JP2008239710A - Polyamide resin and its manufacturing method, and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin capable of imparting sufficient curability even at a low temperature and a resin composition comprising the polyamide resin and exhibiting good low-temperature curability. <P>SOLUTION: The polyamide resin comprises a main chain containing an amide bond and, bonded to the main chain, a side chain bearing a reactive organic group. Preferably, the polyamide resin is obtained by causing a dicarboxylic acid bearing the reactive organic group to react with a diisocyanate. The resin composition comprises the polyamide resin, a curing agent, a curing accelerator and a diluent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  The polyamide resin is generally produced by a polymerization reaction between a diamine and an activated dicarboxylic acid (for example, an acid halide or a condensate). However, according to this method, it is necessary to separate a by-product that is produced in an equal amount to the target polyamide, after the polymerization, so that the manufacturing process is complicated. Therefore, for example, as described in Patent Document 1, a method is known in which a polyamide resin is produced by a polymerization reaction of a dicarboxylic acid and a diisocyanate, thereby generating a gas by-product and facilitating the separation thereof. ing.

It is known that when such a polyamide resin has an unsaturated bond in the molecule, its film-forming property and curability when used as a resin composition are improved. As a method for producing such a polyamide resin, (1) a method of introducing a reactive double bond into an acid site or a hydroxyl group of polyamic acid which is a polyimide or polybenzoxazole precursor (see Patent Documents 2 and 3), ( 2) A method of polymerizing diamine and maleic anhydride (see Patent Document 4), a method of adding a hydrocarbon oligomer having an unsaturated double bond at the end of polyamide (see Patent Document 5), partially reactive double A method of polymerizing with an acid chloride after introducing a bond into polyaniline (see Patent Documents 6 and 7) and the like are disclosed. In addition, the photocurable resin composition containing resin obtained in (1) can also form a corresponding polyimide and benzoxazole by heating after patterning by light irradiation.
JP-A-6-172516 Japanese Patent Laid-Open No. 2-311563 JP 2003-287889 A Japanese Patent Laid-Open No. 10-182837 JP 2001-31759 A Japanese Patent Laid-Open No. 2001-31760 JP-A-4-132733

  In recent years, the polyamide resin as described above has been increasingly applied to, for example, electronic materials. In such an electronic material application, for example, it is mixed with other components to form a resin composition, which is cured to be used as an insulating film or the like. In this case, if curing at a lower temperature is possible, there is an advantage that the application range of a resin composition containing a polyamide resin can be widened. However, all the polyamide resins obtained by the above-described conventional methods tend to have difficulty in imparting sufficient curability at low temperatures, and there is room for improvement in this respect.

  Then, this invention is made | formed in view of such a situation, and it aims at providing the polyamide resin which can provide sufficient sclerosis | hardenability also at low temperature. Moreover, it aims at providing the manufacturing method of such a polyamide resin, and the resin composition which has the said polyamide resin and has favorable low-temperature curability.

  In order to achieve the above object, the polyamide resin of the present invention is characterized by having a main chain containing an amide bond and a side chain having a reactive organic group and bonded to the main chain.

  Since the polyamide resin having such a structure has a reactive organic group in the side chain, for example, when it is cured as a resin composition, it is relatively easily three-dimensional due to the reactive organic group in the curing reaction. Crosslinking can occur. Therefore, according to the polyamide resin of the present invention, low temperature curability capable of good curing can be imparted even under low temperature conditions.

  The polyamide resin of the present invention preferably has a plurality of side chains having a reactive organic group. In this way, the three-dimensional crosslinking as described above is more likely to occur, and better low-temperature curability can be imparted.

  The polyamide resin of the present invention is preferably obtained by reacting a dicarboxylic acid having a reactive organic group with diisocyanate. Since such a polyamide resin has a reactive organic group for each structural unit derived from dicarboxylic acid, three-dimensional crosslinking can be more favorably generated.

  Further, the polyamide resin of the present invention may be obtained by reacting a first carboxylic acid having a reactive organic group, a second dicarboxylic acid not having a reactive organic group, and a diisocyanate. Good. In this way, the polyamide resin partially includes units that are structural units derived from dicarboxylic acid and do not have a reactive organic group. For example, when it is not preferable that excessive three-dimensional crosslinking occurs. , Suitable curability can be imparted.

  In the method for producing a polyamide resin of the present invention, a dicarboxylic acid having a reactive organic group and a diisocyanate are reacted to have a main chain containing an amide bond and a reactive organic group and bonded to the main chain. A polyamide resin having a side chain is obtained.

  According to the method for producing a polyamide resin of the present invention, a polyamide resin having a reactive organic group in the side chain can be easily produced. Moreover, according to this method, since the by-product accompanying the reaction is mainly in a gaseous state, it is almost unnecessary to remove the by-product, and the reaction operation can be facilitated.

