JP2009108307A - Curable resin composition and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition capable of forming a cured product having favorable solvent resistance, and to provide an electronic component containing the cured product of the curable resin composition. <P>SOLUTION: The curable resin composition comprises a polyamide-imide resin, an epoxy resin and a curing accelerator, wherein the product, in which the amount dissolved in N-methyl-2-pyrrolidone at 25°C is ≤3.0 g per 1 m<SP>2</SP>of a surface area, is formed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable resin composition and an electronic component.

  Polyamideimide resins are widely used in electronic material applications. For example, an insulating film used as an electronic material can be obtained by mixing a polyamideimide resin with a curing agent or the like to obtain a curable resin composition and curing it.

  As a method for producing a polyamide-imide resin, a direct polymerization method in which a polyvalent amine is reacted with a polyvalent carboxylic acid (see Patent Document 1), or an acid chloride method in which a diamine is reacted with trimellitic anhydride chloride (Patent Document) 2 and 3) are known. According to the direct polymerization method, it may be necessary to separate the resin and the catalyst after the polymerization, and according to the acid chloride method, it may be necessary to separate the resin from the by-product chloride after the polymerization.

  On the other hand, an isocyanate method in which a dicarboxylic acid and a diisocyanate are reacted is also known as a method for producing a polyamideimide resin (see Patent Document 4). According to the isocyanate method, it is not necessary to add a catalyst, and since the by-product is a gas, it is not necessary to separate the resin from the catalyst or the by-product after polymerization. In this respect, the isocyanate method is more productive than the direct polymerization method or the acid chloride method.

Patent Document 5 discloses a polyamide-imide resin having an unsaturated bond at the molecular end obtained by polymerization of diamine and maleic anhydride, and Patent Document 6 discloses a diamine having a carbonyl compound and a phenolic hydroxyl group. And a polyamide-imide resin containing a phenolic hydroxyl group, obtained by directly reacting the above with a polymerization method.
JP 2001-270939 A Japanese Patent Publication No. 4-018562 Japanese Patent Publication No. 61-44928 JP-A-6-172516 Japanese Patent No. 2582636 JP 2004-91734 A

  However, a curable resin composition containing a polyamideimide resin produced by a conventional method may not have sufficient solvent resistance when used as a cured product.

  Then, an object of this invention is to provide the curable resin composition which can form hardened | cured material with favorable solvent resistance. Another object of the present invention is to provide an electronic component containing a cured product of the curable resin composition.

The present invention is a curable resin composition comprising a polyamideimide resin, an epoxy resin, and a curing accelerator, and the amount dissolved in N-methyl-2-pyrrolidone at 25 ° C. is 3 per 1 m ^{2 of} surface area. It is a curable resin composition that forms a cured product of 0.0 g or less. When the curable resin composition according to the present invention is heated, curing proceeds efficiently, and a cured product having good solvent resistance and heat resistance is formed. This cured product has a solubility in N-methyl-2-pyrrolidone at 25 ° C. of not more than 3.0 g / m ^{2 of} surface area, that is, a solubility in N-methyl-2-pyrrolidone at 25 ° C. of 3.0 g / m. ² or less.

  It is preferable that the compounding quantity of an epoxy resin is 10-15 mass parts with respect to 100 mass parts of polyamideimide resins. When the compounding amount of the epoxy resin is less than the above lower limit, a sufficiently good solvent resistance tends to be hardly obtained. On the other hand, when the compounding amount of the epoxy resin is larger than the above upper limit, characteristics such as Tg of the cured product tend to be insufficient due to an increase in unreacted epoxy groups. Moreover, when there are more compounding quantities of an epoxy resin than the said upper limit, when hardened | cured material contacts a solvent, there exists a tendency for it to become easy to swell. When the cured product swells, inconveniences such as poor dimensional stability may occur.

  The polyamideimide resin is preferably obtained by a reaction between a carbonyl compound containing a carboxylic acid and / or an acid anhydride and a diisocyanate. When a polyamideimide resin is produced by a method of reacting a carboxylic acid and / or an acid anhydride with a diisocyanate (isocyanate method), a catalyst is unnecessary and the by-product is a gas. There is no need to separate the product. In this respect, the isocyanate method is more productive than the direct polymerization method or the acid chloride method.

