JP2008280513A - Polyamide resin and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin which can give sufficient curability even at low temperature, even when forming a resin composition or the like, and to provide a resin composition which contains the polyamide resin and has good low temperature curability. <P>SOLUTION: A preferable polyamide resin is characterized by being soluble in cyclohexane or methyl ethyl ketone and having an amide bond-containing main chain and reactive organic group-containing sides bound to the main chain. A preferable resin composition contains the polyamide resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyamide resin and a resin composition.

  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 addition, it is known that if the polyamide resin has an unsaturated bond in the molecule, the film formability and curability when used as a resin composition are improved. As a method for producing a polyamide resin having an unsaturated bond, (1) a method in which a reactive double bond is introduced into an acid site or a hydroxyl group of a polyamic acid which is a polyimide or polybenzoxazole precursor (for example, Patent Documents 2 and 3). (2) A method of polymerizing diamine and maleic anhydride (see, for example, Patent Document 4), (3) A method of adding a hydrocarbon oligomer having an unsaturated double bond to a polyamide terminal (for example, Patent Document) 5), (4) a method in which a reactive double bond is partially introduced into polyaniline and then polymerized with an acid chloride (for example, see Patent Documents 6 and 7) and the like. In addition, it is shown that the photocurable resin composition containing the polyamide resin obtained in (1) can form a corresponding polyimide or benzoxazole by heating after patterning by light irradiation. ing.

Examples of the general solvent used in the above-described method for producing a polyamide resin include N, N-dimethylformamide, N, N-dimethylacetamide, gamma butyrolactone, N-methyl-2-pyrrolidone and the like. In addition, it is known that the obtained polyamide resin has poor solubility in a solvent as its degree of polymerization increases (see, for example, Patent Document 8).
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 JP 2006-28367 A

  In recent years, polyamide resins are increasingly applied to electronic materials. In such electronic material applications, for example, a polyamide resin is mixed with other components to form a resin composition, which is used as an insulating film or the like by being cured. In this case, a resin composition containing a polyamide resin is preferable if it can be cured at as low a temperature as possible because it can be applied to a wide range of uses. However, the polyamide resins obtained by the above-mentioned conventional production methods tend to be difficult to obtain sufficient curability at low temperatures when all are resin compositions, and there is room for improvement in this respect. was there.

  Then, this invention is made | formed in view of such a situation, and when it is set as a resin composition etc., it aims at providing the polyamide resin from which sufficient sclerosis | hardenability is obtained even at low temperature. Another object of the present invention is to provide a resin composition containing this polyamide resin and having good low-temperature curability.

  In order to achieve the above object, the polyamide resin of the present invention is soluble in cyclohexanone or methyl ethyl ketone, and has a main chain containing an amide bond and a side chain containing a reactive organic group bonded to the main chain. Features. Here, the “reactive organic group” means a functional group capable of reacting with a functional group such as a curing agent to be added in the case of a resin composition to form a bond.

  Since the polyamide resin of the present invention has a side chain having a reactive organic group in the molecule, for example, when the resin is cured as a resin composition, the reactive organic group also becomes a reactive site and crosslinks. The structure can be generated efficiently. Therefore, it can be sufficiently cured even at a low temperature as compared with the conventional case. Moreover, when forming an insulating film or the like as described above, the resin composition is usually formed into a film by applying it in a state dissolved in a solvent, removing the solvent, and then curing. Since the polyamide resin can be dissolved in a solvent having a lower boiling point than that of the conventional cyclohexanone or methyl ethyl ketone, the solvent can be removed at a low temperature during film formation. As described above, the polyamide resin of the present invention can perform both solvent removal and curing reaction even at a low temperature. Therefore, according to the resin composition containing this polyamide resin, a series of processes for forming an insulating film or the like by curing. Can be performed at a low temperature.

  Such a polyamide resin of the present invention more preferably has a plurality of side chains containing the above-described reactive organic groups. By having a plurality of such side chains in one molecule, more cross-linked structures can be formed at the time of curing, and a curing reaction can be sufficiently generated even at a lower temperature.

  In particular, the reactive organic group is preferably a phenolic hydroxyl group. The phenolic hydroxyl group is particularly likely to cause a crosslinking reaction of the polyamide resin, and by having the phenolic hydroxyl group as a reactive organic group, it becomes possible to cause curing at a lower temperature.

  Specifically, the polyamide resin of the present invention is preferably obtained by reaction of a raw material dicarboxylic acid containing a dicarboxylic acid having a reactive organic group and diisocyanate. The polyamide resin obtained by such a reaction includes a reactive organic group derived from the raw material dicarboxylic acid in some of the repeating units, and has a plurality of reactive organic groups in the side chain. Become. And such a polyamide resin tends to become soluble in cyclohexanone or methyl ethyl ketone by selecting the kind of raw material dicarboxylic acid or diisocyanate which are the raw materials.

  Further, when the polyamide resin is obtained in this way, the following advantages can be obtained in the production process. That is, in the reaction between the raw material dicarboxylic acid and the diisocyanate, the by-product accompanying this reaction is mainly a gas, so that it is hardly necessary to remove the by-product and the reaction operation is easy.

  Here, the above-described conventional method for producing a polyamide resin has the following disadvantages. First, in the case of the method described in Patent Document 2, 3 or 7, since an acid halide or a metal catalyst is used for the reaction, by-products derived therefrom are mixed in the polyamide resin after the reaction. was there. However, when a polyamide resin is used for an electronic material, for example, if it contains solid impurities, metal impurities, ionic impurities, etc., it is not preferable because appearance defects and performance deterioration are likely to occur. A method of separating these impurities after the reaction is also conceivable, but in this case, if the impurities are removed to a level that does not affect the characteristics, the polyamide resin production process tends to be extremely complicated.

  In addition, in the case of the methods described in Patent Documents 5 and 6, a reactive double bond is introduced at the terminal, so that three-dimensional crosslinking cannot be sufficiently produced when curing, and even at low temperatures There was a tendency that it was difficult to obtain a cured polyamide resin.