  Here, in the case of the above-described prior art, there are the following disadvantages in the method for producing a polyamide resin. For example, first, in the method described in Patent Document 2, 3 or 7, since an acid halide or a metal catalyst is used in the reaction, a by-product after reaction derived from these was obtained. Sometimes mixed in the polyamide resin. When a polyamide resin is used for an electronic material, it is not preferable that a solid impurity, a metal impurity, an ionic impurity, or the like is included because an appearance defect or a decrease in performance tends to occur. Although the by-product can be separated after the reaction, when the removal is performed to a level that does not affect the properties, the production process of the polyamide resin tends to be extremely complicated.

  Further, in the case of Patent Documents 5 and 6, since reactive double bonds are introduced at the ends, it tends to be difficult to obtain a polyamide resin capable of sufficiently producing three-dimensional crosslinking.

  On the other hand, according to the method for producing a polyamide resin of the present invention, it is possible to efficiently form polyamide units with little by-product contamination, and to introduce a reactive organic group into the side chain. As a result, the disadvantages of the prior art as described above can be greatly reduced.

  In the method for producing a polyamide resin of the present invention, it is more preferable to react a first dicarboxylic acid having a reactive organic group, a second dicarboxylic acid not having a reactive organic group, and a diisocyanate.

  In this case, by changing the blending ratio of the first and second dicarboxylic acids, the number of side chains having a reactive organic group contained in the obtained polyamide resin can be adjusted to a suitable range. Therefore, it is possible to easily obtain a polyamide resin capable of appropriately generating three-dimensional crosslinking.

  From the viewpoint of efficiently obtaining a polyamide resin while suppressing side reactions as much as possible, it is preferable to react 0.7 to 1.3 equivalents of diisocyanate with respect to the total amount of the first dicarboxylic acid and the second dicarboxylic acid.

  The ratio of the first dicarboxylic acid / second dicarboxylic acid is more preferably 0.90 / 0.10 to 0.02 / 0.98 in terms of molar ratio. By doing so, it becomes easier to obtain a polyamide resin into which side chains having reactive organic groups are appropriately introduced.

  Furthermore, in the method for producing a polyamide resin of the present invention, the reactive organic group is preferably a phenolic hydroxyl group. The phenolic hydroxyl group in the polyamide resin tends to cause three-dimensional crosslinking particularly when the resin composition containing the polyamide resin is cured. Therefore, by applying a phenolic hydroxyl group as the reactive organic group, it becomes easy to obtain a polyamide resin capable of imparting further excellent low-temperature curability.

  The present invention also provides a resin composition comprising the polyamide resin of the present invention. This resin composition is curable, and more preferably thermosetting. When the resin composition of the present invention contains the polyamide resin of the present invention, three-dimensional crosslinking is easily formed during the curing reaction. Therefore, it can be cured well even under low-temperature conditions as compared with the prior art.

  According to the present invention, it is possible to provide a polyamide resin capable of imparting sufficient curability even at a low temperature. Moreover, it becomes possible to provide the suitable manufacturing method of such a polyamide resin, and the resin composition which can be hardened | cured favorably also at low temperature by including this polyamide resin.

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

(Polyamide resin and production method thereof)
The polyamide resin of a preferred embodiment has a structure composed of a main chain including an amide bond and a side chain bonded to the main chain. The main chain in the polyamide resin is the longest chain in the structure of molecules constituting the resin. Such a main chain has a structure in which a certain structural unit is repeatedly bonded through an amide bond.

  Moreover, the side chain in the polyamide resin of this embodiment has a reactive organic group. Here, the reactive organic group is an organic group that can form a three-dimensional cross-link when a polyamide resin or a resin composition containing the same is cured. The side chain containing the reactive organic group may be one in which the reactive organic group is contained in a part of the structural unit constituting the side chain, or may be the reactive organic group itself. In the former case, the side chain may contain an amide bond.

  Examples of the reactive organic group that the side chain has include a functional group that can react with an epoxy group or the like to form a bond. More specifically, examples of such reactive organic groups include amino groups, carboxyl groups, carboxylic anhydride groups, alcoholic hydroxyl groups, phenolic hydroxyl groups, epoxy groups, and the like. Preferred is a phenolic hydroxyl group. Here, the phenolic hydroxyl group includes both a hydroxyl group bonded to a benzene ring included in the side chain and a hydroxyl group bonded directly to the benzene ring included in the main chain. In the latter case, the “side chain” of the portion is composed of only a hydroxyl group.