  The polyamideimide resin preferably has a phenolic hydroxyl group. Thereby, the epoxy group contained in the epoxy resin reacts with the phenolic hydroxyl group contained in the polyamideimide resin to form a crosslinked structure, and the curing proceeds more efficiently.

  In another aspect, the present invention is an electronic component comprising a cured product of the curable resin composition. As such an electronic component, for example, a printed wiring board including an insulating film made of the above-described cured product can be cited.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which can form hardened | cured material with favorable solvent resistance, and the electronic component containing the hardened | cured material can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The curable resin composition according to an embodiment of the present invention includes a polyamideimide resin, an epoxy resin, and a curing accelerator. When the curable resin composition having such a structure is heated, curing proceeds efficiently, and a cured product having good solvent resistance and heat resistance is formed. This cured product preferably has a solubility in N-methyl-2-pyrrolidone at 25 ° C. of 3.0 g / m ² or less.

  The polyamideimide resin preferably has a phenolic hydroxyl group. Thereby, the epoxy group contained in the epoxy resin reacts with the phenolic hydroxyl group contained in the polyamideimide resin to form a crosslinked structure, and the curing proceeds more efficiently. For example, the polyamideimide resin according to the present embodiment includes a structural unit represented by the following general formula (1). In the formula, R represents a divalent organic group having a phenolic hydroxyl group.

  That is, the polyamide-imide resin according to the present embodiment includes a main chain having an amide group and an imide group, and a side chain bonded to the main chain, and the side chain may have a phenolic hydroxyl group. . As shown in Formula (1), the phenolic hydroxyl group is often derived from a compound having a carbonyl group (carbonyl compound).

  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.

  The polyamide-imide resin preferably includes a plurality of side chains having a phenolic hydroxyl group in the molecule. By including a plurality of such side chains having a reactive organic group in the molecule, three-dimensional crosslinking is more likely to occur, and a cured product having good heat resistance can be formed.

  The polyamideimide resin according to this embodiment is obtained by an isocyanate method in which a carbonyl compound containing a carboxylic acid and / or an acid anhydride is reacted with a diisocyanate. According to the isocyanate method, since no catalyst is required and the by-product is a gas, an operation for separating the product from the catalyst and the by-product after the reaction is not necessary. In addition, according to the isocyanate method, no catalyst is used, the by-product is a gas, and no separation operation is performed, so that contamination of solid impurities, metallic impurities, ionic impurities and other impurities can be minimized. In addition, it is possible to prevent appearance defects and performance degradation due to the mixing of impurities.

  The carbonyl compound includes, for example, a dicarboxylic acid having a phenolic hydroxyl group and at least one compound having no phenolic hydroxyl group selected from the group consisting of dicarboxylic acid, tricarboxylic acid monoanhydride and tetracarboxylic acid dianhydride. Any of the carbonyl compounds selected from these compounds has an imide group and / or an acid anhydride group.

  When such a carbonyl compound is reacted with a diisocyanate, the resulting polyamideimide resin is derived from a structural unit derived from a dicarboxylic acid having a phenolic hydroxyl group, a structural unit derived from a compound having no phenolic hydroxyl group, and a diisocyanate. The structural unit to be included is included. Each structural unit is repeatedly bonded via an amide bond or an imide bond formed at the ends of these structural units.

  In the polyamideimide resin, the amide bond is generated by a reaction between a carboxyl group contained in the dicarboxylic acid and / or tricarboxylic acid monoanhydride contained in the carbonyl compound and an isocyanate group contained in the diisocyanate. On the other hand, an imide bond is generated by a reaction between an acid anhydride group possessed by tricarboxylic acid monoanhydride and / or tetracarboxylic dianhydride and an isocyanate group possessed by diisocyanate. Moreover, the said polyamideimide resin may contain the imide bond derived from the imide group which the imide dicarboxylic acid which is a carbonyl compound which has an imide group and a carboxyl group has.

  When the carbonyl compound includes not only a dicarboxylic acid having a phenolic hydroxyl group but also a compound not having a phenolic hydroxyl group, the resulting polyamideimide resin appropriately includes a side chain having a phenolic hydroxyl group. . Curability suitable for the resin composition by suppressing excessive formation of the three-dimensional crosslink when it is not preferable that excessive three-dimensional crosslinkage is caused by appropriately including a side chain having a phenolic hydroxyl group. To prevent the resin composition from being excessively cured and becoming brittle. It is also possible to adjust solvent resistance, heat resistance and the like using a specific compound having no phenolic hydroxyl group.

