JPWO2010058734A1 - Phenolic hydroxyl group-containing aromatic polyamide resin and use thereof - Google Patents

Abstract

The present invention provides a cured product having a resin having a low linear expansion coefficient, excellent electrical characteristics, sufficiently satisfying adhesion to various substrates, heat resistance, and flame retardancy, and a composition containing the resin. The purpose is to provide. The resin according to the present invention is a phenolic hydroxyl group-containing polyamide resin (A) represented by the following formula (2). In the formula (2), m and n are average values, 0 ≦ m / (m + n) ≦ 0.8, and m + n is a positive number of 2 to 200. Ar3 is derived from one or more compounds selected from paraphenylenediamine, metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 1,5-naphthalenediamine, and 1,8-naphthalenediamine. It represents a divalent aromatic group, and q is the average number of substituents and is an integer of 1 to 4.

Description

  The present invention provides a cured product excellent in low shrinkage, heat resistance, adhesiveness, electrical insulation properties, and flame retardancy, and has a phenolic hydroxyl group-containing aromatic polyamide resin having sufficient flexibility when formed into a film. The present invention relates to an epoxy resin composition comprising the resin and an epoxy resin as essential components, a material for a flexible printed wiring board using these, and a semiconductor insulating film.

  Some polyamide resins have been developed as additives and curing agents that modify the properties of epoxy resins, etc. Epoxy compositions containing them as a component generally have heat resistance, mechanical properties, and chemical resistance. It is used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. As the main component of such an epoxy resin composition, a bisphenol A type epoxy resin can be given as an epoxy resin that has been most commonly used. In addition, acid anhydrides and amine compounds are known as curing agents for epoxy resins, but novolak resins with excellent electrical reliability are often used in the field of electric and electronic parts in terms of heat resistance. . In Patent Document 1, Patent Document 2, Patent Document 3 and Patent Document 4, a phenolic hydroxyl group-containing polyamide resin and an epoxy resin composition containing them and an epoxy resin are excellent in heat resistance and flame retardancy, and flexible printing. It is described that it is useful as a wiring board material or a fiber reinforcing agent.

  However, the resin disclosed in Patent Literature 1, Patent Literature 2, Patent Literature 3 and Patent Literature 4 and the composition containing the resin have a high linear expansion coefficient, and in combination with a general copper foil or polyimide film A large curl is generated due to the difference in shrinkage rate, which causes a problem in connection reliability in the mounting process.

Japanese open patent; Japanese Patent Publication No. 7-42359 Japanese published patent; JP-A-2000-273168 Japanese published patent; Japanese Patent No. 2909878 International Publication Pamphlet of WO2004 / 048436

  In the present invention, since the cured product has a low linear expansion coefficient, curling does not occur when applied to a film-like substrate and cured, and the cured product has heat resistance, adhesiveness and flame retardancy. An object of the present invention is to provide an epoxy resin composition containing a polyamide resin that is excellent and has sufficient flexibility and electrical reliability even when molded into a sheet.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention provides (1) the following formula (2)

(In formula (2), m and n are average values, satisfy the relationship of 0 ≦ m / (m + n) ≦ 0.8, and m + n is a positive number from 2 to 200. Ar ₃ is paraphenylenediamine. 2 derived from one or more compounds selected from the group consisting of metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 1,5-naphthalenediamine and 1,8-naphthalenediamine A phenolic hydroxyl group-containing polyamide resin (A) represented by the following formula:
(2) m and n in the formula (2) satisfy the relationship of 0 ≦ m / (m + n) ≦ 0.5, and Ar ₃ is derived from paraphenylenediamine, metaphenylenediamine and 4,4′-diaminodiphenylmethane. The phenolic hydroxyl group-containing polyamide resin (A) according to (1), which is a divalent aromatic group derived from one or more compounds selected from the group consisting of:
(3) The phenolic hydroxyl group-containing polyamide resin (A) according to the above (1) or (2), wherein the glass transition temperature is 300 ° C. or more and the linear expansion coefficient between 100 and 200 ° C. is 40 ppm or less.
(4) An epoxy resin composition containing the phenolic hydroxyl group-containing polyamide resin (A) according to any one of (1) to (3) above and an epoxy resin (B),
(5) A film obtained by processing the epoxy resin composition according to the above (4) into a sheet,
(6) The adhesive sheet for flexible printed wiring boards which has the epoxy resin composition as described in said (4),
(7) Article obtained by heat-curing the epoxy resin composition according to (4), the film according to (5) or the sheet according to (6),
(8) Reinforcing plate for flexible printed wiring board having the epoxy resin composition according to (4) or a cured product layer thereof,
(9) A coverlay for a flexible printed wiring board having the epoxy resin composition according to (4) or a cured product layer thereof,
(10) The single-sided or double-sided metal characterized in that one side or both sides of the film or the cured product layer thereof according to (5) is in contact with one side of the metal foil layer or the resin side of the single-sided metal-clad resin laminate Tension resin laminate,
(11) The film described in (5) above, the sheet described in (6) above, the reinforcing plate described in (8) above, the coverlay described in (9) above, and the laminate described in (10) above A flexible printed wiring board using at least one selected from the group consisting of:
(12) A semiconductor insulating film having the epoxy resin composition according to (4) or a cured product layer thereof,
(13) (A) 1 selected from the group consisting of paraphenylenediamine, metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 1,5-naphthalenediamine and 1,8-naphthalenediamine More than one kind of compound,
(B) Phenolic hydroxyl group-containing as described in (1) above, wherein hydroxyphthalic acid and phthalic acid as an optional component (however, 20 mol% to 100 mol% of both are hydroxyphthalic acid) are subjected to a condensation reaction Production method of polyamide resin (A),
(14) (A) one or more compounds selected from the group consisting of paraphenylenediamine, metaphenylenediamine and 4,4′-diaminodiphenylmethane;
(B) A phenolic hydroxyl group-containing compound as described in (2) above, wherein hydroxyphthalic acid and phthalic acid as an optional component (provided that 50 mol% to 100 mol% of both are hydroxyphthalic acid) are subjected to a condensation reaction. Production method of polyamide resin (A),
About.