  The polyamide resin of the present embodiment is preferably obtained by reacting dicarboxylic acid with diisocyanate. Such a polyamide resin has a structural unit derived from dicarboxylic acid and a structural unit derived from diisocyanate. Both structural units are repeatedly bonded via an amide bond at the end of these structural units or an amide bond formed at the ends of these structural units. The side chain is a structural unit that dicarboxylic acid or diisocyanate originally has, and is constituted by a portion that is not incorporated into the main chain by these reactions.

  Hereinafter, suitable embodiment of reaction which obtains a polyamide resin from dicarboxylic acid and diisocyanate is described.

  In the reaction of dicarboxylic acid and diisocyanate, a carboxyl group in dicarboxylic acid and an isocyanate group in diisocyanate react to form an amide bond. A polyamide resin is produced as a result of a polymerization reaction in which such a reaction occurs repeatedly.

  The reaction between the dicarboxylic acid and the diisocyanate is preferably performed at 100 ° C. or higher, and preferably performed at 140 to 180 ° C. By setting it as such reaction temperature, a favorable reaction rate is obtained and it becomes possible to obtain a polyamide resin efficiently. Moreover, a polyamide resin can also be produced | generated more efficiently by using tertiary amines, such as an imidazole and a trialkylamine, as a catalyst. In this case, the reaction can sufficiently occur even when the reaction temperature is lower than the above, so that the side reaction caused by the high temperature condition can be significantly suppressed.

  In the reaction of dicarboxylic acid and diisocyanate, the diisocyanate is preferably used in an amount of 0.7 to 1.3 equivalents (molar equivalent), more preferably 1.00 to 1.20 equivalents, based on the dicarboxylic acid. If the amount of diisocyanate used is 0.7 equivalent or less with respect to the dicarboxylic acid, unreacted dicarboxylic acid tends to remain, and the properties of the resulting polyamide resin may be deteriorated. On the other hand, when it exceeds 1.3 equivalents, the reaction between the unreacted diisocyanate and the phenolic hydroxyl group which is a reactive organic group is likely to occur, which may make it difficult to obtain a polyamide resin having a good molecular weight. .

  The reactive organic group introduced into the side chain of the polyamide resin may have either a dicarboxylic acid or a diisocyanate, but various compounds can be prepared as the dicarboxylic acid having a reactive organic group. It is more preferable to have it. In this case, in the obtained polyamide resin, the structural unit derived from dicarboxylic acid has a side chain containing a reactive organic group.

  The dicarboxylic acid having a reactive organic group is a compound having two carboxyl groups and at least one reactive organic group. The reactive organic group is contained in the side chain bonded to the structural unit between the two carboxyl groups or directly bonded to the structural unit between the two carboxyl groups.

  As the dicarboxylic acid having such a reactive organic group, an aromatic dicarboxylic acid having an aromatic ring in the structural unit between two carboxyl groups is preferable. In this aromatic dicarboxylic acid, the side chain containing a reactive organic group is preferably bonded to an aromatic ring. When the reactive organic group is a phenolic hydroxyl group, it is more preferable that the hydroxyl group is bonded to the aromatic ring in the aromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid having a phenolic hydroxyl group as the reactive organic group include 5-hydroxyisophthalic acid, methylene disalicylic acid, pamoic acid, 4-hydroxyisophthalic acid, 5,5′-thiodisalicylic acid and the like. .

  Further, as the dicarboxylic acid having a reactive organic group, those containing an imide bond in the structural unit between two carboxyl groups are preferred, and diimide dicarboxylic acid containing two imide bonds is more preferred. Diimide dicarboxylic acid can be obtained by (1) reaction of diamine and tricarboxylic acid monoanhydride or (2) reaction of aminobenzoic acid and tetracarboxylic dianhydride.

  When producing diimide dicarboxylic acid, in the case of (1), 2 equivalents of tricarboxylic acid monoanhydride are reacted with diamine. Thereby, the acid anhydride group in the tricarboxylic acid monoanhydride reacts with the two amino groups of the diamine to produce an imide group, and diimide dicarboxylic acid having carboxyl groups at both ends is obtained.

  As the diamine used in this case, an aromatic diamine having an aromatic ring in the structural unit between two amino groups, an aliphatic diamine in which the structural unit between the two amino groups is composed of an aliphatic hydrocarbon, and two amino groups Examples thereof include siloxane diamine having a siloxane structure as a structural unit therebetween. In addition, examples of the aromatic tricarboxylic acid monohydrate include trimellitic anhydride or cyclohexanetricarboxylic acid anhydride.

  More specifically, examples of the aromatic diamine 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-aminophenoxy) benzene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis (trifluoromethyl) ) Biphenyl-4,4'-diamine, 2,6,2 ', 6'-tetramethyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyl-biphenyl-4,4' -Diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenylsulfone, (4,4'-diamino) benzophenone, (3,3'-diamino) benzophenone, (4,4'- Examples include 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. In addition, you may use it combining multiple things mentioned above as diamine.

