JP2909878B2 - Heat resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin composition containing an aromatic polyamide resin and an epoxy compound which can be used in a wide range of fields including electronic equipment and electric equipment as paints, adhesives and coating agents. About.

[0002]

2. Description of the Related Art In general, an epoxy resin is a typical thermosetting resin, and has excellent processability such as being obtained as a liquid and being easily dissolved in an organic solvent, and having an amino group and a hydroxyl group. Not only has excellent reactivity such as easily reacting with many functional groups such as carboxyl group and carboxyl group, but also has excellent electrical properties, adhesive properties, thermal properties, etc. Used in However, epoxy resins are generally incapable of withstanding heat of 200 ° C. or higher, and thus improvement in heat resistance is strongly desired. The heat resistance of the epoxy resin can be achieved to some extent by curing the polyfunctional epoxy compound with an aromatic diamine or the like as a curing agent to obtain an epoxy resin having a high crosslinking density. However, the epoxy resin thus obtained is not only extremely brittle, but also has a large stress strain during curing and easily cracks when heat or mechanical shock is applied. In order to solve this problem, a method has been proposed in which a heat-resistant thermoplastic resin represented by polyimide is mixed with an epoxy resin (“Contact point between thermoplastic and thermosetting resin”, 19).
(Science Forum, Inc., September 30, 1992). However, since this mixing must be performed at a high temperature, workability is difficult, and polyimide is inferior in compatibility with an epoxy resin. Unable to generate a body,
Therefore, there is a problem that a sufficient improvement effect cannot be obtained.

[0003] Among thermoplastic resins, those excellent in heat resistance and the like represented by a polyimide resin are known, but this kind of resin is usually insoluble or insoluble or soluble. It only dissolves in a slightly toxic high-boiling solvent, and has poor processability and low adhesion and adhesion to other materials, so it must be used alone. There are problems such as not. An aromatic polyamide resin is known as a thermoplastic resin having excellent heat resistance. Aromatic polyamide resins are generally soluble only in high-boiling solvents, and the solvents are also limited to highly toxic amide solvents and have the problem of poor processability. Furthermore, depending on the method of obtaining a polyamide resin by a polycondensation reaction between an acid and an amino compound, a functional group such as an amino group, a carboxyl group, or a hydroxyl group necessary for reacting with an epoxy group of an epoxy resin to form a molecular complex. It was difficult to obtain an aromatic polyamide resin having a group. By the way, the present inventors have previously proposed a method by which a polyamide resin can be produced from a monomer having a phenolic hydroxyl group without using a special condensing agent without easily protecting the phenolic hydroxyl group (Japanese Patent Laid-Open No. JP-A-63493), and an aromatic polyamide resin containing a phenolic hydroxyl group has a specific molecular structure, so that it can easily be used in non-amide solvents represented by alcohols and mixed solvents thereof. It was found to dissolve, and a proposal was made.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances in the prior art, and has as its object to maintain excellent properties of an epoxy resin and to provide an excellent heat resistance. An object of the present invention is to provide a heat-resistant resin composition having heat resistance and mechanical properties and excellent in processability. Another object is to mix an epoxy compound with an aromatic polyamide resin having a phenolic hydroxyl group, which is sufficiently compatible with the epoxy resin, is capable of molecular complexation, and has excellent processability and heat resistance. Accordingly, an object of the present invention is to provide an epoxy resin composition having excellent heat resistance and mechanical properties.

[0005]

Means for Solving the Problems The heat-resistant resin composition of the present invention comprises 90 units of a repeating unit represented by the following general formula (1).
It is characterized by containing an aromatic polyamide resin having a phenolic hydroxyl group or a copolymer thereof and a polyfunctional epoxy compound containing at least mol%.

Embedded image (In the formula, R ¹ and R ² each represent a group selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group, but they are not hydrogen atoms at the same time.)