  On the other hand, if the polyamide resin of the present invention is obtained by reaction of a raw material dicarboxylic acid having a reactive organic group and diisocyanate, there is almost no generation of by-products in the production process. Since impurities such as impurities are very rarely mixed and the reactive organic group derived from the raw material dicarboxylic acid is satisfactorily introduced into the side chain, it can be sufficiently cured even at a low temperature.

  The polyamide resin of the present invention is obtained by reacting a diisocyanate with a raw material dicarboxylic acid composed of a first dicarboxylic acid having a reactive organic group and a second dicarboxylic acid not having a reactive organic group. More preferably. When the raw material carboxylic acid is a combination of the first and second dicarboxylic acids, the polyamide resin has moderately reactive organic groups in the side chain, and the resin composition is prevented from being excessively cured and becoming brittle. be able to.

  In this case, the first dicarboxylic acid / second dicarboxylic acid preferably has a molar ratio in the range of 1.0 / 0 to 0.01 / 0.99. If it carries out like this, the ratio of a reactive organic group will become very suitable in the polyamide resin obtained.

  When the polyamide resin is obtained by the reaction of the raw material dicarboxylic acid and diisocyanate as described above, it is particularly preferable that the raw material dicarboxylic acid is soluble in methyl ethyl ketone. The polyamide resin obtained using the raw material dicarboxylic acid soluble in methyl ethyl ketone tends to be soluble in methyl ethyl ketone.

  In addition, the polyamide resin of the present invention is preferably obtained by reacting 0.7 to 1.3 equivalents of diisocyanate with the raw material dicarboxylic acid. The polyamide resin satisfying such conditions has a high molecular weight, and can impart excellent strength and heat resistance to the cured product of the resin composition.

  The present invention also provides a resin composition comprising the polyamide resin of the present invention. Since such a resin composition is curable and contains the polyamide resin of the present invention, it can be sufficiently cured even at a low temperature, and the solvent can be removed at a low temperature when forming a film or the like. it can.

  ADVANTAGE OF THE INVENTION According to this invention, when it is set as a resin composition etc., it becomes possible to provide the polyamide resin from which sufficient sclerosis | hardenability is obtained even at low temperature. In addition, it is possible to provide a resin composition containing such a polyamide resin and capable of performing film formation and curing reaction even at a low temperature.

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

(Polyamide resin)
The polyamide resin of a preferred embodiment is soluble in cyclohexanone or methyl ethyl ketone, and has a main chain containing an amide bond and a side chain containing a reactive organic group bonded to the main chain.

  Here, the polyamide resin soluble in cyclohexanone or methyl ethyl ketone can be dissolved in a certain amount or more in these solvents which are liquid at 25 ° C. For example, as a polyamide resin, what can melt | dissolve 5 mass parts or more with respect to 100 mass parts of solvent at 25 degreeC is preferable, and what can melt | dissolve 10 mass parts or more is more preferable. If the amount that can be dissolved at 25 is less than 5 parts by mass, for example, it may be difficult to dissolve the polyamide resin in a solvent and apply it to the substrate. However, for example, when forming a thin film of 5 μm or less, it is sufficient that the polyamide resin can be dissolved at least to an extent sufficient for film formation, and the amount of dissolution may be less than 5 parts by mass. In the present specification, a value based on mass (for example, “parts by mass”) and a value based on weight (for example, “parts by weight”) are considered to be substantially equivalent.

  The main chain which the polyamide resin of this embodiment has is the longest chain which comprises the said resin. This main chain preferably has a structure in which a certain structural unit is repeatedly bonded via an amide bond.

  Moreover, as a reactive organic group which the side chain of a polyamide resin has, the functional group which can react with an epoxy group etc. and can produce | generate a bond is preferable. Examples of such reactive organic groups include amino groups, carboxyl groups, carboxylic anhydride groups, alcoholic hydroxyl groups, phenolic hydroxyl groups, and epoxy groups. As the reactive organic group, a phenolic hydroxyl group is particularly preferable. When the reactive organic group is a phenolic hydroxyl group, three-dimensional crosslinking tends to be particularly easily formed when a resin composition containing a polyamide resin is cured. Therefore, when it has a phenolic hydroxyl group as a reactive organic group, it exists in the tendency for more excellent low-temperature curability to be obtained easily.

  Here, the phenolic hydroxyl group means a hydroxyl group bonded to a benzene ring. This phenolic hydroxyl group includes both a hydroxyl group bonded to a benzene ring possessed by a side chain and a hydroxyl group directly bonded to a benzene ring possessed by a main chain. In the latter case, the “side chain” of the portion is composed of only a hydroxyl group.

  If the polyamide resin has a plurality of side chains containing such reactive organic groups, three-dimensional crosslinking is likely to occur, and curing is advantageous. For example, as described above, when the main chain of the polyamide resin has a structure in which a certain structural unit is repeatedly bonded via an amide bond, the reactive organic group is preferably bonded to a plurality of structural units. .

  When the main chain of the polyamide resin has a structure in which certain structural units are repeatedly bonded through amide bonds, each structural unit includes an ethyloxy group, an isopropyloxy group, or a structure in which these are repeated. And preferred. When certain structural units constituting the polyamide resin have these structures, the polyamide resin tends to be excellent in solubility in cyclohexanone or methyl ethyl ketone.

  The polyamide resin as described above is preferably obtained by a production method as described below. That is, the polyamide resin is preferably obtained by a reaction between a raw material dicarboxylic acid (raw material dicarboxylic acid) and diisocyanate.

  Such a polyamide resin has a structural unit derived from a raw material dicarboxylic acid and a structural unit derived from diisocyanate. Both structural units are repeatedly bonded via 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, a method for obtaining a polyamide resin by a reaction between a raw material dicarboxylic acid and a diisocyanate will be specifically described.