  When diimide dicarboxylic acid is obtained by the reaction of (1) above, either one of diamine and tricarboxylic acid monoanhydride may be present, or both may be present. In particular, from the viewpoint of advantageously producing diimide dicarboxylic acid, it is preferable that the reactive organic group has a diamine. In this case, the reactive organic group is contained in the side chain bonded to the structural unit between the two amino groups or directly bonded to this structural unit.

  Examples of the diamine containing a reactive organic group include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, and 4,4′-diamino-2,2. '-Dimethyl-5,5'-dihydroxybiphenyl, 4,4'-diamino-2,2'-di (trifluoromethyl) -5,5'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) Propane, bis (4-amino-3-hydroxyphenyl) propane, bis (4-amino-2-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxy) Phenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis Aromatic diamines such as (4-amino-2-methyl-5hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, etc. Is mentioned.

  On the other hand, when diimide dicarboxylic acid is obtained by the reaction of (2), 2 equivalents of aminobenzoic acid are reacted with tetracarboxylic dianhydride. Thereby, with respect to two acid anhydride groups in tetracarboxylic dianhydride, an amino group in aminobenzoic acid reacts to generate an imide group, and diimide dicarboxylic acid having carboxyl groups at both ends is obtained.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride Anhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 1- Trifluoromethyl 2,3,5,6-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3- Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-di Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether Dianhydride Benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3-benzophenone tetracarboxylic dianhydride 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid Dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyl Tetracarboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) ) Methylpheny Silane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3, 4-Dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butane Tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1, 2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, , 2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo- (2,2,2) -oct (7) -ene 2,3,5,6-tetracarboxylic dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4 '-(4,4'isopropylidenediphenoxy) -bis (phthalic anhydride), tetrahydrofuran-2,3,4,5- Examples thereof include tetracarboxylic dianhydride and bis (exobicyclo (2,2,1) heptane-2,3-dicarboxylic dianhydride) sulfone. These tetracarboxylic dianhydrides may be used alone or in combination.

  Even when diimide dicarboxylic acid is obtained by the reaction of (2) above, one of tetracarboxylic dianhydride and aminobenzoic acid may have a reactive organic group, or both may have. Examples of aminobenzoic acid having a reactive organic group include 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 4-amino-3-hydroxybenzoic acid, 3-hydroxyanthranilic acid, and 5-hydroxyanthranilic acid. , 3-amino-4-hydroxybenzoic acid and the like.

  As mentioned above, although the dicarboxylic acid which has a reactive organic group was illustrated, in manufacture of a polyamide resin, in addition to the dicarboxylic acid (1st dicarboxylic acid) and diisocyanate which have a reactive organic group, it does not have a reactive organic group. A dicarboxylic acid (second dicarboxylic acid) may be further reacted. By carrying out like this, the number of the reactive organic group which a polyamide resin has can be adjusted moderately, and it becomes easy to obtain favorable sclerosis | hardenability. In this case, the blending amount of the diisocyanate should satisfy the suitable blending ratio as described above with respect to the total amount of the first and second dicarboxylic acids.

  When the first and second dicarboxylic acids are used in combination, for example, a dicarboxylic acid having a reactive organic group is used as the first dicarboxylic acid, and a diimide dicarboxylic acid having no reactive organic group is used as the second dicarboxylic acid. It is preferable to use it. Diimide dicarboxylic acids having no reactive organic groups are all reactive as raw material compounds (diamine, tricarboxylic acid monoanhydride, aminobenzoic acid, tetracarboxylic dianhydride) in the production of diimide dicarboxylic acid as described above. It can be obtained by using a compound having no organic group. The ratio of the first dicarboxylic acid / second dicarboxylic acid is preferably 0.90 / 0.10 to 0.02 / 0.98 in terms of molar ratio, 0.50 / 0.50 to 0.10. /0.90 is more preferable.

  In the production of the polyamide resin, a carboxylic acid having a reactive organic group may be further used. The carboxylic acid having a reactive organic group is a compound having one carboxyl group and at least one reactive organic group. By further using such a compound, a polyamide resin having a structural unit derived from a carboxylic acid having a reactive organic group at the terminal can be obtained. And since this polyamide resin has a reactive organic group also at the terminal, it can give better low temperature curability. When using the carboxylic acid which has a reactive organic group, the ratio of dicarboxylic acid which has a reactive organic group / carboxylic acid which has a reactive organic group is 0.70 / 0.30-0.97 / 0. Preferably it is about 03.