  The phenolic hydroxyl group-containing polyamide resin of the present invention is excellent in heat resistance and has a low linear expansion coefficient even when molded into a thin film. In addition, the epoxy resin composition of the present invention containing the polyamide resin and the epoxy resin maintains the heat resistance and low linear expansion coefficient that are characteristic of the polyamide resin even in a film-like cured product processed into a sheet shape. Furthermore, since it has excellent adhesiveness, flame retardancy and electrical reliability, it can be widely used in the production of flexible printed wiring boards and semiconductor insulating materials, etc. Very useful in the field.

The phenolic hydroxyl group-containing aromatic polyamide resin (A) of the present invention is obtained by subjecting the following compound group (a) and compound group (b) to a condensation reaction.
Compound group (a)
One or more compound compounds (b) selected from paraphenylenediamine, metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 1,5-naphthalenediamine or 1,8-naphthalenediamine
Hydroxyphthalic acid and optional phthalic acid

  Since the aromatic diamine of the compound group (a) (hereinafter also simply referred to as “aromatic diamine”) has extremely high crystallinity, the aromatic dicarboxylic acid (hereinafter simply referred to as “aromatic dicarboxylic acid”) of the compound group (b). With the progress of the condensation reaction, the solvent solubility is drastically reduced, and in some cases, it may be precipitated as crystals during the condensation reaction, but the hydroxy group having a phenolic hydroxyl group among the aromatic dicarboxylic acids. By using phthalic acid, preferably hydroxyisophthalic acid in a certain amount or more, precipitation of aromatic diamine during the condensation reaction can be suppressed, and in addition, phenolic hydroxyl group having a high glass transition point and a low linear expansion coefficient. A contained aromatic polyamide resin can be obtained.

  The phenolic hydroxyl group-containing polyamide resin (A) of the present invention preferably has a linear expansion coefficient between 100 and 200 ° C. of 40 ppm or less. When the linear expansion coefficient in this temperature range exceeds 40 ppm, there is a possibility that large curl may be generated in various heat treatment processes such as solder reflow on a film or a flexible printed wiring board using a phenolic hydroxyl group-containing polyamide resin. The general copper foil and polyimide film used for flexible printed wiring plates have a linear expansion coefficient between 100 and 200 ° C. of about 20 ppm, and the closer to this value, the less the curl. Accordingly, the phenolic hydroxyl group-containing polyamide resin (A) is more preferably one having a linear expansion coefficient between 100 and 200 ° C. close to 20 ppm.

The phenolic hydroxyl group-containing polyamide resin (A) of the present invention can be prepared by subjecting an aromatic diamine and an aromatic dicarboxylic acid to a condensation reaction by applying a method described in, for example, Japanese Patent No. 2969585.
The amount of the aromatic diamine used in the condensation reaction is usually 50 to 200 mol, preferably 80 to 125 mol, more preferably 90 to 110 mol, particularly preferably 95 to 105 mol, per 100 mol of the aromatic dicarboxylic acid. is there. The molecular weight of the phenolic hydroxyl group-containing polyamide resin (A) obtained increases as the molar ratio of the aromatic diamine and aromatic dicarboxylic acid used in the condensation reaction approaches 1: 1.

  The condensation reaction between the aromatic diamine and the aromatic dicarboxylic acid is performed using a phosphorus condensing agent in an organic solvent in the presence of a pyridine derivative. As the phosphorus condensing agent, phosphite is preferable. Further, when an inorganic salt such as lithium chloride or calcium chloride is added during the reaction, a phenolic hydroxyl group-containing polyamide resin (A) having a higher molecular weight can be obtained. According to this production method, a phenolic hydroxyl group-containing aromatic can be produced without causing a reaction between the phenolic hydroxyl group and another reactive group such as a carboxyl group or an amino group without protecting the functional phenolic hydroxyl group. Polyamide resin can be easily produced, and the condensation reaction can be performed at a low temperature of about 150 ° C. or lower.

  Hereinafter, the synthesis method of the phenolic hydroxyl group-containing polyamide resin (A) of the present invention will be described in more detail. As the aromatic diamine used in the synthesis, paraphenylene diamine, metaphenylene diamine, 4,4′-diaminodiphenyl ether or 4,4′-diaminodiphenylmethane is preferable, and the obtained phenolic hydroxyl group-containing aromatic polyamide resin (A) is used. Paraphenylenediamine, metaphenylenediamine or 4,4′-diaminodiphenylmethane having a lower linear expansion coefficient is more preferred, and paraphenylenediamine is particularly preferred.