  In the reaction of the raw material dicarboxylic acid and the diisocyanate, the carboxyl group in the raw material dicarboxylic acid and the isocyanate group in the diisocyanate react to form an amide bond. And a polyamide resin can be obtained by the polymerization reaction which such a reaction repeats. When the polyamide resin is obtained in this way, it is preferable that the raw material dicarboxylic acid is soluble in cyclohexanone or methyl ethyl ketone because the obtained polyamide resin is also easily soluble in these.

  The reaction between the raw material dicarboxylic acid and the diisocyanate is preferably performed at 100 ° C. or higher, and is 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. In the above reaction, a tertiary amine such as imidazole or trialkylamine may be used as a catalyst. By using these catalysts, it becomes possible to produce a polyamide resin more efficiently. In this case, the reaction occurs sufficiently even when the reaction temperature is lower than the above, and therefore, side reactions and the like caused by high temperature conditions can be significantly suppressed.

  Moreover, in reaction of raw material dicarboxylic acid and diisocyanate, it is preferable to use 0.7-1.3 equivalent (molar equivalent) of diisocyanate with respect to the total amount of raw material dicarboxylic acid, and use 1.0-1.2 equivalent. Is more preferable. If the amount of diisocyanate used is less than 0.7 equivalents relative to the raw material dicarboxylic acid, unreacted raw material dicarboxylic acid tends to remain, and the properties of the resulting polyamide resin may deteriorate. On the other hand, if it exceeds 1.3 equivalents, unreacted diisocyanate tends to remain, making it difficult to obtain a high molecular weight polyamide resin, heat resistance and the like are reduced, or conversely, handling becomes worse due to high molecular weight. There is a risk of

  Either or both of the raw material dicarboxylic acid and diisocyanate that are raw materials may have the reactive organic group that the side chain of the polyamide resin has, but the reactive organic group is more likely to have dicarboxylic acid. preferable. Since dicarboxylic acids having a reactive organic group can prepare various compounds, the preparation of raw materials tends to be extremely easy. In this case, in the obtained polyamide resin, the structural unit derived from dicarboxylic acid has a side chain containing a reactive organic group. And the structural unit derived from raw material dicarboxylic acid has a reactive organic group as a side chain, respectively, and it becomes easy to obtain the polyamide resin which tends to produce a three-dimensional bridge | crosslinking.

  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.

  For example, examples of the compound having a phenolic hydroxyl group as a reactive organic group include 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, methylene disalicylic acid, pamoic 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. By using diimide dicarboxylic acid as the raw material dicarboxylic acid, the resulting polyamide resin has a polyamideimide structure including an imide bond, and the heat resistance and strength of the polyamide resin tend to be improved. This diimide dicarboxylic acid can be obtained by (1) reaction of diamine and tricarboxylic acid monoanhydride or (2) reaction of amino acid and tetracarboxylic dianhydride.

  When diimide dicarboxylic acid is obtained by the method (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 as a result, a diimide dicarboxylic acid having carboxyl groups at both ends is obtained.

  In this case, the reactive organic group may be contained in one of the raw material diamine and tricarboxylic acid monoanhydride, or both. When using the diamine which has a reactive organic group, as a tricarboxylic acid monoanhydride, what has a reactive organic group and what does not have a reactive organic group can be used together. Conversely, when a tricarboxylic acid monoanhydride having a reactive organic group is used, a diamine having a reactive organic group and a diamine having no reactive organic group can be used in combination. 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.

  The diamine used in the method (1) includes an aromatic diamine containing an aromatic ring in the structure between two amino groups, an aliphatic diamine in which the structure between the two amino groups is composed of an aliphatic hydrocarbon, and two amino groups. Examples include a siloxane diamine containing a siloxane structure in the structure between groups. Tricarboxylic acid monoanhydride includes trimellitic anhydride or cyclohexanetricarboxylic acid anhydride.

  Specifically, as a diamine having no reactive organic group, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl as an aromatic diamine ] 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) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2,2 '-Sulphonyl-biphenyl-4,4'-diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenylsulfone, (4,4'-diamino) benzophenone, (3,3'- Examples include diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, and (3,3′-diamino) diphenyl ether.

  Examples of the aliphatic diamine include (4,4′-diamino) dicyclohexylmethane and polypropylene oxide diamine (trade name Jeffamine). Examples of the siloxane diamine include 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 combining what was mentioned above as diamine which does not have a reactive organic group.

  On the other hand, examples of the diamine having 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-hydroxy Phenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (4-amino-2-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3) -Hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxypheny) ) Ether, bis (4-amino-2-methyl-5hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, etc. An aromatic diamine etc. can be illustrated. In addition, as the diamine having a reactive organic group, a plurality of the above-described ones may be used in combination.

  Moreover, when obtaining diimide dicarboxylic acid by the method of said (2), 2 equivalent amino acid is made to react with tetracarboxylic dianhydride. Thereby, the amino group in the amino acid reacts with the two acid anhydride groups in the tetracarboxylic dianhydride to form an imide group, and as a result, a diimide dicarboxylic acid having carboxyl groups at both ends is obtained. .

  Also when obtaining diimide dicarboxylic acid by the method of (2), one of tetracarboxylic dianhydride and an amino acid may have a reactive organic group, and both may have. When tetracarboxylic dianhydride having a reactive organic group is used, amino acids having a reactive organic group and those having no reactive organic group can be used in combination. On the contrary, when using the amino acid which has a reactive organic group, as tetracarboxylic dianhydride, what has a reactive organic group and what does not have a reactive organic group can be used together.

Specifically, examples of the tetracarboxylic dianhydride having no reactive organic group include pyromellitic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2, 3 , 6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4, 4'-sulfonyldiphthalic acid dinone Water, 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-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis ( 3,4-dicarboxy Phenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic 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 dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4, 3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis ( 3,4-dicarboxyl ) Methyl phenyl silane dianhydride, bis (3,4-carboxyphenyl)
Diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3
3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitate anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic 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, 1,2,3,4-cyclobutanetetracarboxylic dianhydride Bicyclo- (2,2,2) -oct (7) -ene 2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane Anhydride 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4 '-(4,4' isopropylidenediphenoxy) -bis (phthalic anhydride), tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, bis (exobicyclo (2,2,1) heptane -2,3-dicarboxylic dianhydride) sulfone and the like. These tetracarboxylic dianhydrides may be used alone or in combination.