  Examples of the carboxylic acid having a reactive organic group include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,6 -Dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 2,3,5-tri Hydroxybenzoic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-methylsalicylic acid, 3-hydroxy-o-toluic acid, 3-hydroxy-p-toluic acid, 2,6-dihydroxy-4-methylbenzoic acid, 4 -Hydroxy-3,5-dimethylbenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydro Ci-1-naphthoic acid, 6-hydroxy-1-naphthoic acid, 6-hydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, phenolphthalein , Diphenolic acid, 4- (4-hydroxyphenoxy) benzoic acid and the like. These 1 type (s) or 2 or more types can be used.

(Resin composition)
Next, a preferred embodiment of the resin composition containing the polyamide resin described above will be described. As the resin composition, in addition to the polyamide resin, those further containing a curing agent, a curing accelerator and a diluent are preferable. First, a hardening | curing agent is a component which can produce the hardening reaction of a polyamide resin favorably.

  An example of the curing agent is an epoxy resin. For example, bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, 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, biphenyl novolac type epoxy resin, bisphenol A novolak type epoxy resin, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenols, diester of alcohols Examples thereof include glycidyl etherified products, alkyl substituted products, halides, hydrogenated products and the like thereof. These epoxy resins may be used alone or in combination of two or more.

  The curing accelerator is a component that can accelerate the curing of the polyamide resin. By including this curing accelerator, crosslinking easily occurs in the resin composition, and it becomes easier to impart sufficient low-temperature curability. 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-phenyl Imidazoline, 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 From nitrogen-containing compounds such as aminosilane and phenylaminosilane Curing accelerator and the like that. These are preferably selected and blended appropriately according to the curing temperature, and the above may be blended alone or in combination.

  Although the compounding quantity of a hardening accelerator is not restrict | limited in particular, For example, in order to maintain the characteristic of a polyamide resin, it is preferable in it being 0.01-20 mass parts with respect to 100 mass parts of polyamide resins, 0.05-10 More preferably, it is part by mass. In the present specification, “part by mass” is substantially equivalent to “part by weight” (the same applies hereinafter).

  Moreover, since the resin composition further contains a diluent, it becomes possible to dissolve or disperse components such as a polyamide resin, and the handleability of the resin composition is improved.

  As the diluent, those capable of satisfactorily dissolving or dispersing other components of the resin composition such as polyamide resin and curing accelerator 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. These can use 1 type (s) or 2 or more types.

  Furthermore, the resin composition may further contain a crosslinking agent. By including a crosslinking agent, the curability of the resin composition tends to be further improved. Although it does not restrict | limit especially as a crosslinking agent, For example, a phenol type, an amine type, an acid anhydride type, and an epoxy type crosslinking agent are suitable.

  The compounding quantity of a crosslinking agent can be 1-90 mass parts with respect to 100 mass parts of polyamide resins, and it is more preferable when it is 5-70 mass parts. When the compounding quantity of a crosslinking agent is 1 mass part or less with respect to a polyamide resin, it exists in the tendency for the effect mentioned above as a crosslinking agent to be hard to be acquired. On the other hand, when it exceeds 90 parts by mass, the properties of the crosslinking agent become dominant, and the properties inherent to the polyamide resin may not be sufficiently obtained.

  The resin composition may further contain particles, particularly inorganic particles. By including such particles, the thermal expansion coefficient and electrical characteristics of the resin composition and the cured product thereof can be improved. As the particles, for example, inorganic particles made of silica, alumina, titania, zirconia or the like are preferable. It is preferable to contain particles having a maximum particle size of 500 nm or less. When particles having a maximum particle diameter exceeding 500 nm are used, when a film made of a cured product of the resin composition is formed, the proportion of particles in the film becomes too large depending on the film thickness, which causes defects in the film. It may be a factor.

  The amount of the particles in the resin composition is preferably 1 to 90 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the polyamide resin. When the blending amount of the particles is less than 1 part by mass, the above-described effects due to the addition of the particles may not be sufficiently obtained. On the other hand, when it exceeds 90 mass parts, when the cured film of a resin composition is formed, possibility that the defect resulting from particle | grains will arise increases and there exists a possibility of causing the fall of reliability.

  Furthermore, the resin composition may further contain a flame retardant. When a flame retardant is included, the flame retardancy of the resin composition and its cured product is improved. As the flame retardant, a general additive-type flame retardant can be contained without any particular limitation. The blending amount of the flame retardant is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyamide resin. If the blending amount of the flame retardant is less than 0.1 parts by mass, sufficient flame retardancy may not be obtained, and if it exceeds 50 parts by mass, the physical properties of the resin composition may be undesirably lowered.