Hereinafter, the present invention will be described in detail. The aromatic polyamide resin or its copolymer in the present invention must contain the repeating unit represented by the general formula (1) in an amount of 90 mol% or more. When the content of the repeating unit represented by the general formula (1) is lower than 90 mol%, the processability for forming a complex with the epoxy compound becomes difficult, and therefore, it is inappropriate to use in the present invention. It is. Further, the aromatic polyamide resin or the copolymer thereof in the present invention has a molecular weight of 5,000 to 150,000.
0 and a glass transition point (Tg) of 200
Those having a temperature of at least ° C are preferred. Such an aromatic polyamide resin has a feature that, when compounded with an epoxy compound, not only improves the heat resistance but also improves the mechanical properties by increasing the Tg of the obtained epoxy resin. Things.

The aromatic polyamide resin having a repeating unit represented by the general formula (1) in the present invention can be easily produced by an amidation polycondensation reaction between an aromatic dicarboxylic acid and an aromatic diamine. As the aromatic dicarboxylic acid, an aromatic dicarboxylic acid having a phenolic hydroxyl group represented by the following general formula (2) or a mixture thereof with another aromatic dicarboxylic acid and a derivative thereof is used. Can be used an aromatic diamine represented by the following general formula (3) or a mixture thereof with another aromatic diamine.

Embedded image (In the formula, R ¹ and R ² each represent a group selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group, but they are not hydrogen atoms at the same time.)

The aromatic dicarboxylic acid having a phenolic hydroxyl group represented by the above general formula (2) which can be used in the present invention includes 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, Examples include, but are not limited to, 3-hydroxyphthalic acid, 2-hydroxyterephthalic acid, and the like.

Other aromatic dicarboxylic acids and derivatives thereof which can be used in combination with the aromatic dicarboxylic acid having a phenolic hydroxyl group represented by the general formula (2) include isophthalic acid, terephthalic acid, 4'-biphenyldicarboxylic acid, 3,3'-methylene dibenzoic acid,
4,4'-methylene dibenzoic acid, 4,4'-oxydibenzoic acid, 3,4'-oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,
4'-carbonyldibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-
Naphthalenedicarboxylic acid, ethylenediaminebisphthalimide-4,4'-dicarboxylic acid, 3,3'-bis (4
-Carboxyphenyl) propane, 3,3'-bis (4
-Carboxyphenyl) hexafluoropropane, bis (4-carboxyphenyl) methane, 3,3'-bis (4-carboxyphenyl) hexafluoropropane, and derivatives thereof, but are not limited thereto. is not.

On the other hand, as the aromatic diamine represented by the general formula (3) which can be used in the present invention, bis (4-amino-3-methylphenyl) methane,
Bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3-ethylphenyl) methane,
Bis (4-amino-3,5-diethylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl)
Examples include, but are not limited to, methane, bis (4-amino-3-isopropylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, and the like.

Other aromatic diamines which can be used in combination with the aromatic diamine represented by the general formula (3) include, for example, p-phenylenediamine, 4,4'-
Diaminophenyl ether, 3,3'-dimethyl-4,
4'-diaminophenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide,
Metatolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
4,4'-diaminophenylthioether, 3,3'-
Dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,
3'-dimethyl-4,4'-diaminobenzophenone,
3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,
4'-diaminodiphenylmethane, 2,2'-bis (3
-Aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfoxide, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, , 3'-
Diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, 3,3'-dihydroxy-4,4 '
-Diaminobiphenyl, 3,3'-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, etc., and these can be used alone or in combination.

In the present invention, the amidation polycondensation reaction between the aromatic dicarboxylic acid and the aromatic diamine is carried out by a known method using a condensing agent such as phosphorous acid or a derivative thereof and a pyridine derivative. be able to. For example, the method can be carried out according to the method described on page 183 of "Polymer Functional Material Series 2 Synthesis and Reaction of Polymer", edited by The Society of Polymer Science, 1991. That is, the above-mentioned monomers composed of the aromatic dicarboxylic acid component and the aromatic diamine component are dissolved in the reaction solvent so as to contain 5 to 30% by weight, and the phosphorous acid and its derivative and the pyridine derivative are used as the condensing agent. Reaction temperature in the presence of room temperature to 160 ° C
By reacting for about 30 minutes to several hours, the aromatic polyamide resin of the present invention can be obtained.
Lithium chloride, calcium chloride, or the like is added as a stabilizer to this polymerization reaction as needed.