  Further, as the tetracarboxylic dianhydride having a reactive organic group, in the above-described tetracarboxylic dianhydride, a reactive organic group is formed in a part of the structural unit arranged between two acid anhydride groups. The combination is mentioned.

  As amino acids having a reactive organic group, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 4-amino-3-hydroxybenzoic acid, 3-hydroxyanthranilic acid, 5-hydroxyanthranilic acid, 3-amino Examples include -4-hydroxybenzoic acid, 2- (4-hydroxyphenyl) glycine, m-tyrosine, o-tyrosine, tyrosine, 3-fluoro-tyrosine, 3- (3,4-dihydroxyphenyl) alanine, and the like. In addition, as an amino acid, these things can be used individually or in combination of multiple types.

  On the other hand, amino acids having no reactive organic group include glycine, alanine, aminoheptanoic acid, aminohexanoic acid, aminovaleric acid, aminobutyric acid, aminolauric acid, 2-phenylglycine, 2-fluorophenylalanine, 3- Fluorophenylalanine, homophenylalanine, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3-amino-p-toluic acid, 3-amino-o-toluic acid, 2-amino-m-toluic acid 4-amino-m-toluic acid, 6-amino-m-toluic acid, 6-amino-o-toluic acid, 3,5-dimethylanthranilic acid, p-aminomethylbenzoic acid and the like. These can also be used alone or in combination.

  As mentioned above, although the example of the dicarboxylic acid which has a reactive organic group which is raw material dicarboxylic acid was demonstrated, as such diisocyanate made to react with such raw material dicarboxylic acid, for example, methylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate etc. Is mentioned. As the diisocyanate, only a single compound may be used, or a plurality of types may be used in combination.

  As described above, a suitable polyamide resin is obtained by reacting a raw material dicarboxylic acid containing a dicarboxylic acid having a reactive organic group with a diisocyanate. The raw material dicarboxylic acid has a reactive organic group. In addition to the dicarboxylic acid (first dicarboxylic acid), a dicarboxylic acid (second dicarboxylic acid) having no reactive organic group is preferably included. That is, the polyamide resin is preferably obtained by reacting the first dicarboxylic acid, the second dicarboxylic acid and the diisocyanate. In this case, the blending amount of the diisocyanate used for the reaction may satisfy the above-described suitable blending ratio with respect to the total amount of the first and second dicarboxylic acids. Further, in this case, it is preferable that both the first dicarboxylic acid and the second dicarboxylic acid are soluble in cyclohexanone or methyl ethyl ketone, but at least one, in particular, only the second dicarboxylic acid is soluble. The resulting polyamide resin can be soluble in these solvents.

  The polyamide resin thus obtained includes a structural unit having no reactive organic group derived from the second dicarboxylic acid among the repeating structural units constituting the resin. And when the structural unit which does not have this reactive organic group is contained moderately, when it is not preferable that excessive three-dimensional bridge | crosslinking arises, the excessive formation of three-dimensional bridge | crosslinking is suppressed and suitable sclerosis | hardenability. Can be granted.

  The dicarboxylic acid having no reactive organic group (second dicarboxylic acid) has a structure in which the reactive organic group is removed from the dicarboxylic acid having the reactive organic group (first dicarboxylic acid) described above. Can be mentioned. In particular, when the second dicarboxylic acid is diimide dicarboxylic acid, the diimide dicarboxylic acid is a raw material that does not have any reactive organic group in the above-described production method (1) or (2). What was obtained using can be illustrated.

  When the raw material dicarboxylic acid is composed of the first and second dicarboxylic acids, specifically, the first dicarboxylic acid is a dicarboxylic acid that is not the diimide dicarboxylic acid described above, and the second dicarboxylic acid is a diimide dicarboxylic acid. The combination of is most preferred. When such a combination is used, it becomes easy to adjust the amount and position of the reactive organic group in the obtained polyamide resin, and the desired characteristics tend to be easily obtained. In particular, when the second dicarboxylic acid is diimide dicarboxylic acid, it is obtained by a reaction between a diamine and tricarboxylic acid monoanhydride. As the diamine, an aliphatic diamine, particularly a polypropylene oxide diamine (trade name) If a product using Jeffamine is used, the solubility of the resulting polyamide resin in cyclohexanone or methyl ethyl ketone tends to be extremely good.

  In this case, the molar ratio of the first dicarboxylic acid / second dicarboxylic acid is preferably 1.0 / 0 to 0.01 / 0.99, and 1.0 / 0.0 to 0.05 / 0. 0.95 is more preferable, and 0.5 / 0.5 to 0.1 / 0.9 is even more preferable. By satisfying these ranges, a three-dimensional cross-linking can be satisfactorily generated, and a polyamide resin capable of imparting appropriate curability to the cured product of the resin composition can be obtained.

  Moreover, in manufacture of a polyamide resin, in addition to raw material dicarboxylic acid and diisocyanate, you may further contain the carboxylic acid which has a reactive organic group. The carboxylic acid having a reactive organic group is a compound having one carboxyl group and at least one reactive organic group. The carboxylic acid having a reactive organic group reacts with the terminal portion during the reaction between the raw material dicarboxylic acid and diisocyanate. Accordingly, by further using a carboxylic acid having such a reactive organic group, a polyamide resin having a reactive organic group derived from this compound at the terminal can be obtained. Since such a polyamide resin also has a reactive organic group at the terminal, it can impart further excellent low-temperature curability.

  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 5,5′-thiodisalicylic acid, diphenolic acid, 4- (4-hydroxyphenoxy) benzoic acid, and the like. These can be used alone or in combination of two or more.

(Resin composition)
Next, a preferred embodiment of the resin composition containing the polyamide resin as described above will be described.