  The resin composition of this embodiment is usually capable of being cured by heat. For example, when the resin composition has photocurability due to the inclusion of a structure or component that promotes curing by light, etc. Further, a sensitizer may be further contained. By containing a sensitizer, light absorption is promoted and better curing tends to be possible. As the sensitizer, a known compound can be applied, and it is preferable to select appropriately according to the wavelength of the irradiated light. It is preferable that the compounding quantity of a sensitizer is 0.01-20 mass% with respect to solid content of a resin composition, and it is more preferable to set it as 0.1-10 mass%. By including the sensitizer within such a range, it is possible to perform good curing while maintaining the characteristics of the resin composition.

  In addition to the components described above, the resin composition of the present embodiment may contain a rubber elastomer, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent, and the like according to desired characteristics.

(Adhesive layer comprising resin composition and method for producing the same)
The resin composition described above can form a resin composition layer. The layer composed of the resin composition is formed on, for example, a substrate mounted on an electronic component or the like, and functions as an adhesive layer that adheres to another substrate or the like formed thereon. it can. Further, the resin composition layer can be further cured to form a protective layer for protecting the substrate or the like and an interlayer insulating layer. The adhesive layer can be formed by a method in which the adhesive layer is directly applied onto a substrate on which the adhesive layer is to be formed, or a method in which a resin composition film is once formed and then bonded to the substrate.

  First, when the resin composition layer is formed by direct coating, the resin composition is coated on a desired surface of the substrate with a spin coater, a multi-coater or the like as it is or in a solution in an organic solvent. . Next, when the resin composition contains a diluent or when an organic solvent is used, the diluent or organic solvent is volatilized and removed by heating the layer formed by coating or blowing hot air on the layer. To do. Thus, a resin composition layer composed of the resin composition (mainly solid content) is obtained.

  On the other hand, in the method using a film, after a resin composition is applied on a predetermined support to obtain a resin composition film, the film is laminated on the substrate and the like, thereby laminating the resin composition. Form a layer. The resin composition film is formed by volatilizing and removing a diluent and an organic solvent from a layer after application by applying the resin composition as it is or in the above-described solution state on a support, and then heating or blowing hot air from the layer after application. can do. Removal of the support from the resin composition film may be performed before or after lamination on the substrate on which the resin composition layer is formed.

  Examples of the support for forming the resin composition film include films made of polyethylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, tetrafluoroethylene, release paper, or metal foil such as copper foil and aluminum foil. Is applicable. The thickness of these supports is preferably 10 to 150 μm. The surface of the support (for example, the surface on which the film of the resin composition is formed) may be further subjected to mat treatment, corona treatment, mold release treatment, and the like.

  The resin composition film can be stored as a single film from which the support is peeled off or in the state of a laminate laminated on the support. From the viewpoint of reducing deterioration due to storage, it is preferable to store the laminate in a state. Storage of the resin composition film can be carried out by cutting it into a certain length to form a sheet, or winding it into a roll. From the viewpoint of improving storability, workability and productivity, in the above laminate, it is preferable that the surface of the resin composition film is further covered with a protective film and then wound into a roll and stored. . Examples of the protective film include films made of polyethylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and tetrafluoroethylene, and release paper. These protective films may be subjected to mat treatment, embossing, and mold release treatment on the surface facing the film made of the resin composition.

  The substrate on which the resin composition layer as described above is to be formed is not particularly limited, and a substrate made of a metal such as copper or aluminum, a resin such as polyimide, or an inorganic material such as ceramic or glass can be applied. For example, it can be formed on a substrate in which a wiring made of metal is formed on an insulating substrate made of resin. And the resin composition layer formed on the base | substrate can have a function as a protective layer, an adhesive layer, an insulating layer, etc. by hardening | curing. Curing can be caused by heating, but depending on the type of polyamide resin or the like contained in the resin composition, it can also be caused by light irradiation. In the case of curing by heating, the suitable temperature varies depending on the presence or absence of the curing accelerator in the resin composition and its type, but 130 to 230 ° C. is less likely to deteriorate the properties of the cured product layer of the resin composition, Moreover, it is preferable because workability is good.

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 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer and a stirrer, 45 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound, 94.5 mmol of trimellitic anhydride And 133.3 g of N-methyl-2-pyrrolidone (NMP) 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.

  After cooling the solution in the flask to room temperature, 30 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid containing a reactive organic group was dissolved in this solution, and then 82.5 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate. The temperature was raised to 150 ° C. and reacted for 2 hours to obtain an NMP solution of the polyamide resin of Example 1.

(Example 2)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer and a stirrer, 54 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound, and 113.4 mmol of trimellitic anhydride And 140.9 g of N-methyl-2-pyrrolidone (NMP) 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.