  Of the aromatic dicarboxylic acids used in the synthesis, the hydroxyphthalic acid may be any one having 1 to 4 hydroxy groups substituted, such as 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid. Examples thereof include acid, 3-hydroxyisophthalic acid, and 2-hydroxyterephthalic acid. Among them, 5-hydroxyisophthalate is obtained from the standpoints of solvent solubility, purity, and epoxy resin composition of the resulting phenolic hydroxyl group-containing aromatic polyamide resin (A), electrical properties when used as an epoxy resin composition, and adhesion to metal foil and polyimide. Acid is most preferred. Among the aromatic dicarboxylic acids used in the synthesis, as the optional phthalic acid, orthophthalic acid, metaphthalic acid (isophthalic acid) and paraphthalic acid (terephthalic acid) can be used. preferable.

When the content of hydroxyphthalic acid in the aromatic dicarboxylic acid component decreases, crystals of aromatic diamine may precipitate during synthesis. The amount of hydroxyphthalic acid used to suppress precipitation of aromatic diamine is usually 20 mol% or more and 100 mol% or less, preferably 50 mol% or more and 100 mol% or less, more preferably 75 in the total aromatic dicarboxylic acid. It is from mol% to 100 mol%. By using the amount of hydroxyphthalic acid as described above, the repeating units m and n in the formula (2) are 0 ≦ m / (m + n) ≦ 0.8, preferably 0 ≦ m / (m + n). A phenolic hydroxyl group-containing aromatic polyamide resin (A) satisfying the relationship of ≦ 0.5 is obtained.
Japanese Patent No. 2969585 describes a phenolic hydroxyl group-containing polyamide resin in which the amount of dicarboxylic acid having a phenolic hydroxyl group is 5 mol% or more of the total carboxylic acid component. There is no description that the use of a specific amount of acid has the effect of suppressing the precipitation of aromatic diamine during the condensation reaction.

  Specific examples of phosphites used as condensing agents in the synthesis include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, and tri-m-tolyl phosphite. , Tri-p-tolyl phosphite, di-p-tolyl phosphite, di-p-chlorophenyl phosphite, tri-p-chlorophenyl phosphite and di-p-chlorophenyl phosphite. It is not limited.

  Examples of pyridine derivatives used with phosphite esters include pyridine, 2-picoline, 3-picoline, 4-picoline, and 2,4-lutidine.

  The phosphite is generally used as a condensing agent in a mixture of a pyridine derivative and an organic solvent. As the organic solvent, a phenolic hydroxyl group-containing polyamide resin which has a property of not dissolving substantially with the phosphite ester and dissolving the aromatic diamine and the aromatic dicarboxylic acid satisfactorily and which is a reaction product ( A good solvent for A) is desirable. Examples of such an organic solvent include amide solvents such as N-methylpyrrolidone and N, N-dimethylacetamide, toluene, methyl ethyl ketone, and mixed solvents of these with amide solvents, among which N-methyl- 2-pyrrolidone is preferred. The usage-amount of a pyridine derivative is 5-30 weight% normally in the mixture of a pyridine derivative and an organic solvent.

  Further, in order to obtain a phenolic hydroxyl group-containing polyamide resin (A) having a high degree of polymerization, it is preferable to add inorganic salts such as lithium chloride and calcium chloride in addition to the phosphite ester and pyridine derivative.

  Hereinafter, the most preferable example of the manufacturing method of the phenolic hydroxyl group-containing polyamide resin (A) of the present invention will be specifically described. First, a phosphite and an inorganic salt are added to a mixed solvent composed of an organic solvent containing a pyridine derivative, and 5-hydroxyisophthalic acid and, optionally, isophthalic acid, and 50 to 50 mol per 100 mol of these dicarboxylic acid components. 200 moles of paraphenylenediamine is added and then heated and stirred under an inert atmosphere such as nitrogen. After completion of the reaction, a poor solvent such as water, methanol or hexane is added to the reaction liquid, or the reaction liquid is poured into the poor solvent to separate the produced polymer, followed by purification by a reprecipitation method to produce a by-product. By removing inorganic salts and the like, the phenolic hydroxyl group-containing aromatic polyamide resin (A) represented by the formula (2) can be obtained.

  In the above production method, the addition amount of the phosphite, which is a condensing agent, is usually equimolar or more with respect to the amino group, but it is not efficient when it is 30 or more moles. Further, when phosphorous acid triester is used, the by-product phosphorous acid diester also acts as a condensing agent, so that it may be about 80 mol%. The amount of the pyridine derivative needs to be equimolar or more with respect to the amino group. However, in practice, the pyridine derivative is often used in a large excess in the role of a reaction solvent. The amount of the mixture composed of the pyridine derivative and the organic solvent is preferably in a range where the concentration of the theoretically obtained phenolic hydroxyl group-containing aromatic polyamide resin is 5 to 30% by weight. The reaction temperature is usually 60 to 180 ° C, preferably 80 to 120 ° C. The reaction time is greatly influenced by the reaction temperature, but in any case, it is preferable to stir the reaction system until the maximum viscosity representing the maximum degree of polymerization is obtained, usually from several minutes to about 20 hours, preferably 5 to 12 hours. It's time.

  Under the above preferred reaction conditions, when equimolar amounts of 5-hydroxyisophthalic acid and optionally isophthalic acid and paraphenylenediamine are used, the phenolic hydroxyl group-containing aromatic having the most preferred average degree of polymerization of about 2 to 200 repeat units. A polyamide resin (A) can be obtained.