  At this time, the molar ratio (A / B) of the dicarboxylic acid (A) having a phenolic hydroxyl group and the compound (B) having no phenolic hydroxyl group contained in the carbonyl compound is 0.99 / 0.01-0. The range is preferably 0.01 / 0.99, more preferably 0.75 / 0.25 to 0.1 / 0.9. Thereby, the three-dimensional bridge | crosslinking produces favorably and the polyamide imide resin which can provide moderate sclerosis | hardenability to a resin composition is obtained.

  In the polyamideimide resin according to the present embodiment, the carbonyl compound is reacted with 0.7 to 1.3 equivalent (molar equivalent) of a diisocyanate with respect to the total amount of acid anhydride group and carboxyl group contained in the carbonyl compound. It is preferable that it is obtained by reacting with 1.0 to 1.2 equivalents of diisocyanate. By setting the amount of diisocyanate to be reacted in the above range, a polyamideimide resin having a large molecular weight and having good strength and heat resistance when cured as a resin composition can be obtained. When the amount of diisocyanate to be reacted with respect to the carbonyl compound is less than 0.7 equivalent, unreacted carbonyl compound tends to remain, and the properties of the resulting polyamideimide resin tend to be insufficient. On the other hand, when the amount of diisocyanate exceeds 1.3 equivalents, unreacted diisocyanate tends to remain, and the molecular weight and heat resistance of the resulting polyamideimide resin tend to be insufficient, or conversely, the obtained polyamideimide resin is high. By increasing the molecular weight, the handleability tends not to be sufficiently good.

  The reaction between the carbonyl compound and the diisocyanate is preferably performed at 100 ° C. or higher, and more 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-imide 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 is possible to generate the polyamideimide resin more efficiently. In addition, when a catalyst is used, the reaction proceeds sufficiently even when the reaction temperature is less than 100 ° C., so that side reactions and the like caused by high temperature conditions can be significantly suppressed.

  The dicarboxylic acid having a phenolic hydroxyl group is a compound having two carboxyl groups and at least one phenolic hydroxyl group. In the compound, the phenolic hydroxyl 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.

  Examples of the dicarboxylic acid having a phenolic hydroxyl group include 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, methylenedisalicylic acid, pamoic acid, and 5,5′-thiodisalicylic acid. These can be used alone or in combination of two or more.

  The dicarboxylic acid having a phenolic hydroxyl group may be an imidodicarboxylic acid obtained by reacting an amino acid having a phenolic hydroxyl group with tricarboxylic acid monoanhydride and / or tetracarboxylic acid dianhydride. The imidodicarboxylic acid having a phenolic hydroxyl group has at least one phenolic hydroxyl group and at least one imide group in a constituent unit between two carboxyl groups. For example, an imidodicarboxylic acid having a phenolic hydroxyl group can be obtained by reacting an amino acid having a phenolic hydroxyl group with 1 equivalent of tricarboxylic acid monoanhydride or 0.5 equivalent of tetracarboxylic acid dianhydride.

  Examples of amino acids having a phenolic hydroxyl group include 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 4-amino-3-hydroxybenzoic acid, 3-hydroxyanthranilic acid, 5-hydroxyanthranilic acid, 3-amino- 4-hydroxybenzoic acid, 2- (4-hydroxyphenyl) glycine, m-tyrosine, o-tyrosine, tyrosine, 3-fluoro-tyrosine, 3- (3,4-dihydroxyphenyl) alanine and the like. These can be used alone or in combination of two or more.

  Examples of tricarboxylic acid monoanhydrides include trimellitic anhydride and cyclohexanetricarboxylic acid anhydride, and these can be used alone or in combination. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 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 dianhydride 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 1-trifluoro Methyl-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-dicarboxyphenyl) ether dianhydride, Benze -1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3-benzophenone tetracarboxylic dianhydride 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) Methylphenylsilane Anhydride, 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-butanetetracarboxylic Acid 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, , 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) 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 can be used alone or in combination of two or more.

  Examples of the dicarboxylic acid having no phenolic hydroxyl group include isophthalic acid, terephthalic acid, adipic acid, and sebacic acid. These can be used alone or in combination of two or more. Further, the dicarboxylic acid having no phenolic hydroxyl group may be an imide dicarboxylic acid having an imide group in a structural unit between two carboxyl groups.