[0013] Phosphorous acid and its derivatives usable in this case include triphenyl phosphite, diphenyl phosphite, -o-tolyl phosphite, di-o-tolyl phosphite, and tri-phosphite. m-tolyl, di-m-tolyl phosphite, di-p-tolyl phosphite, tri-p-tolyl phosphite, di-p-chlorophenyl phosphite, tri-phosphite
p-chlorophenyl and the like; and pyridine derivatives include pyridine, 4-methylpyridine, 3-methylpyridine, 2,4-lutidine, 2,5-lutidine,
Examples include, but are not limited to, 3,5-lutidine and the like.

As the reaction solvent used in the above reaction, a usual reaction solvent can be used. Generally, in the production of a polyamide resin using triphenyl phosphite and a pyridine derivative, N-type is mainly used. -Methyl-2-
Pyrrolidone, dimethylacetamide, pyridine, 1,3
An amide solvent represented by -dimethyl-2-imidazolidinone or the like can be used.

In synthesizing the aromatic polyamide resin, in order to contain the repeating unit represented by the general formula (1) in an amount of 90 mol% or more, the aromatic dicarboxylic acid component and the aromatic diamine component should be used. The amounts of the aromatic dicarboxylic acid having a phenolic hydroxyl group represented by the general formula (2) and the aromatic diamine represented by the general formula (3) may be appropriately controlled.

A reaction solution containing an aromatic polyamide resin having a phenolic hydroxyl group or a copolymer thereof produced by the amidation condensation polymerization reaction is introduced into water, a mixture of water and methanol or a mixture of water and ethanol. Or,
Alternatively, water, a mixed solution of water and methanol or water and ethanol, or the like is introduced into these reaction solutions, whereby the aromatic polyamide resin used in the present invention can be obtained.

The aromatic polyamide resin having a phenolic hydroxyl group of the present invention obtained as described above is soluble in alcohol, and the alcohol used for producing the alcohol solution includes methanol, ethanol, and the like. Propanol is preferred, and methanol is particularly preferred. This resin, besides these alcohols,
Aromatic solvents such as benzene and toluene; ketone solvents such as acetone and methyl ethyl ketone; halogen solvents such as chloroform and chlorobenzene; ester solvents such as ethyl acetate; nitro group-containing solvents such as nitrobenzene and nitromethane; acetonitrile; It is soluble in nitrile solvents such as nitrile, amine solvents such as triethylamine and piperidine, and ether solvents such as diethyl ether and tetrahydrofuran, and these can be appropriately selected as needed.

The polyfunctional epoxy compound used in the heat-resistant resin composition of the present invention may be of any type as long as it is a compound having two or more epoxy groups in one molecule. For example, glycidyl ethers, Glycidyl esters, glycidylamines, linear aliphatic epoxides,
Resins composed of alicyclic epoxides, hydantoin-type epoxies, and the like. Examples of glycidyl ethers include glycidyl ether of biphenyl, glycidyl ether of bisphenol, polyglycidyl ether of phenol novolak, glycidylyl ether of alkylene glycol or polyalkylene glycol, and naphthalenediglycidyl ether. Also,
Examples of the glycidyl ether of bisphenol include bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, tetramethylbisphenol A type, tetramethylbisphenol F type, tetramethylbisphenol AD type, tetramethylbisphenol S type, and tetrachloroform. Examples include diglycidyl ethers of dihydric phenols such as bisphenol A type and tetrabromobisphenol A type. Further, as polyglycidyl ether of phenol novolak, for example,
Polyglycidyl ethers of novolak resins such as phenol novolak, cresol novolak, brominated phenol novolak, and ortho-cresol novolak are exemplified. Furthermore, polyphenylol type glycidyl ether,
Examples of the diglycidyl ether of aralkylene glycol or polyalkylene glycol include diglycidyl ethers of glycols such as polyethylene glycol, polypropylene glycol, and butanediol.