  The number average molecular weight of the phenolic hydroxyl group-containing aromatic polyamide resin (A) obtained as described above is usually about 3000 to 60000, preferably about 10,000 to 40000, and the weight average molecular weight is usually about 10,000 to 250,000, preferably 70000 to The calculated value of the active hydrogen equivalent is usually 180 to 5000 g / eq. , Preferably 200 to 1000 g / eq. , More preferably 200 to 500 g / eq. And more preferably 200 to 400 g / eq. , Most preferably 220 to 350 g / eq. It is. In general, whether or not the polymer has a preferable average degree of polymerization is determined by referring to the molecular weight. If the weight average molecular weight is less than 10,000, film formation and properties as an aromatic polyamide resin are insufficient, which is not preferable. On the other hand, if the molecular weight is larger than 250,000, the degree of polymerization is so high that the solvent solubility is deteriorated and the moldability is deteriorated. The number average molecular weight and the weight average molecular weight are numerical values converted to polystyrene by gel permeation chromatography (the same applies hereinafter).

  As a simple method for adjusting the degree of polymerization of the phenolic hydroxyl group-containing aromatic polyamide resin (A), there can be mentioned a method in which either one of aromatic diamine or aromatic dicarboxylic acid is used in excess.

Next, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention is a composition containing a phenolic hydroxyl group-containing aromatic polyamide resin (A) and an epoxy resin (B). The epoxy resin (B) used in the epoxy resin composition of the present invention is reacted with the phenolic hydroxyl group and the terminal carboxyl group or / and the terminal amino group in the phenolic hydroxyl group-containing aromatic polyamide resin (A). Added to purpose. By reacting the phenolic hydroxyl group-containing aromatic polyamide resin (A) and the epoxy resin (B), the crosslinking density of the polyamide resin of the present invention increases, and the heat resistance of the cured product of the epoxy resin composition of the present invention Adhesion to the substrate is improved. The epoxy resin (B) that can be used is not particularly limited as long as it has two or more epoxy groups in one molecule. However, from the viewpoint of mechanical strength and flame retardancy, it may be a benzene ring, biphenyl ring, naphthalene ring or the like. It has a preferable aromatic ring and has two or more epoxy groups in one molecule. Specific examples include novolac type epoxy resins, xylylene skeleton-containing phenol novolac type epoxy resins, biphenyl skeleton-containing novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, tetramethylbiphenol type epoxy resins, and the like. From the viewpoint of compatibility with the phenolic hydroxyl group-containing polyamide resin (A), an epoxy resin having a biphenyl skeleton is particularly preferable.
The amount of the epoxy resin (B) used in the epoxy resin composition of the present invention is usually 0.05 to 1 equivalent to 1 equivalent of active hydrogen of the phenolic hydroxyl group-containing aromatic polyamide resin (A) contained in the epoxy resin composition. 1.2 equivalents, preferably 0.05 to 0.5 equivalents, more preferably 0.05 to 0.3 equivalents. The active hydrogen equivalent of the phenolic hydroxyl group-containing aromatic polyamide resin (A) can be calculated from the total of the phenolic hydroxyl group-containing aromatic dicarboxylic acid and excess diamine component or dicarboxylic acid component charged during the reaction.

You may mix | blend a hardening | curing agent with the epoxy resin composition of this invention. Specific examples of curing agents that can be blended include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, anhydrous Trimellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenolic hydroxyl group-containing resin, triphenylmethane And modified products thereof, imidazole, BF ₃ -amine complexes, guanidine derivatives and the like, but are not limited thereto. When blending these curing agents, the proportion of the phenolic hydroxyl group-containing aromatic polyamide resin (A) in the epoxy resin composition in the total curing agent is usually 20% by weight or more, preferably 30% by weight or more.

  Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5. -Imidazoles such as hydroxymethylimidazole, tertiary amines such as 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene-7, triphenylphosphine, etc. Examples thereof include metal compounds such as phosphines and tin octylate. The curing accelerator is used as necessary in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

  The epoxy resin composition of the present invention contains an inorganic filler as necessary. Specific examples of the inorganic filler that can be used include silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, calcium phosphate, alumina, talc, and short glass fiber. The inorganic filler is used in an amount of 0 to 90% by weight in the epoxy resin composition of the present invention. Furthermore, various compounding agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, calcium stearate, and pigments can be added to the epoxy resin composition of the present invention.

  If necessary, the epoxy resin composition of the present invention may be dissolved in a solvent. Examples of solvents that can be used include amide solvents such as γ-butyrolactones, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and the like. , Sulfones such as tetramethylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone And ketone solvents such as cyclohexanone and aromatic solvents such as toluene and xylene. These solvents are used in an amount such that the solid content concentration excluding the solvent in the resin composition is usually 10 to 70% by weight, preferably 30 to 70% by weight.

  The epoxy resin composition of the present invention is characterized in that the cured product has a linear expansion coefficient between 100 and 200 ° C. of 50 ppm or less. When the linear expansion coefficient exceeds 50 ppm, a large curl is generated by various processing steps such as solder reflow during the production of a film after forming a coating film or a flexible printed wiring board. A general copper foil and polyimide film used for a flexible printed wiring board have a linear expansion coefficient of about 20 ppm between 100 and 200 ° C., and the closer to this value, the less curl.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin composition and, optionally, a curing agent, and if necessary, a curing accelerator and an inorganic filler and a compounding agent are thoroughly mixed using an extruder, kneader, roll, etc. as necessary until uniform. The epoxy resin composition is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like, and further heated at 80 to 200 ° C. for 2 to 10 hours to obtain the cured product of the present invention. be able to.