  The imidodicarboxylic acid not having a phenolic hydroxyl group includes an amino compound having no phenolic hydroxyl group containing a diamine and / or an amino acid, includes a tricarboxylic acid monoanhydride and / or a tetracarboxylic acid dianhydride, and is included in the amino compound. It is obtained by reacting with an acid anhydride having no phenolic hydroxyl group selected so as to contain one acid anhydride group and two carboxyl groups with respect to the amino group. At this time, an imide bond is generated by a reaction between the amino group contained in the amino compound and the acid anhydride group contained in the acid anhydride.

An imidodicarboxylic acid having no phenolic hydroxyl group can be obtained, for example, by the following methods (1) to (4).
(1) A diamine having no phenolic hydroxyl group is reacted with 2 equivalents of tetracarboxylic dianhydride or tricarboxylic monoanhydride with respect to the diamine.
(2) A diamine having no phenolic hydroxyl group is reacted with tetracarboxylic dianhydride and tricarboxylic acid monoanhydride. For example, a diamine having no phenolic hydroxyl group is reacted with 0.5 equivalent of tetracarboxylic dianhydride with respect to the diamine, and then reacted with 1 equivalent of tricarboxylic acid monoanhydride with respect to the diamine.
(3) An amino acid having no phenolic hydroxyl group is reacted with 1 equivalent of tricarboxylic acid monoanhydride with respect to the amino acid.
(4) An amino acid having no phenolic hydroxyl group is reacted with 0.5 equivalent of tetracarboxylic dianhydride with respect to the amino acid.
Note that the tetracarboxylic dianhydride and tricarboxylic monoanhydride used in the above (1) to (4) do not have any phenolic hydroxyl group.

  Examples of the diamine having no phenolic hydroxyl group include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4-amino). Phenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-amino) Phenoxy) 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 (trifluoro) Methyl) 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) diphenyl sulfone, (4,4'-diamino) benzophenone, (3,3'-diamino) benzophenone, (4,4' -Diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, aromatic diamines such as (3,3′-diamino) diphenyl ether, (4,4′-diamino) dicyclohexylmethane, polypropylene oxide diamine (trade name Jeffamine) Aliphatic diamines such as polydimethylsiloxane diamine (silicone oil X-22-161AS (amine equivalent 4 50), 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 Examples thereof include siloxane diamine such as -8010 (amine equivalent 415) (manufactured by Shin-Etsu Chemical Co., Ltd.) These can be used alone or in combination of two or more.

  Amino acids having no phenolic hydroxyl group include glycine, alanine, aminoheptanoic acid, aminohexanoic acid, aminovaleric acid, aminobutyric acid, aminolauric acid, 2-phenylglycine, 2-fluorophenylalanine, 3-fluorophenylalanine, homo Phenylalanine, 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 be used alone or in combination of two or more.

  As mentioned above, although the method of obtaining the imide dicarboxylic acid which does not have a phenolic hydroxyl group was illustrated, the method of obtaining the imide dicarboxylic acid which does not have a phenolic hydroxyl group is not limited to these.

  Examples of the diisocyanate include methylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, and the like. These can be used alone or in combination of two or more.

  The carbonyl compound to be reacted with the diisocyanate may further contain a carboxylic acid having one carboxyl group in the molecule. The carboxylic acid may or may not have a phenolic hydroxyl group, but preferably has a phenolic hydroxyl group. This carboxylic acid is bonded to the terminal portion of the polyamideimide resin during the reaction with the diisocyanate. Therefore, by using such a carboxylic acid, a polyamideimide resin further having a structural unit derived from the carboxylic acid can be obtained. In this case, it is preferable to use a carboxylic acid having a phenolic hydroxyl group, because it has a phenolic hydroxyl group at the terminal, which makes it possible to obtain a polyamideimide resin that is more likely to cause three-dimensional crosslinking.

  Examples of the carboxylic acid having a phenolic hydroxyl group include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, and 2,6-dihydroxybenzoic acid. Acid, 3,5-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 2,3,5-trihydroxybenzoic 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-hydroxy -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.