  As a resin composition of a preferred embodiment, a resin composition further containing a curing agent, a curing accelerator and a diluent in addition to the polyamide resin is preferable. First, a hardening | curing agent is a component which can react and couple | bond with the reactive group of a polyamide resin, and can form a crosslinked structure in a polyamide resin. As the curing agent, a compound conventionally used as a curing agent can be applied without particular limitation, and an epoxy resin is preferable. 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 thereof, halides, hydrogenated products, and the like. These epoxy resins can be used alone or in combination of two or more.

  The compounding amount of such a curing agent is preferably 1 to 90 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the polyamide resin. When the compounding quantity of this hardening | curing agent is less than 1 mass part with respect to a polyamide resin, it exists in the tendency for the above effects as a hardening | curing agent to become difficult to be acquired. On the other hand, when it exceeds 90 parts by mass, the properties of the curing agent become dominant, and the properties inherent to the polyamide resin may not be sufficiently obtained.

  Moreover, a hardening accelerator is a component which can accelerate | stimulate hardening with a polyamide resin and a hardening | curing agent. By including this curing accelerator, the resin composition is more easily cross-linked, and it becomes possible to obtain sufficient low-temperature curability. Although there is no restriction | limiting in particular as a hardening accelerator, The following compounds can be suitably selected according to the hardening temperature to be used.

  Examples of the curing accelerator include imidazole, 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2 -Phenylimidazoline, naphthimidazole, pyrazole, triazole, tetrazole, indazole, pyridine, pyrazine, pyridazine, pyrimidine, benzotriazole, purine, imidazoline, pyrazoline, quinoline, isoquinoline, dipyri , Diquinolyl, phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, benzoquinoline, benzoisoquinoline, benzocinnoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, carboline, perimidine, triazine, tetrazine, Pteridine, oxazole, benzoxazole, isoxazole, benzoisoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazole, thiadiazole, pyrroldione, isoindoledione, pyrrolidinedione, benzoisoquinolinedione, triethylenediamine, hexa Nitrogenation of methylenetetramine, aminosilane, phenylaminosilane, etc. Thing, and the like. These are preferably selected and blended appropriately according to the curing temperature, and the above may be used 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.

  Moreover, the resin composition can be in a state where 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.

  Furthermore, the resin composition may further include 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 size 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. May be a factor.

  It is preferable that the compounding quantity of the particle | grains in a resin composition shall be 1-90 mass parts with respect to 100 mass parts of polyamide resins, and it is more preferable to set it as 10-50 mass parts. 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 flame retardant can be contained. 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 addition 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.

  Such a resin composition of the present embodiment is usually capable of being cured by heat. For example, the resin composition is photocurable by including a structure or a component that is accelerated by light. May have. In this case, the resin composition may further contain a sensitizer. 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.

  Moreover, it is preferable that it is 0.01-20 mass% with respect to solid content of a resin composition, and, as for the compounding quantity of a sensitizer, 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 above-described components, the resin composition of the present embodiment may further contain a rubber elastomer, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent, and the like depending on desired characteristics.

(Resin composition layer (adhesive layer) and production method thereof)
The above-described resin composition can be applied as a resin composition layer formed in a layer shape. This resin composition layer is formed on, for example, a substrate mounted on an electronic component or the like, and can function as an adhesive layer that adheres the substrate to another substrate laminated thereon. 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 resin composition layer is, for example, a method in which the resin composition is directly applied onto a substrate on which an adhesive layer is to be formed, or a method in which a film (adhesive film) made of the resin composition is formed and then bonded to the substrate. Etc. can be formed.

  In the case of the method of directly applying the resin composition, for example, the resin composition is used as it is or as a solution dissolved in an organic solvent, and this is applied onto a desired surface of the substrate using a spin coater, a multi coater or the like. . Thereafter, the layer formed by coating is heated, or hot air is blown onto the layer to volatilize the diluent and the organic solvent from the layer and remove them. Thereby, the resin composition layer comprised from the resin composition (mainly solid content) is formed.

  On the other hand, in the method using the latter film, a film in which a film made of a resin composition is formed in advance on a predetermined support is prepared, and this film is laminated on the substrate, etc. A composition layer is formed. In this case, the film is applied to the support as it is or as a solution in which the resin composition is dissolved in the solvent as described above, and then the diluent or organic solvent is applied from the layer after application by heating or hot air blowing. Can be formed by volatilizing and removing. The support may be removed from the film before lamination on the substrate or may be removed after lamination.

  Examples of the support used for film formation include films made of polyethylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, tetrafluoroethylene, release paper, or metal foil such as copper foil or aluminum foil. The thickness of the support is not particularly limited, but is preferably 10 to 150 μm. The surface of the support (particularly the surface on which the film of the resin composition is formed) may be subjected to mud treatment, corona treatment, mold release treatment, and the like.

  Such a film can be stored in the state of a single film with the support peeled off or in the state of a laminate in which the film is laminated on the support. Examples of the storage method include a method of cutting a film or a laminate into a predetermined length and storing it in a sheet form, and a method of further winding it and storing it in a roll form. From the viewpoints of storage stability, productivity, and workability, it is preferable that the laminate is further covered with a protective film to be protected, and then wound into a roll and stored. 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.

  The substrate on which the above-described resin composition layer 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, an inorganic material such as ceramic or glass can be applied. Further, for example, a substrate in which a wiring made of metal is formed on an insulating substrate made of resin may be used.