  The film which processed the epoxy resin composition of this invention into the sheet form, and its hardened | cured material are obtained from what melt | dissolved the epoxy resin composition of this invention in the solvent. Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone and the like. , Sulfones such as tetramethylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone And ketone solvents such as cyclohexanone and aromatic solvents such as toluene and xylene. The solid content concentration in the obtained varnish is usually 20 to 80% by weight, preferably 30 to 70% by weight.

  The film of the present invention has a thickness after drying the above epoxy resin composition on a planar support by various coating methods such as a gravure coating method, screen printing, metal mask method, and spin coating method known per se. Is obtained after coating so as to have a predetermined thickness, for example, 5 to 500 μm. Which coating method is used is appropriately selected depending on the type, shape, size, and film thickness of the coating film. . Examples of the base material include various polymers such as polyamide, polyimide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetheretherketone, polyetherimide, polyetherketone, polyketone, polyethylene, and polypropylene, and / or its It is a film made from a copolymer or a metal foil such as a copper foil, and a polyimide or a metal foil is preferred. By further heating this film, a sheet-like cured product can be obtained. Preferred uses of the film of the present invention include a flexible printed wiring board adhesive sheet, a flexible printed wiring board reinforcing plate, a flexible printed wiring board cover lay, a resin layer of a single-sided or double-sided metal-clad resin laminate (hereinafter these are combined). The epoxy resin composition of the present invention acts as an adhesive or a resin layer for the flexible printed wiring board constituting them. In such applications, the planar support often has a function as a release film.

  Also, the varnish obtained above is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, aramid fiber, zylon fiber, alumina fiber, paper, etc. It can also be obtained. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.

Synthesis Example 1
A flask equipped with a thermometer, a condenser and a stirrer was purged with nitrogen gas, and in this, 20.66 g (0.11 mol) of 5-hydroxyisophthalic acid and 12.51 g (0.12 mol) of paraphenylenediamine were added. , 0.96 g of lithium chloride, 120.98 g of N-methyl-2-pyrrolidone and 26.80 g of pyridine were stirred and dissolved, and then 58.09 g of triphenyl phosphite was added and reacted at 95 ° C. for 8 hours. Following formula (4)

The reaction liquid of the phenolic hydroxyl group containing aromatic polyamide resin (A) of this invention represented by these was obtained. After cooling the reaction solution to room temperature, 50 g of methanol and 200 g of water were added, and the precipitated resin was filtered off, further washed with 200 g of methanol, and then purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the resin powder was obtained (this resin is set to A-1). The yield was 27.8 g, and the yield was 95.6%. The molecular weight of this resin powder was 37900 in number average molecular weight and 169000 in weight average molecular weight. The active hydrogen equivalent capable of reacting with the epoxy group is calculated to be 246.6 g / eq. (The hydroxyl group equivalent was 256.4 g / eq.).

Synthesis Example 2
A flask equipped with a thermometer, a condenser and a stirrer was purged with nitrogen gas. In this, 15.71 g (0.09 mol) of 5-hydroxyisophthalic acid, 4.78 g (0.03 mol) of isophthalic acid, 12.69 g (0.12 mol) of paraphenylenediamine, 0.955 g of lithium chloride, 129.80 g of N-methyl-2-pyrrolidone and 27.18 g of pyridine were stirred and dissolved, and then 58.90 g of triphenyl phosphite. And reacted at 90 ° C. for 8 hours to obtain the following formula (5)

The reaction liquid of the phenolic hydroxyl group containing aromatic polyamide resin (A) of this invention represented by these was obtained. After cooling the reaction solution to room temperature, 50 g of methanol and 200 g of water were added, and the precipitated resin was filtered off, further washed with 200 g of methanol, and then purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the resin powder was obtained (this resin is set to A-2). The yield was 28.0 g, and the yield was 96.4%. The molecular weight of this resin powder was 39000 in number average molecular weight and 139400 in weight average molecular weight. The active hydrogen equivalent that can react with the epoxy group is calculated to be 319.54 g / eq. (The hydroxyl group equivalent was 336.58 g / eq.).

Synthesis Example 3
A flask equipped with a thermometer, a condenser and a stirrer was purged with nitrogen gas, and 20.66 g (0.11 mol) of 5-hydroxyisophthalic acid and 12.51 g (0.12 mol) of metaphenylenediamine were contained therein. , 0.96 g of lithium chloride, 100.98 g of N-methyl-2-pyrrolidone and 26.80 g of pyridine were stirred and dissolved, and then 58.09 g of triphenyl phosphite was added and reacted at 95 ° C. for 8 hours. Following formula (6)

The reaction liquid of the phenolic hydroxyl group containing aromatic polyamide resin (A) of this invention represented by these was obtained. After cooling the reaction solution to room temperature, 50 g of methanol and 200 g of water were added, and the precipitated resin was filtered off, further washed with 200 g of methanol, and then purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the resin powder was obtained (this resin is set to A-3). The yield was 25.2 g, and the yield was 86.6%. The molecular weight of this resin powder was 19300 in terms of number average molecular weight and 97200 in terms of weight average molecular weight. The active hydrogen equivalent capable of reacting with the epoxy group is calculated to be 246.6 g / eq. (The hydroxyl group equivalent was 256.4 g / eq.).