  Examples of the carboxylic acid having no phenolic hydroxyl group include carboxylic acids having a structure obtained by removing the phenolic hydroxyl group from the carboxylic acid having the phenolic hydroxyl group.

  The curable resin composition according to this embodiment includes an epoxy resin as a curing agent in addition to the polyamideimide resin as described above. Thereby, the epoxy group contained in the epoxy resin reacts with the phenolic hydroxyl group contained in the polyamide-imide resin, and three-dimensional crosslinking is likely to occur, and the solvent resistance of the cured product is improved.

  It is preferable that the compounding quantity of an epoxy resin is 10-15 mass parts with respect to 100 mass parts of polyamideimide resins. Moreover, it is preferable to mix | blend the compounding quantity of an epoxy resin so that it may have an epoxy group of 0.6-3.0 equivalent with respect to the hydroxyl group of the polyamide-imide resin which has a phenolic hydroxyl group, and 0.9-2. More preferably, it is 0 equivalent. When the compounding amount of the epoxy resin is less than the above lower limit, a sufficiently good solvent resistance tends to be hardly obtained. On the other hand, when the compounding amount of the epoxy resin is larger than the above upper limit, characteristics such as Tg of the cured product tend to be insufficient due to an increase in unreacted epoxy groups.

  Epoxy resins include 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 epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, bisphenol A novolac epoxy resin, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenol, alcohol Diglycidyl etherified compounds, alkyl substituted products, halides, hydrogenated products and the like thereof. These epoxy resins can be used alone or in combination of two or more.

  The curable resin composition according to the present embodiment may include a further curing agent in addition to the epoxy resin. The curing agent is a component that can react with and bond to the polyamideimide resin, and can form a crosslinked structure in the polyamideimide resin. As the curing agent, a compound conventionally used as a curing agent can be applied without particular limitation.

  Furthermore, the curable resin composition according to the present embodiment includes a curing accelerator. A hardening accelerator is a component which can accelerate | stimulate hardening with a polyamide-imide resin and an epoxy resin. By including this curing accelerator, crosslinking is more likely to occur in the resin composition.

  The blending amount of the curing accelerator is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin, and 0.95 to 1.2 parts by mass. Part is more preferable. If the blending amount of the curing accelerator is less than the above lower limit, sufficiently good solvent resistance tends to be difficult to obtain, and if more than the above upper limit, the amount of the unreacted curing accelerator increases, There is a tendency that characteristics such as Tg are not sufficient.

  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 , Nitrogen-containing compounds such as aminosilane and phenylaminosilane It is. These are preferably selected and blended appropriately according to the curing temperature, and can be used alone or in combination of two or more.

  The curable resin composition may further contain a diluent. By including the diluent, the polyamideimide resin, the epoxy resin, the curing accelerator and the like are dissolved or dispersed, and the working efficiency is improved. The diluent is not particularly limited, but 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 and the like can be mentioned. These can be used alone or in combination of two or more.

  The curable resin composition may further include particles such as inorganic particles. By including the particles, the thermal expansion coefficient and electrical characteristics of the resin composition and its cured product can be improved. As such particles, inorganic particles made of silica, alumina, titania, zirconia or the like are preferable. The maximum particle size of the particles is preferably 500 nm or less. When particles having a maximum particle size exceeding 500 nm are used, when a film (cured 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. Tends to cause defects in the film.

  The blending amount of the particles is preferably 1 to 90 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polyamideimide resin and the epoxy 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 the blending amount of the particles exceeds 90 parts by mass, defects due to the particles tend to occur when a cured film is formed.

  The curable resin composition may further contain a flame retardant. By including a flame retardant, the flame retardancy of the curable resin composition and its cured product is improved. As the flame retardant, a general flame retardant can be used. 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 total amount of the polyamideimide resin and the epoxy resin. When the addition amount of the flame retardant is less than 0.1 parts by mass, sufficient flame retardancy tends to be difficult to obtain, and when it exceeds 50 parts by mass, the physical properties of the curable resin composition tend to be unsuitable. .

  The curable resin composition may further include a component that reacts with an epoxy group in addition to the polyamideimide resin. The component that reacts with the epoxy group is not particularly limited, and examples thereof include those generally used as an epoxy resin curing agent such as an amine curing agent and an acid anhydride curing agent. For example, a phenol resin or dicyandiamide can be used as such a component. The phenol resin may be of any type such as a novolak type, a cresol novolak type, and a bisphenol novolak type.