  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, for example, by heating the resin composition layer. Further, depending on the type of polyamide resin or the like contained in the resin composition, it can also be generated by light irradiation. In the case of curing by heating, the suitable temperature varies depending on the presence or absence of the effect accelerator in the resin composition and the type thereof, but setting it to 130 to 230 ° C. can reduce deterioration of the properties of the cured 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, 60.0 mmol of Jeffamine D400 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, 123.0 mmol of trimellitic anhydride, aprotic As a polar solvent, 144.9 g of N-methyl-2-pyrrolidone (NMP) was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 15.0 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After dissolving 3 mmol, 82.5 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, and the temperature was raised to 160 ° C. 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, 30.0 mmol of Jeffamine D2000 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, 61.5 mmol of trimellitic anhydride, aprotic As a polar solvent, 169.9 g of N-methyl-2-pyrrolidone (NMP) was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 7.5 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After 1 mmol was dissolved, 41.3 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, and the temperature was raised to 160 ° C. 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, thermometer, and stirrer, 67.5 mmol of Jeffamine D400 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, 138.4 mmol of trimellitic anhydride, aprotic 148.6 g of N-methyl-2-pyrrolidone (NMP) was added as a polar solvent, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 16.9 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After 5 mmol was dissolved, 92.8 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 3. It was.

Example 4
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 82.5 mmol of Jeffamine D230 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, 169.1 mmol of trimellitic anhydride, aprotic As a polar solvent, 153.2 g of N-methyl-2-pyrrolidone (NMP) was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  2. After cooling the solution in the flask to room temperature (25 ° C.), 20.6 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group After 1 mmol was dissolved, 113.4 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 4. It was.

(Example 5)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, 63.0 mmol of Jeffamine D400 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, 129.2 mmol of trimellitic anhydride, aprotic As a polar solvent, 147.4 g of N-methyl-2-pyrrolidone (NMP) was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 27.0 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After 7 mmol was dissolved, 99.0 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 5. It was.

(Example 6)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, 75.0 mmol of Jeffamine D230 (manufactured by Mitsui Chemicals Fine) as a diamine compound, 153.8 mmol of trimellitic anhydride, aprotic As a polar solvent, 149.6 g of N-methyl-2-pyrrolidone (NMP) was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 32.1 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group After 2 mmol was dissolved, 117.9 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 6. It was.

(Example 7)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, Jeffamine D400 (Mitsui Chemical Fine Co., Ltd.) 56.3 mmol as a diamine compound, m-TB-HG (Wakayama Seika Kogyo Co., Ltd.) 18.8 mmol, 153.8 mmol of trimellitic anhydride, 158.0 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 18.8 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After dissolving 8 mmol, as a diisocyanate, 103.1 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added, the temperature was raised to 160 ° C. and reacted for 2 hours to obtain an NMP solution of the polyamide resin of Example 7 It was.

(Example 8)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 37.5 mmol of Jeffamine D400 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, m-TB-HG (Wakayama Seika Kogyo Co., Ltd.) 37.5 mmol, trimellitic anhydride 153.8 mmol, and 150.9 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 18.8 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After 8 mmol was dissolved, 103.1 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 8. It was.

Example 9
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 20.6 mmol of Jeffamine D400 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, m-TB-HG (Wakayama Seika Kogyo Co., Ltd.) (Company) 61.9 mmol, trimellitic anhydride 169.1 mmol, N-methyl-2-pyrrolidone (NMP) 158.1 g as an aprotic polar solvent was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  2. After cooling the solution in the flask to room temperature (25 ° C.), 20.6 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group After 1 mmol was dissolved, 113.4 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 9. It was.

(Example 10)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 37.5 mmol of Jeffamine D400 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, m-TB-HG (Wakayama Seika Kogyo Co., Ltd.) (Company) 37.5 mmol, trimellitic anhydride 153.8 mmol, N-methyl-2-pyrrolidone (NMP) 161.2 g as an aprotic polar solvent was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 32.1 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group After 2 mmol was dissolved, 117.9 mol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 10. It was.

(Example 11)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 67.5 mmol of Jeffamine D230 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, m-TB-HG (Wakayama Seika Kogyo Co., Ltd.) 67.5mmol, 276.8mmol of trimellitic anhydride, and 266.8g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, and 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 57.9 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group After 8 mmol was dissolved, 212.1 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Example 11 It was.

(Comparative Example 1)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 70.5 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine compound, trimellitic anhydride 148 0.1 mmol, 169.8 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 110 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 17.6 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After 6 mmol was dissolved, 105.8 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Comparative Example 1.

(Comparative Example 2)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 67.5 mmol of TPE-R (manufactured by Wakayama Seika Kogyo Co., Ltd.) as a diamine compound, 141.8 mmol of cyclohexanetricarboxylic acid anhydride, non As a protic polar solvent, 145.2 g of N-methyl-2-pyrrolidone (NMP) was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 110 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 16.9 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After 2 mmol was dissolved, 92.8 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, the temperature was raised to 160 ° C., and the mixture was reacted for 2 hours to obtain an NMP solution of the polyamide resin of Comparative Example 2.

(Comparative Example 3)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 67.5 mmol of LP-7100 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a diamine compound, 138.4 mmol of trimellitic anhydride, aprotic 136.0 g of N-methyl-2-pyrrolidone (NMP) was added as a 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 16.9 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After 5 mmol was dissolved, 92.8 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Comparative Example 3.

(Comparative Example 4)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 67.5 mmol of Jeffamine D230 (Mitsui Chemical Fine Co., Ltd.) as a diamine compound, m-TB-HG (Wakayama Seika Kogyo Co., Ltd.) 67.5 mmol, trimellitic anhydride 276.8 mmol and 299.6 g of N-methyl-2-pyrrolidone (NMP) 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 57.9 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group After 8 mmol was dissolved, 212.1 mmol of 4,4′-diphenylmethane diisocyanate was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of a polyamide resin of Comparative Example 4.

(Comparative Example 5)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 56.3 mmol of Jeffamine D230 (manufactured by Mitsui Chemicals Fine) as a diamine compound, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane 56.3 mmol, trimellitic anhydride 230.6 mmol, N-methyl-2-pyrrolidone (NMP) 272.3 g as an aprotic polar solvent was added, and the temperature was raised to 80 ° C. for 30 minutes. Stir.

  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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 48.2 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group, and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group. After dissolving 8 mmol, as a diisocyanate, 176.8 mmol of 4,4′-diphenylmethane diisocyanate was added, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of the polyamide resin of Comparative Example 5.