Synthesis Example 4
A flask equipped with a thermometer, a condenser and a stirrer was purged with nitrogen gas, and 15.72 g (0.09 mol) of 5-hydroxyisophthalic acid and 17.45 g (0,4) of 4,4′-diaminodiphenylmethane were contained therein. 0.09 mol), 0.96 g of lithium chloride, 101.28 g of N-methyl-2-pyrrolidone and 20.39 g of pyridine were stirred and dissolved, and then 44.20 g of triphenyl phosphite was added and the mixture was heated at 95 ° C. for 8 hours. The following reaction (7)

The reaction liquid of the phenolic hydroxyl group containing aromatic polyamide resin (A) of this invention represented by these was obtained. After cooling the reaction solution to room temperature, 50 g of methanol and 200 g of water were added, and the precipitated resin was filtered off, further washed with 200 g of methanol, and then purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the resin powder was obtained (this resin is set to A-4). The yield was 27.6 g, and the yield was 91.8%. The molecular weight of this resin powder was 30300 in terms of number average molecular weight and 120800 in terms of weight average molecular weight. The active hydrogen equivalent capable of reacting with the epoxy group is 335.0 g / eq. (The hydroxyl group equivalent was 348.4 g / eq.).

Synthesis Example 5
A flask equipped with a thermometer, a condenser and a stirrer was purged with nitrogen gas, and 15.64 g (0.09 mol) of 5-hydroxyisophthalic acid and 17.54 g (0,4) of 4,4′-diaminodiphenyl ether were contained therein. 0.09 mol), 0.96 g of lithium chloride, 101.62 g of N-methyl-2-pyrrolidone, and 20.29 g of pyridine were stirred and dissolved, and then 43.97 g of triphenyl phosphite was added and the mixture was heated at 95 ° C. for 8 hours. The following reaction (8)

The reaction liquid of the phenolic hydroxyl group containing aromatic polyamide resin (A) of this invention represented by these was obtained. After cooling the reaction solution to room temperature, 50 g of methanol and 200 g of water were added, and the precipitated resin was filtered off, further washed with 200 g of methanol, and then purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the resin powder was obtained (this resin is set to A-5). The yield was 28.4 g, and the yield was 94.4%. The molecular weight of this resin powder was 40000 in terms of number average molecular weight and 164200 in terms of weight average molecular weight. The active hydrogen equivalent that can react with the epoxy group is 336.8 g / eq. (The hydroxyl group equivalent was 350.3 g / eq.).

Comparative Synthesis Example 1
A flask equipped with a thermometer, a condenser and a stirrer was purged with nitrogen gas, and 0.44 g (0.002 mol) of 5-hydroxyisophthalic acid, 19.52 g (0.12 mol) of isophthalic acid, After charging 13.22 g (0.12 mol) of paraphenylenediamine, 0.96 g of lithium chloride, 76.16 g of N-methyl-2-pyrrolidone and 28.32 g of pyridine and stirring and dissolving, 61.38 g of triphenyl phosphite And reacted at 90 ° C. to obtain the following formula (9)

When a reaction solution of a comparative phenolic hydroxyl group-containing aromatic polyamide resin represented by the formula (1) was obtained, it was confirmed that the reaction product precipitated and did not dissolve in the solvent.

Comparative Synthesis Example 2
A flask equipped with a thermometer, a condenser and a stirrer was purged with nitrogen gas, and 12.00 g (0.07 mol) of 5-hydroxyisophthalic acid, 3,3 ′, 5,5′-tetraethyl- After charging 20.86 g (0.07 mol) of 4,4′-diaminodiphenylmethane, 2.88 g of lithium chloride, 114.98 g of N-methyl-2-pyrrolidone and 15.56 g of pyridine, stirring and dissolving, After adding 33.73 g of phenyl and reacting at 95 ° C. for 8 hours, the following formula (10)

The reaction liquid of the phenolic hydroxyl group containing aromatic polyamide resin for comparison represented by these was obtained. After cooling the reaction solution to room temperature, 50 g of methanol and 200 g of water were added, and the precipitated resin was filtered off, further washed with 200 g of methanol, and then purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the resin powder was obtained (this resin is set to R-2). The yield was 28.0 g, and the yield was 91.9%. The molecular weight of this resin powder was 19300 in terms of number average molecular weight and 69100 in terms of weight average molecular weight. The active hydrogen equivalent capable of reacting with the epoxy group is 445.0 g / eq. (Hydroxyl equivalent was 462.8 g / eq.).

Comparative Synthesis Example 3
A flask equipped with a thermometer, a condenser and a stirrer was purged with nitrogen gas. In this, 14.57 g (0.09 mol) of isophthalic acid, 0.33 g (0.002 mol) of 5-hydroxyisophthalic acid, First, 18.28 g (0.09 mol) of 3,4'-diaminodiphenyl ether, 0.96 g of lithium chloride, 98.90 g of N-methyl-2-pyrrolidone and 21.15 g of pyridine were stirred and dissolved, and then triphosphite trichloride. 45.83 g of phenyl was added and reacted at 95 ° C. for 8 hours to obtain the following formula (11)

The reaction liquid of the phenolic hydroxyl group containing aromatic polyamide resin for comparison represented by these was obtained. After cooling the reaction solution to room temperature, 50 g of methanol and 200 g of water were added, and the precipitated resin was filtered off, further washed with 200 g of methanol, and then purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the resin powder was obtained (this resin is set to R-3). The yield was 27.7 g, and the yield was 92.5%. The molecular weight of the resin powder was 44,000 in terms of number average molecular weight and 106,000 in terms of weight average molecular weight. The active hydrogen equivalent that can react with the epoxy group is 5577 g / eq. (Hydroxyl equivalent was 16731 g / eq.).