  Thus, when making the curable resin composition contain the component which reacts with an epoxy group further, in addition to the compounding quantity of the suitable epoxy resin mentioned above, an epoxy resin can be further mix | blended. In that case, the compounding amount of the epoxy resin is preferably an amount having 0.5 to 2.0 equivalents of an epoxy group with respect to the functional group reactive with the epoxy group contained in the above component, 0.9 to More preferably, the amount has 1.5 equivalents of an epoxy group.

  The curable resin composition is usually cured by heat, but the curable resin composition may have photocurability due to the inclusion of a structure and components that are accelerated by light. In this case, the curable resin composition may further contain a sensitizer. By including a sensitizer, light absorption is promoted and curing tends to proceed better. A known compound can be applied as the sensitizer, and can be appropriately selected 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 curable resin composition, and it is more preferable to set it as 0.1-10 mass%. By including a sensitizer within such a range, it is possible to perform good curing while maintaining the characteristics of the curable resin composition.

  Furthermore, the curable resin composition may contain a rubber-based elastomer, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent and the like according to desired properties.

  A curable resin composition layer can be formed by applying the curable resin composition described above onto a substrate. In that case, for example, the curable resin composition is used as it is or as a solution dissolved in an organic solvent or the like, 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. Thus, the curable resin composition layer comprised from the curable resin composition (mainly solid content) is formed.

  Although it does not specifically limit as a base | substrate, The base | substrate which consists of inorganic materials, such as metals, such as copper and aluminum, resin, such as a polyimide, ceramic, glass, etc. is mentioned. For example, the substrate may be mounted on an electronic component or the like, and may be such that a metal wiring is formed on a resin insulating substrate (printed wiring board or the like).

  As a method for forming the curable resin composition layer on the substrate, in addition to the above-described direct coating method, a film (curable resin film) made of the curable resin composition is formed, and this is applied to the substrate. There is a way to match.

  When the curable resin film is formed, the curable resin composition is applied onto a support in the same manner as when the curable resin composition layer is formed, and the solvent and the like are removed by heating or the like. In this way, a curable resin film is formed on the support. Thereafter, the support is peeled off from the curable resin film and removed, and the curable resin film is bonded to the substrate, whereby a curable resin composition layer can be formed on the substrate. The support may be removed after being laminated on the substrate.

  Examples of the support include films made of polyethylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, tetrafluoroethylene, release paper, metal foil such as copper foil and 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 curable resin film is formed) may be subjected to mat treatment, corona treatment, mold release treatment, and the like.

  The curable resin film can be stored in the state of a curable resin film from which the support is removed or in the state of a laminate in which the curable resin film is laminated on the support. Examples of the storage method include a method of cutting the curable resin film or the laminate into a certain length and storing it in a sheet form, and a method of further winding this and storing it in a roll form. From the viewpoints of storage stability, productivity, and workability, it is preferable that the laminate is further protected by covering the curable resin film with a protective film and wound up into a roll. 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.

  Thus, the curable resin composition layer formed on the substrate can function as an adhesive layer for bonding the substrate to another substrate or the like laminated on the curable resin composition layer. Further, by further curing, it can function as a protective layer for protecting the substrate or an insulating layer.

  Curing can be caused, for example, by heating the curable resin composition layer. In the case of curing by heating, a suitable temperature varies depending on the presence or absence of the curing accelerator in the curable resin composition and its type, but 130 to 230 ° C. can reduce deterioration of the properties of the cured product layer. It is preferable because workability is good. Depending on the type of polyamideimide resin or the like, the curable resin composition layer can be cured by light irradiation.

  Thus, the electronic component which concerns on one Embodiment of this invention is obtained by hardening the curable resin composition layer formed on the base | substrate. This electronic component includes a cured product of the curable resin composition according to the above-described embodiment. For example, the electronic component according to the present embodiment is a printed wiring board including a cured product of a curable resin composition that functions as an insulating layer or a protective layer.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Polyamideimide resin having phenolic hydroxyl group (Synthesis Example 1)
In a 500 mL separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, 9.3 mmol of polyoxypropylenediamine (produced by Mitsui Chemicals Fine Co., Ltd.) and (4,4′-diamino) were added. ) Wandamine HM which is dicyclohexylmethane (made by Shin Nippon Rika Co., Ltd.) 37.2 mmol, 97.7 mmol of trimellitic anhydride, and 142.9 g of N-methyl-2-pyrrolidone (NMP) which is an aprotic polar solvent And a reaction solution was prepared. The resulting reaction solution was warmed and stirred at 80 ° C. for 30 minutes.