(Comparative Example 6)
In a 1000 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, Jeffamine D230 (made by Mitsui Chemicals Fine) 60.0 mmol as a diamine compound, TPE-R (made by Wakayama Seika Kogyo Co., Ltd.) ) 60.0 mmol, trimellitic anhydride 246.0 mmol, 276.0 g of N-methyl-2-pyrrolidone (NMP) 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  After cooling the solution in the flask to room temperature (25 ° C.), 51.4 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group After dissolving 1 mmol, as a diisocyanate, 188.6 mmol of 4,4′-diphenylmethane diisocyanate was added, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of polyamide resin of Comparative Example 6.

(Comparative Example 7)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 82.5 mmol of m-TB-HG (manufactured by Wakayama Seika Kogyo Co., Ltd.) as a diamine compound, 169.1 mmol of trimellitic anhydride, As an aprotic polar solvent, 146.5 g of N-methyl-2-pyrrolidone (NMP) was added, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes.

  After the completion of stirring, 120 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

  2. After cooling the solution in the flask to room temperature (25 ° C.), 20.6 mmol of 5-hydroxyisophthalic acid as a dicarboxylic acid having a reactive organic group and 2,4-dihydroxybenzoic acid as a carboxylic acid having a reactive organic group After 1 mmol was dissolved, 113.4 mmol of Coronate T-80 (manufactured by Nippon Polyurethane Industry) was added as a diisocyanate, and the temperature was raised to 160 ° C. for 2 hours to obtain an NMP solution of polyamide resin of Comparative Example 7. It was.

(Comparative Example 8)
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, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 1500) 9 mmol, trimellitic anhydride 378 mmol, 424.7 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent was added, and the temperature was 80 ° C. The mixture was warmed to 30 minutes 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 water is no longer being distilled, remove the water and toluene in the moisture determination receiver and raise the temperature to 180 ° C to react the reaction solution. The toluene in it was removed.

After cooling the solution in the flask to room temperature (25 ° C.), 198 mmol of 4-4′-diphenylmethane diisocyanate was added as the diisocyanate, the temperature was raised to 150 ° C., and the reaction was performed for 2 hours. Got.
[Evaluation of polyamide resin]

(Measurement of molecular weight)
Table 1 shows the weight average molecular weights (MW: polystyrene equivalent) of the polyamides of Examples 1 to 11 and Comparative Examples 1 to 8. In addition, the measurement of a weight average molecular weight (polystyrene conversion) uses what connected two GL-S300MDT-5 (made by Hitachi Chemical Co., Ltd.) in series as a measurement column, and used 1 L of dimethylformamide for liquid chromatography as an eluent. Then, 0.03 mol of lithium bromide monohydrate and 0.06 mol of phosphoric acid were added and dissolved, followed by addition of 1 L of tetrahydrofuran for liquid chromatography.

(Evaluation of solubility of polyamide resin in various solvents)
The NMP solutions of the polyamide resins of Examples 1 to 11 and Comparative Examples 1 to 8 were collected by precipitation filtration with a poor solvent and then dried with a vacuum dryer. 1 g of the obtained resin was dissolved in 1 g of the solvent shown in Table 2. Table 2 shows the solubility of the polyamide resin in various solvents. In the table, ◯ indicates the case where the polyamide resin is completely dissolved in the target solvent, and x indicates the case where the polyamide resin cannot be dissolved in the target solvent.

As shown in Table 2, the polyamide resins of Examples 1 to 11 showed good solubility in either cyclohexanone or methyl ethyl ketone. In contrast, the polyamide resins of Comparative Examples 1 to 8 did not dissolve in either cyclohexanone or methyl ethyl ketone.
[Preparation of resin composition]

(Example 12)
0.75 g of NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) and 0.0075 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator are added to 25 g of the NMP solution of polyamide resin of Example 1. The resin composition was prepared.

(Example 13)
After the polyamide resin of Example 3 was collected by precipitation with a poor solvent, 7 g of the resin obtained by vacuum drying was dissolved in 18.16 g of methyl ethyl ketone, and NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) And 0.777 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator were arranged to prepare a resin composition.

(Example 14)
After the polyamide resin of Example 4 was collected by precipitation filtration with a poor solvent, 12.27 g of cyclohexanone and 3.07 g of methyl ethyl ketone were added and dissolved in 9 g of the resin obtained by vacuum drying, and NC-3000H (Nipponization) 1.22 g (trade name, manufactured by Yakuhin Co., Ltd.) and 0.012 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator were arranged to prepare a resin composition.

(Example 15)
After the polyamide resin of Example 5 was collected by precipitation filtration using a poor solvent, 12.61 g of cyclohexanone and 3.15 g of methyl ethyl ketone were added to and dissolved in 9 g of the resin obtained by vacuum drying. 1.49 g (trade name, manufactured by Yakuhin Co., Ltd.) and 0.015 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator were arranged to prepare a resin composition.

(Example 16)
After the polyamide resin of Example 6 was collected by precipitation filtration using a poor solvent, 12.99 g of cyclohexanone and 3.25 g of methyl ethyl ketone were added and dissolved in 9 g of the resin obtained by vacuum drying, and NC-3000H (Nipponization) 1.80 g (trade name, manufactured by Yakuhin Co., Ltd.) and 0.018 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator were disposed to prepare a resin composition.

(Example 17)
After the polyamide resin of Example 7 was collected by precipitation filtration with a poor solvent, 12.07 g of cyclohexanone and 3.02 g of methyl ethyl ketone were added and dissolved in 9 g of the resin obtained by vacuum drying, and NC-3000H (Nipponization) 1.05 g (trade name, manufactured by Yakuhin Co., Ltd.) and 0.010 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator were arranged to prepare a resin composition.

(Example 18)
After the polyamide resin of Example 8 was collected by precipitation filtration with a poor solvent, 12.14 g of cyclohexanone and 3.04 g of methyl ethyl ketone were added and dissolved in 9 g of the resin obtained by vacuum drying, and NC-3000H (Nipponization) 1.11 g (trade name, manufactured by Yakuhin Co., Ltd.) and 0.011 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator were arranged to prepare a resin composition.