Test Examples Resin powders obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 2 and 3 (A-1, A-2, A-3, A-4, A-5, R-2, R-3) Was diluted with N, N-dimethylacetamide so that the solid concentration was 20% by weight to obtain a phenolic hydroxyl group-containing aromatic polyamide resin solution. This resin solution was applied onto a PET film so that the thickness after drying was 20 μm, then dried at 140 ° C. for 10 minutes to remove the PET film, and then fixed to a mold and added at 200 ° C. for 60 minutes. By drying, a film of the present invention and a comparative phenolic hydroxyl group-containing polyamide resin alone was obtained.

  About the obtained film, a glass transition temperature (Tg) and a linear expansion coefficient between 100 to 200 ° C. when the temperature was raised from 50 ° C. to 400 ° C. at 5 ° C./min using a TMA apparatus (manufactured by PerkinElmer) The measurement results of (CTE) are shown in Table 1.

Examples 1, 2, 3 Comparative Example 1
The phenolic hydroxyl group-containing aromatic polyamide resin (A-1) obtained in Synthesis Example 1, the phenolic hydroxyl group-containing aromatic polyamide resin (R-3) obtained in Comparative Synthesis Example 3, an epoxy resin, a curing agent, A curing accelerator and a solvent (DMAC; dimethylaminocinnamaldehyde) were mixed at a ratio (parts by weight) shown in Table 2 to obtain an epoxy resin composition for comparison with the present invention.

* 1: Epoxy resin, manufactured by Nippon Kayaku Co., Ltd., biphenyl skeleton epoxy resin, epoxy equivalent 280 g / eq.
* 2: Curing agent, manufactured by Nippon Kayaku Co., Ltd., biphenyl skeleton phenolic hydroxyl group-containing resin, active hydrogen equivalent 205 g / eq.
* 3: Curing accelerator, manufactured by Shikoku Kasei Co., Ltd., 2-phenyl-4,5-dihydroxymethylimidazole

Examples 4, 5, and 6 Comparative Example 2
By applying the resin compositions of Examples 1, 2, 3 and Comparative Example 1 on a PET film so that the thickness after drying was 20 μm, and drying at 140 ° C. for 10 minutes, and then removing the PET film The films of the present invention and comparative epoxy resin compositions were obtained.

Examples 7, 8, and 9 Comparative Example 3
A comb-shaped electrode (conductor / line spacing = 50 μm / 50 μm) defined in IPC-SM-840 formed using polyimide copper-clad laminate IUPICEL D (trade name, manufactured by Ube Industries, Ltd.) is used as an evaluation circuit. Then, the present invention and the comparative film prepared in Examples 4, 5, and 6 and Comparative Example 2 were bonded together, and heat-pressed at 200 ° C. and 5 MPa for 60 minutes to obtain an electrical reliability test sample (the present invention and comparison). Laminate). The insulation resistance value was continuously measured (PCBT) for 1000 hours as the upper limit while applying a DC voltage of 50 V between the electrodes in an environment of 121 ° C. and 100% RH using an ion migration acceleration tester. As a result of measuring the time when the insulation resistance value became 10 5 ohms or less, all were 1000 hours or more.

Examples 10, 11, 12 Comparative Example 4
The films obtained in Examples 4, 5, 6 and Comparative Example 2 were cut into 20 cm squares and sandwiched between Teflon (registered trademark) plates and cured by heat treatment at 200 ° C. and 5 MPa for 60 minutes using a hot plate press. The present invention and comparative film cured products were obtained. Table 3 shows the flame retardancy of this cured product, the glass transition temperature (Tg) measured by TMA and the linear expansion coefficient (CTE) between 100-200 ° C, the glass transition temperature (Tg) measured by DMA, and the elastic modulus at 30 ° C. It was shown to.

Examples 13, 14, and 15 Comparative Example 5
Using the roll coater on the resin compositions of Examples 1, 2, 3 and Comparative Example 1 on polyimide having a thickness of 25 μm (Upilex 25SGA, manufactured by Ube Industries, Ltd.), the thickness after drying becomes 20 μm. Then, the solvent was removed under drying conditions at 140 ° C. for 10 minutes to obtain an upilex film with an adhesive layer (the present invention and a coverlay for comparison).

Examples 16, 17, 18 Comparative Example 6
On the adhesive layer surface of the Upilex film with an adhesive layer obtained in Examples 13, 14, 15 and Comparative Example 5, a roughened surface of rolled copper foil (manufactured by Nikko Materials Co., Ltd., BHN foil) having a thickness of 18 μm. Were bonded together by thermocompression bonding at 230 ° C. and 5 MPa for 60 minutes using a hot plate press to obtain a single-sided copper-clad resin laminate for the present invention and comparison. About the obtained single-sided copper-clad resin laminated board, as a result of measuring the peeling strength of copper foil and a resin layer by the method based on JISC6481, using a Tensilon testing machine (product made from Toyo Baldwin Co., Ltd.), all are 8- It was 11 N / cm.