  After cooling the solution in the flask to room temperature, 23.1 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid containing a reactive organic group was dissolved in this solution, and then, 44.9 mmol of 4,4′-diphenylmethane diisocyanate as a diisocyanate. And the temperature was raised to 150 ° C. and reacted for 2 hours to obtain an NMP solution of the polyamide resin of Example 2.

(Example 3)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer and a stirrer, 57 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound, 119.7 mmol of trimellitic anhydride And 139.3 g of N-methyl-2-pyrrolidone (NMP) 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.

  After cooling the solution in the flask to room temperature, 14.3 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid containing a reactive organic group was dissolved in this solution, and then 48.4′-diphenylmethane diisocyanate as a diisocyanate was 78.4 mmol. And the temperature was raised to 150 ° C. and reacted for 2 hours to obtain an NMP solution of the polyamide resin of Example 3.

Example 4
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer and a stirrer, 57 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound, 119.7 mmol of trimellitic anhydride And 140.9 g of N-methyl-2-pyrrolidone (NMP) 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.

  After cooling the solution in the flask to room temperature, 14.3 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid containing a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid containing a reactive organic group were added to this solution. After 4 mmol was dissolved, 78.4 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, and the temperature was raised to 150 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 4.

(Example 5)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer and a stirrer, 57 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound, 119.7 mmol of trimellitic anhydride And 139.7 g of N-methyl-2-pyrrolidone (NMP) 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.

  After cooling the solution in the flask to room temperature, 14.3 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid containing a reactive organic group and 1.4 mmol of 4-hydroxybenzoic acid as a carboxylic acid containing a reactive organic group were added to this solution. After dissolution, 78.4 mmol of 4,4′-diphenylmethane diisocyanate was added as diisocyanate, the temperature was raised to 150 ° C., and the mixture was reacted for 2 hours to obtain an NMP solution of the polyamide resin of Example 5.

(Example 6)
In a 300 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer and stirrer, 45 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound, 94.5 mmol of trimellitic anhydride And 108.8 g of N-methyl-2-pyrrolidone (NMP) 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.

  After cooling the flask solution to room temperature, 11.3 mmol of isophthalic acid as a dicarboxylic acid and 1.1 mmol of 2,4-dihydroxybenzoic acid as a carboxylic acid containing a reactive organic group were dissolved in this solution, and then as diisocyanate. 4,4′-diphenylmethane diisocyanate 61.9 mmol was added, the temperature was raised to 150 ° C., and the mixture was reacted for 2 hours to obtain an NMP solution of the polyamide resin of Example 6.

(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 X-22- as a siloxane diamine 161-B (trade name, amine equivalent 1500, manufactured by Shin-Etsu Chemical Co., Ltd.) 9 mmol, trimellitic anhydride 378 mmol, and 424.7 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added. Was heated 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.

After cooling the solution in the flask to room temperature, 198 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate to this solution, 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.
[Evaluation of polyamide resin]

  As a result of calculating | requiring the polystyrene equivalent weight average molecular weight (Mw) of the polyamide resin of Examples 1-6 and Comparative Example 1, it became the result shown in Table 1. The weight average molecular weight was measured by using two GL-S300MDT-5 (manufactured by Hitachi Chemical Co., Ltd.) in series as a measurement column. At this time, as an eluent, 0.03 mol of lithium bromide and 0.06 mol of phosphoric acid were added to 1 L of dimethylformamide for liquid chromatography and dissolved, and then 1 L of tetrahydrofuran for liquid chromatography was further added. .

［樹脂組成物の調製］

[Preparation of resin composition]

(Example 7)
1.58 g of NC-3000H (epoxy resin; trade name, manufactured by Nippon Kayaku Co., Ltd.) is added to 30 g of the NMP solution of the polyamide resin of Example 1, and 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator. 0.016 g was added, and this was diluted with N, N-dimethylacetamide until an appropriate viscosity was obtained to prepare a resin composition.

(Example 8)
NC-3000H (epoxy resin; trade name, manufactured by Nippon Kayaku Co., Ltd.) 1.22 g and 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator to 30 g of NMP solution of polyamide resin of Example 2 0.012 g was added, and this was diluted to an appropriate viscosity with N, N-dimethylacetamide to prepare a resin composition.

Example 9
30 g of NMP solution of polyamide resin of Example 3 is 0.29 g of NC-3000H (epoxy resin; trade name, manufactured by Nippon Kayaku Co., Ltd.), and 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator. 0.003 g was added, and this was diluted with N, N-dimethylacetamide to an appropriate viscosity to prepare a resin composition.

(Example 10)
0.88 g of NC-3000H (epoxy resin; trade name, manufactured by Nippon Kayaku Co., Ltd.) and 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator were added to 30 g of the NMP solution of polyamide resin of Example 4. 0.009 g was added, and this was diluted with N, N-dimethylacetamide to an appropriate viscosity to prepare a resin composition.