  After stirring, 120 mL of toluene, which is an aromatic hydrocarbon azeotropic with water, was added to the reaction solution, and the reaction solution was heated to reflux at 160 ° C. for 4 hours. After confirming that the theoretical amount of water has accumulated in the moisture determination receiver and that water is no longer distilled, remove the water and toluene in the moisture determination receiver, and raise the temperature of the reaction solution to 180 ° C. Thus, toluene in the reaction solution was removed. The reaction solution thus obtained contains any of the imide dicarboxylic acids that are generated by the above reaction and that are each represented by the following general formula (2) or (3) and have no phenolic hydroxyl group. .

  After cooling the reaction liquid containing these imidodicarboxylic acids to room temperature (25 ° C.), 19.9 mmol of 5-hydroxyisophthalic acid which is a dicarboxylic acid having a phenolic hydroxyl group and 2,4 which is a carboxylic acid having a phenolic hydroxyl group -2.0 mmol of dihydroxybenzoic acid was added to the reaction solution and dissolved. Subsequently, 79.7 mmol of 4,4′-diphenylmethane diisocyanate was added to the reaction solution, and the reaction solution was heated and reacted at 160 ° C. for 2 hours. In this way, an NMP solution of polyamideimide resin containing all the structural units represented by the following general formula (1a), (2a), (3a) or (4a) was obtained.

The compounding amount of each compound used in Synthesis Example 1 is as shown below.
Compound amount Jeffamine D2000 9.3 mmol
Wandamine HM 37.2mmol
Trimellitic anhydride 97.7mmol
NMP 142.9g
5-hydroxyisophthalic acid 19.9 mmol
2,4-dihydroxybenzoic acid 2.0 mmol
4,4'-diphenylmethane
Diisocyanate 79.7mmol

(Synthesis Example 2)
Polyamide was used in the same manner as in Synthesis Example 1 except that Jeffamine D400 (manufactured by Mitsui Chemicals, Inc.) was used instead of Jeffamine D2000 as the polyoxypropylenediamine, and the compounding amounts of the respective compounds were as follows. An NMP solution of an imide resin was obtained.

Compound Formulation Jeffamine D400 12.3mmol
Wandamine HM 49.2mmol
Trimellitic anhydride 129.2 mmol
NMP 143.1g
2-Hydroxyisophthalic acid 26.4mmol
2,4-dihydroxybenzoic acid 2.6 mmol
4,4'-diphenylmethane
Diisocyanate 105.4mmol

Polyamideimide resin having no phenolic hydroxyl group (Synthesis Example 3)
In Synthesis Example 1, the reaction solution containing the imide dicarboxylic acid was cooled to room temperature, and then 4,4′-diphenylmethane diisocyanate was added without adding 5-hydroxyisophthalic acid and 2,4-dihydroxybenzoic acid to the reaction solution. 8 mmol was added to the reaction solution, and the reaction solution was heated and reacted at 150 ° C. for 2 hours. Moreover, the compounding quantity of NMP was 122.4g. Except for the above, an NMP solution of polyamideimide resin was obtained in the same manner as in Synthesis Example 1.

The compounding amount of each compound used in Synthesis Example 3 is as shown below.
Compound amount Jeffamine D2000 9.3 mmol
Wandamine HM 37.2mmol
Trimellitic anhydride 97.7mmol
NMP 122.4g
4,4'-diphenylmethane
Diisocyanate 55.8mmol

(Synthesis Example 4)
As the diamine compound, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) was used instead of Jeffamine D2000 and Wandamine HM, and the compounding amounts of each compound were as follows. Except that, an NMP solution of polyamideimide resin was obtained in the same manner as in Synthesis Example 3.
Compound loading BAPP 75.0mmol
Trimellitic anhydride 157.5mmol
NMP 238.0g
4,4'-diphenylmethane
Diisocyanate 90.0mmol

Molecular weight Using the NMP solution of the polyamideimide resin obtained in Synthesis Examples 1 to 4, the weight average molecular weight (Mw: converted to polystyrene) of the polyamideimide resin synthesized in each synthesis example was measured. As the measurement column, a column in which two GL-S300MDT-5 (manufactured by Hitachi Chemical Co., Ltd.) were connected in series was used. As an eluent, 1 L of dimethylformamide for liquid chromatography was dissolved by adding 0.03 mol of lithium bromide monohydrate and 0.06 mol of phosphoric acid, and then 1 L of tetrahydrofuran for liquid chromatography was further added. It was. The results are shown in Table 1.

