, α′-di (t-butylperoxy) diisopropylbenzene (Nippon Yushi Co., Ltd., Perbutyl P) as a curing accelerator was added to 1% by weight of the total solid weight. It was added to become. Furthermore, it diluted with N, N- dimethylacetamide to the appropriate viscosity, and the solution of the curable resin composition was obtained.

(Comparative Example 5)
To the NMP solution of the polyamide resin obtained in Comparative Example 2, α, α′-di (t-butylperoxy) diisopropylbenzene (Nippon Yushi Co., Ltd., Perbutyl P) as a curing accelerator is 1% by weight of the total solid weight. It was added to become. Furthermore, it diluted with N, N- dimethylacetamide to the appropriate viscosity, and the solution of the curable resin composition was obtained.

(Comparative Example 6)
To the NMP solution of the polyamide resin obtained in Comparative Example 3, α, α′-di (t-butylperoxy) diisopropylbenzene (Nippon Yushi Co., Ltd., Perbutyl P) as a curing accelerator was added to 1% by weight of the total solid weight. It was added to become. Furthermore, it diluted with N, N- dimethylacetamide to the appropriate viscosity, and the solution of the curable resin composition was obtained.
[Evaluation of polyamide resin and curable resin composition]

(Percentage of structural units derived from epoxy acrylate of polyamide resin)
When the ratios of the structural units derived from epoxy acrylate in the polyamide resins obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were calculated, Example 1 was 26.3 mol% and Example 2 was 12 respectively. 2 mol%, Example 3 16.7 mol%, Example 4 16.7 mol%, Comparative Example 1 0 mol%, Comparative Example 2 12.2 mol%, Comparative Example 3 11.8 Mol%.

(Evaluation of solubility of polyamide resin in methyl ethyl ketone)
The polyamide resins of Examples 1 to 4 and Comparative Example 1 were precipitated with methanol, collected by filtration, and further vacuum-dried 5.0 g of the sample was dissolved in 5.0 g of methyl ethyl ketone. As a result, the solubility of the polyamide resin sample corresponding to each example or comparative example in methyl ethyl ketone was as shown in Table 1.

(Measurement of molecular weight of polyamide resin)
When the weight average molecular weight (Mw; styrene conversion) of the polyamide resin obtained in Examples 1-4 and Comparative Examples 1-3 was measured, it was as shown in Table 2.

(Evaluation of curability of curable resin composition)
First, the solutions of the curable resin compositions prepared in Examples 5 to 8 and Comparative Examples 4 to 6 were uniformly applied on a PET film and dried at 100 ° C. for 15 minutes. Thereafter, the dried film was peeled off from the PET film to obtain an uncured resin film made of the curable resin composition.

Subsequently, about each resin film (10 mg) produced using the curable resin composition of Examples 5-8 and Comparative Examples 4-6, it is a calorific value in the temperature range (50 degreeC / min temperature rise) of 50-350 degreeC. The exothermic temperature was measured. For the measurement, a differential scanning calorimeter (DSC: PYRIS1 DSC manufactured by Perkin Elma) was used. The obtained results are shown in Table 3. In Table 3, the calorific value is a value obtained by subtracting the blank value of only the curing accelerator, and the temperature is a temperature indicating the maximum calorific value.

  As shown above, the polyamide resins of Examples 1 to 4 were all soluble in methyl ethyl ketone and had a sufficient molecular weight. Moreover, it was confirmed that the curable resin composition containing the polyamide resin of Examples 1-4 can obtain a large calorific value at a low temperature as compared with the case of using the polyamide resin of Comparative Examples 1-3. From these results, according to the polyamide resins of Examples 1 to 4, a curable resin composition having high heat resistance, capable of forming a film by low-temperature curing, and excellent in film formability is obtained. It was confirmed.

Claims (10)

  A polyamide resin that is soluble in methyl ethyl ketone and has a reactive double bond.   The polyamide resin of Claim 1 which has 2-30 mol% of structural units derived from an epoxy (meth) acrylate compound. In the method for producing a polyamide resin having a reactive double bond,
Having a step of reacting dicarboxylic acid and diisocyanate to produce a polyamide resin,
The said dicarboxylic acid is a manufacturing method of a polyamide resin containing the dicarboxylic acid which has a reactive double bond.   The method for producing a polyamide resin according to claim 3, wherein the dicarboxylic acid having a reactive double bond is soluble in methyl ethyl ketone.   The dicarboxylic acid having a reactive double bond includes a functional group capable of generating a carboxyl group by reaction with a carboxylic acid anhydride group, a (meth) acrylate compound having a (meth) acryloyl group, and a carboxylic acid anhydride. The manufacturing method of the polyamide resin of Claim 3 or 4 obtained by reaction with these.   The manufacturing method of the polyamide resin of Claim 5 whose functional group which can produce | generate a carboxyl group by reaction with a carboxylic anhydride group is a hydroxyl group.   The said (meth) acrylate compound is a manufacturing method of the polyamide resin of Claim 5 or 6 which is the epoxy (meth) acrylate obtained by reaction of a bifunctional epoxy compound and (meth) acrylic acid.   The polyamide resin obtained by the manufacturing method as described in any one of Claims 3-7.   A curable resin composition comprising the polyamide resin according to any one of claims 1, 2, and 8.   The curable resin composition according to claim 9, which is cured by heat or light.