(Example 11)
0.83 g of NC-3000H (epoxy resin; trade name, manufactured by Nippon Kayaku Co., Ltd.) and 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator were added to 30 g of the NMP solution of the polyamide resin of Example 5. 0.008 g was added, and this was diluted with N, N-dimethylacetamide to an appropriate viscosity to prepare a resin composition.

(Example 12)
0.14 g of NC-3000H (epoxy resin; trade name manufactured by Nippon Kayaku Co., Ltd.) and 2PZ-CNS (trade name of product manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator were added to 30 g of the NMP solution of polyamide resin of Example 6. 0.001 g was added, and this was diluted with N, N-dimethylacetamide to an appropriate viscosity to prepare a resin composition.

(Comparative Example 2)
1.58 g of NC-3000H (epoxy resin; trade name, manufactured by Nippon Kayaku Co., Ltd.) and 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator were added to 30 g of the NMP solution of polyamide resin of Comparative Example 1. 0.016 g was added, and this was diluted with N, N-dimethylacetamide to an appropriate viscosity to prepare a resin composition.
[Characteristic evaluation]

(Preparation of resin composition film)
The resin composition solutions obtained in Examples 7 to 12 and Comparative Example 2 were uniformly applied onto a polyethylene terephthalate (PET) film as a support, and then dried by heating at 130 ° C. for 15 minutes. A resin composition film was formed on the film. Thereafter, the PET film was peeled off to obtain a resin composition film.

(DSC measurement)
About each resin composition film (5 mg) of Examples 7-12 and the comparative example 2, using a differential scanning calorimeter (DSC: Perkin Elma PYRIS1 DSC), the temperature range (10 degree-C / min) of 50-350 degreeC. The temperature and temperature were measured. The obtained results are shown in Table 2.

(Measurement of dynamic viscoelasticity)
The resin composition films of Examples 7 to 12 and Comparative Example 2 were further heated at 200 ° C. for 1 hour to cure the resin composition and obtain a cured film. About each obtained cured film, using a dynamic viscoelasticity measuring apparatus (DVE: UBM Co., Ltd. wide area dynamic viscoelasticity measuring apparatus E-4000), the temperature rising rate was 5 ° C./min, the distance between chucks was 20 mm, and the frequency. The maximum value of tan δ (Tg: glass transition temperature) in the temperature range of 50 to 350 ° C. was determined by 10 Hz, amplitude 5 μm, automatic static load, and tension method. The obtained results are shown in Table 2.

  From Table 2, each resin composition film obtained from the resin compositions of Examples 7 to 12 showed a clear exothermic peak at a lower temperature than the resin composition film of Comparative Example 2, and even at low temperatures. It was found that efficient curing occurred. Moreover, each cured film obtained from the resin composition of Examples 7-12 all had high Tg, and it was also confirmed that it has sufficient heat resistance.

Claims (12)

  A polyamide resin comprising a main chain containing an amide bond and a side chain having a reactive organic group and bonded to the main chain.   The polyamide resin according to claim 1, wherein the polyamide resin has a plurality of side chains each having the reactive organic group.   3. The polyamide resin according to claim 1, wherein the polyamide resin is obtained by reacting a dicarboxylic acid having a reactive organic group with a diisocyanate.   Any one of Claims 1-3 obtained by making the 1st dicarboxylic acid which has the said reactive organic group, the 2nd dicarboxylic acid which does not have the said reactive organic group, and diisocyanate react. The polyamide resin according to claim 1.   The polyamide resin according to claim 1, wherein the reactive organic group is a phenolic hydroxyl group.   A dicarboxylic acid having a reactive organic group and diisocyanate are reacted to obtain a polyamide resin having a main chain containing an amide bond and a side chain having the reactive organic group and bonded to the main chain. A process for producing a polyamide resin, characterized in that   The method for producing a polyamide resin according to claim 6, wherein the first dicarboxylic acid having a reactive organic group, the second dicarboxylic acid not having a reactive organic group, and a diisocyanate are reacted.   The method for producing a polyamide resin according to claim 7, wherein 0.7 to 1.3 equivalents of the diisocyanate are reacted with respect to the total amount of the first dicarboxylic acid and the second dicarboxylic acid.   The polyamide according to claim 7 or 8, wherein the ratio of the first dicarboxylic acid / the second dicarboxylic acid is 0.90 / 0.10 to 0.02 / 0.98 in terms of molar ratio. Manufacturing method of resin.   The method for producing a polyamide resin according to any one of claims 6 to 9, wherein the reactive organic group is a phenolic hydroxyl group.   A resin composition comprising the polyamide resin according to any one of claims 1 to 5.   The resin composition according to claim 10, which is curable.