Curable resin composition To the NMP solution of the polyamideimide resin obtained in Synthesis Examples 1 to 4, an epoxy resin and a curing accelerator are added, and further, N, N-dimethylacetamide is added to adjust the solution to an appropriate viscosity. Dilution was performed to obtain a curable resin composition. As the epoxy resin, phenol biphenyl aralkyl type epoxy resin “NC-3000H” (manufactured by Nippon Kayaku Co., Ltd., trade name) was used. As the curing accelerator, 1-cyanoethyl-2-phenylimidazolium trimellitate “2PZ-CNS” (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was used. Curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 10 were prepared according to the compositions shown in Table 2. All the numerical values in Table 2 indicate the mass (g) of each solid content.

Resin film The curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 10 are uniformly applied on PET and dried at 130 ° C. for 15 minutes to form a curable resin composition layer on PET. did. This curable resin composition layer was peeled off from PET to obtain a film (curable resin film) made of the curable resin composition. The curable resin film was heated at 180 ° C. for 1 hour to obtain a cured product (resin film) of the curable resin film.

Heat resistance With respect to the resin films obtained from the curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 10, the maximum value (Tg) of tan δ in the temperature range of 50 to 350 ° C. was obtained under the following conditions. . The results are shown in Table 3.
Conditions Device: Dynamic Viscoelasticity Measuring Device (DVE)
“E-4000” (trade name, manufactured by UBM)
Temperature increase rate: 5 ° C / min Distance between chucks: 20mm
Frequency: 10Hz
Amplitude: 5 μm
Automatic static load tension method

Solvent resistance The resin films obtained from the curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 10 were each cut into 3 cm squares. After the cut resin film (surface area = 1.8 × 10 ⁻³ m ² ) was dried at 105 ° C. for 30 minutes, the mass of the resin film (referred to as W1) was measured. Next, the resin film was impregnated with 50 mL of an NMP solution at 25 ° C. for 24 hours. The resin film after impregnation was taken out, washed with water, dried at 105 ° C. for 30 minutes, and then the mass of the resin film (referred to as W2) was measured. From the difference between W1 and W2, the solubility (g / m ² ) in NMP per 1 m ² of the surface area of the resin film was determined. The results are shown in Table 3.

As shown in Table 3, the solubility of each of the resin films obtained from the curable resin compositions of Examples 1 to 8 in NMP at 25 ° C. is 3.0 g / m ² or less. It was lower than the case of 7. That is, it became clear that the curable resin compositions of Examples 1 to 8 can form a cured product having sufficiently good solvent resistance. In addition, about the resin film obtained from the curable resin composition of Example 3 and 8, although the said solubility was 0 g / m < ² >, when the external appearance was observed, it swelled remarkably. Regarding heat resistance, it was revealed that the resin films obtained from the curable resin compositions of Examples 1 to 8 all had sufficiently high Tg and had sufficiently good heat resistance.

  The cured product of the curable resin composition provided by the present invention is suitably used as a protective film or insulating film having good heat resistance and solvent resistance in electronic components such as printed wiring boards.

Claims (4)

A curable resin composition comprising a polyamideimide resin, an epoxy resin, and a curing accelerator,
A curable resin composition that forms a cured product in which the amount dissolved in N-methyl-2-pyrrolidone at 25 ° C. is 3.0 g or less per 1 m ^{2 of} surface area.   The curable resin composition of Claim 1 whose compounding quantity of the said epoxy resin is 10-15 mass parts with respect to 100 mass parts of said polyamideimide resins.   The curable resin composition according to claim 1 or 2, wherein the polyamideimide resin is obtained by a reaction between a carbonyl compound containing a carboxylic acid and / or an acid anhydride and a diisocyanate.   The electronic component containing the hardened | cured material of the curable resin composition as described in any one of Claims 1-3.