Examples 19, 20, 21 Comparative Example 7
The epoxy resin compositions of Examples 1, 2, 3 and Comparative Example 1 were dried on a roughened surface of a rolled copper foil (manufactured by Nikko Materials Co., Ltd., BHN foil) having a thickness of 18 μm. It apply | coated using the roll coater so that it might become 20 micrometers, and the solvent was removed on 140 degreeC and the drying conditions for 10 minutes. Thereafter, two rolled copper foils with an adhesive layer were cut into 20 cm squares, their adhesive layer surfaces were brought into contact with each other, and heat-pressed at 230 ° C. and 5 MPa for 60 minutes using a hot plate press, both sides for comparison with the present invention. A copper-clad resin laminate was obtained. About the obtained double-sided copper-clad resin laminated board, as a result of measuring the peeling strength of copper foil and copper foil by the method based on JISC6481, using the Tensilon test machine (product made from Toyo Baldwin Co., Ltd.), all are 10-. 14 N / cm.

Examples 22, 23, 24 Comparative Example 8
The films of Examples 4, 5, 6 and Comparative Example 2 were sandwiched with 25 μm-thick polyimide (Iupilex 25SGA, manufactured by Ube Industries, Ltd.) and heat-pressed at 230 ° C. and 5 MPa for 60 minutes to form an epoxy resin composition film And a polyimide laminate was obtained. About the obtained laminated body, as a result of measuring the peeling strength of a polyimide and a polyimide by the method based on JIS C6481 using the Tensilon tester (made by Toyo Baldwin Co., Ltd.), all were 8-9 N / cm. .

  As described above, the phenolic hydroxyl aromatic polyamide resin of the present invention is solvent-soluble, and the epoxy resin composition containing it has a low coefficient of linear expansion without deteriorating various properties of the composition and its cured product. Gives a cured product with excellent properties. Therefore, the phenol resin of the present invention sufficiently satisfies adhesion to various base materials, heat resistance, and flame retardancy, and is useful for adhesive sheets, coverlays, reinforcing plates, resin laminates, and the like.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2008-295022) for which it applied on November 19, 2008, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

Claims (14)

Following formula (2)

(In formula (2), m and n are average values, satisfy the relationship of 0 ≦ m / (m + n) ≦ 0.8, and m + n is a positive number from 2 to 200. Ar ₃ is paraphenylenediamine. 2 derived from one or more compounds selected from the group consisting of metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 1,5-naphthalenediamine and 1,8-naphthalenediamine A phenolic hydroxyl group-containing polyamide resin (A) represented by a valent aromatic group, q being an average number of substituents and an integer of 1 to 4. M and n in the formula (2) satisfy the relationship of 0 ≦ m / (m + n) ≦ 0.5, and Ar ₃ is selected from the group consisting of paraphenylenediamine, metaphenylenediamine and 4,4′-diaminodiphenylmethane. The phenolic hydroxyl group-containing polyamide resin (A) according to claim 1, which is a divalent aromatic group derived from one or more selected compounds.   The phenolic hydroxyl group-containing polyamide resin (A) according to claim 1 or 2, wherein the glass transition temperature is 300 ° C or higher and the linear expansion coefficient between 100 and 200 ° C is 40 ppm or lower.   An epoxy resin composition comprising the phenolic hydroxyl group-containing polyamide resin (A) according to any one of claims 1 to 3 and an epoxy resin (B).   The film which processed the epoxy resin composition of Claim 4 into the sheet form.   The adhesive sheet for flexible printed wiring boards which has the epoxy resin composition of Claim 4.   An article obtained by heat-curing the epoxy resin composition according to claim 4, the film according to claim 5, or the sheet according to claim 6.   The reinforcement board for flexible printed wiring boards which has the epoxy resin composition of Claim 4, or its hardened | cured material layer.   The coverlay for flexible printed wiring boards which has the epoxy resin composition of Claim 4, or its hardened | cured material layer.   A single-sided or double-sided metal-clad resin laminate, wherein one side or both sides of the film according to claim 5 or a cured product layer thereof is in contact with the single-sided or single-sided metal-clad resin laminate of the metal foil layer. .   One type selected from the group consisting of the film according to claim 5, the sheet according to claim 6, the reinforcing plate according to claim 8, the cover lay according to claim 9, and the laminated plate according to claim 10. Flexible printed wiring board using the above.   The semiconductor insulating film which has an epoxy resin composition of Claim 4, or its hardened | cured material layer. (A) one or more selected from the group consisting of paraphenylenediamine, metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 1,5-naphthalenediamine and 1,8-naphthalenediamine A compound,
The phenolic hydroxyl group-containing polyamide according to claim 1, wherein (B) hydroxyphthalic acid and phthalic acid as an optional component (provided that 20 mol% to 100 mol% of both are hydroxyphthalic acid) are subjected to a condensation reaction. Manufacturing method of resin (A). (A) one or more compounds selected from the group consisting of paraphenylenediamine, metaphenylenediamine and 4,4′-diaminodiphenylmethane;
The phenolic hydroxyl group-containing polyamide according to claim 2, wherein (B) hydroxyphthalic acid and phthalic acid as an optional component (provided that 50 mol% or more and 100 mol% or less of them are hydroxyphthalic acid) are subjected to a condensation reaction. Manufacturing method of resin (A).