(Example 19)
After the polyamide resin of Example 10 was collected by precipitation filtration using a poor solvent, 12.80 g of cyclohexanone and 3.20 g of methyl ethyl ketone were added to and dissolved in 9 g of the resin obtained by vacuum drying, and NC-3000H (Nipponization) 1.65 g (trade name, manufactured by Yakuhin Co., Ltd.) and 0.016 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator were arranged to prepare a resin composition.

(Example 20)
After the polyamide resin of Example 11 was collected by precipitation filtration using a poor solvent, 13.01 g of cyclohexanone and 3.25 g of methyl ethyl ketone were added and dissolved in 9 g of the resin obtained by vacuum drying, and NC-3000H (Nipponization) 1.82 g (trade name, manufactured by Yakuhin Co., Ltd.) and 0.018 g of 2PZ-CNS (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an accelerator were disposed to prepare a resin composition.

(Comparative Example 9)
NC-3000H (Nippon Kayaku Co., Ltd. trade name) 0.87g and 2PZ-CNS (Shikoku Kasei Kogyo Co., Ltd. trade name) 0.0087g as an accelerator to 30g of NMP solution of polyamide resin of Comparative Example 3 The resin composition was prepared.

(Comparative Example 10)
NC-3000H (Nippon Kayaku Co., Ltd. trade name) 1.04 g and 2PZ-CNS (Shikoku Kasei Kogyo Co., Ltd. trade name) 0.010 g as an accelerator to 25 g of NMP solution of polyamide resin of Comparative Example 7 The resin composition was prepared.

(Comparative Example 11)
NC-3000H (Nippon Kayaku Co., Ltd. trade name) 1.58 g and 2PZ-CNS (Shikoku Kasei Kogyo Co., Ltd. trade name) 0.016 g as an accelerator to 30 g of NMP solution of polyamide resin of Comparative Example 8 The resin composition was prepared.
[Production of resin film]

The resin composition solutions prepared in Examples 12 to 20 and Comparative Examples 9 to 11 were uniformly applied onto PET and dried at 100 ° C. for 15 minutes. The film was peeled from PET to obtain a resin film.
[Measurement of DSC]

50-350 degreeC of each resin film (5 mg) obtained from the resin composition of Examples 13-17, 19 and Comparative Example 11 using a differential scanning calorimeter (DSC: PYRIS1 DSC by Perkin Elma). The calorific value (J / g) and the exothermic temperature (° C.) were measured in the temperature range (temperature increase of 10 ° C./min). The obtained results are shown in Table 3. The temperature is a temperature indicating the maximum calorific value.

[Measurement of Tg]

The resin films obtained from the resin compositions of Examples 12 to 20 and Comparative Examples 9 to 11 were further heated at 200 ° C. for 1 hour to obtain cured films. Then, using a thermomechanical analyzer TMA-4000 manufactured by Mac Science Co., Ltd., corresponding to Examples 12 to 20 and Comparative Examples 9 to 11 by a heating rate of 5 ° C./min, a measurement length of 15 mm, a load of 5 g, and a tension method. The Tg (TMA) of the cured film was determined. The inflection point of the temperature-thermal expansion curve is Tg, and the results are shown in Table 4.

[Measurement of dynamic viscoelasticity]

  The resin films obtained from the polyamide resin compositions of Examples 12 and 13 and Comparative Examples 9 to 11 were further heated at 200 ° C. for 1 hour to obtain cured films.

Using a dynamic viscoelasticity measuring device (DVE: Wide-area dynamic viscoelasticity measuring device E-4000 manufactured by UBM Co., Ltd.), a temperature rising rate of 5 ° C./min, a distance between chucks of 20 mm, a frequency of 10 Hz, an amplitude of 5 μm, and an automatic static load The maximum value (Tg (DVE)) of tan δ in the temperature range of 50 to 350 ° C. of the polyamide films of Examples 12 to 20 and Comparative Examples 9 to 11 was determined by a tensile method. The results obtained are shown in Table 5.

  As shown in Tables 3 to 5, the polyamide film obtained using the resin composition corresponding to the examples of the present invention has a clear exothermic peak, and the curing proceeds efficiently by the reactive organic group. It was confirmed that Moreover, Tg was low compared with the thing of the comparative example.

From the above, it was confirmed that the polyamide resin having a reactive organic group in the side chain of the present invention can provide a polyamide resin having sufficiently high heat resistance and good film forming properties. Further, it has been found that the resin composition containing the polyamide resin having a reactive organic group in the side chain of the present invention can be efficiently cured even at a low temperature.

Claims (10)

  A polyamide resin which is soluble in cyclohexanone or methyl ethyl ketone and has a main chain containing an amide bond and a side chain containing a reactive organic group bonded to the main chain.   The polyamide resin according to claim 1, comprising a plurality of the side chains.   3. The polyamide resin according to claim 1, wherein the reactive organic group is a phenolic hydroxyl group.   The polyamide resin according to any one of claims 1 to 3, which is obtained by a reaction between a raw material dicarboxylic acid containing a dicarboxylic acid having a reactive organic group and a diisocyanate.   2. A product obtained by reacting a diisocyanate with a raw material dicarboxylic acid comprising a first dicarboxylic acid having a reactive organic group and a second dicarboxylic acid not having a reactive organic group. The polyamide resin as described in any one of -4.   6. The polyamide resin according to claim 5, wherein the first dicarboxylic acid / the second dicarboxylic acid has a molar ratio in the range of 1.0 / 0 to 0.01 / 0.99.   The polyamide resin according to any one of claims 4 to 6, wherein the raw material dicarboxylic acid is soluble in cyclohexanone or methyl ethyl ketone.   The polyamide resin according to any one of claims 4 to 7, obtained by reacting 0.7 to 1.3 equivalents of diisocyanate with the raw material dicarboxylic acid.   A resin composition comprising the polyamide resin according to claim 1.   The resin composition according to claim 9, which is curable.