Examples of the glycidyl esters include glycidyl esters of hexahydrophthalic acid and glycidyl esters of dimer acid. Examples of the glycidyl amines include triglycidylaminophenylmethane and triglycidylamino. Examples include phenol and triglycidyl isocyanate. Further, examples of linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil, and examples of alicyclic epoxides include 3,4-epoxy-6-methylcyclohexylmethyl carboxylate, 3,4-epoxycyclohexylmethyl carboxylate, hydrogenated bisphenol epoxy, and the like. Examples of the hydantoin-type epoxies include diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and tris (hydroxyphenyl) methane-based polyfunctional epoxy compound, tetraglycidyloxyphenylsulfone, and biphenyl novolak-type glycidyl ether. It is not limited to these.

In the heat-resistant resin composition of the present invention, the mixing ratio of the above-mentioned aromatic polyamide and polyfunctional epoxy compound can be arbitrarily changed according to the purpose of use and the type of epoxy compound to be used. , 1:
In the range of 99-99: 1, preferably 5: 95-9.
The range is 5: 5.

In the present invention, chemical substances other than the aromatic polyamide having a phenolic hydroxyl group to be reacted with the above-mentioned polyfunctional epoxy compound and its copolymer can be used as required. Such chemicals include:
Generally known as a curing agent for epoxy resin,
For example, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, 1,5-diaminonaphthalene, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-
Aromatic amine compounds such as 1,4-phenylenediamine, 1,3-di (p-aminophenyl) propane, m-xylenediamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, Aliphatic amine compounds such as sendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polymethylenediamine, and polyetherdiamine;
Amines, including tertiary and tertiary amines, carboxylic acids, polyaminoamide compounds, aliphatic and aromatic polyamide oligomers and polymers, fats such as dodecyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride Alicyclic acid anhydrides such as aliphatic acid anhydrides, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, and glycerol tristriate Aromatic acid anhydrides such as melitate, phenolic compounds and phenolic resins, amino resins, urea resins, melamine resins, dihydrazines, imidazoles, Lewis acids, Bronsted acid salts, polymercaptons, isocyanates, blocked isocyanates Kind, polyvinyl Nord acids, N, N'-substituted bis-but maleimide and the like, but is not limited thereto.

In the present invention, a reaction accelerator may be added, if necessary, to accelerate the reaction between the aromatic polyamide resin and the epoxy compound. Examples of the reaction accelerator include phosphorus compounds such as triphenylphosphine and / or triethylamine, triethanolamine, 1,8-diaza-bicyclo [5,4,
0] -7-undecene (DBU), tertiary amines such as N, N-dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole, N-methylpiperazine Compounds and boron compounds such as 1,8-diazabicyclo [5,4,0] -7-undecenium tetraphenylborate are used.

The heat-resistant resin composition of the present invention includes a composition before the reaction between the hydroxyl group of the aromatic polyamide having a phenolic hydroxyl group and the epoxy group of the polyfunctional epoxy compound, and a composition after the reaction. Articles and molded articles are also included.
In the present invention, the reaction is generally carried out at room temperature to room temperature.
The reaction can be carried out in a temperature range of 250 ° C. for several hours or at room temperature, and the reaction method is not limited at all.

The heat-resistant resin composition of the present invention may contain other additives as necessary. For example, release agents such as natural waxes, synthetic waxes, long-chain aliphatic acids and metal salts thereof, acid amides, esters, paraffins, etc., and stress relaxation agents such as silicone rubber, nitrile rubber, butadiene rubber polysiloxane, etc. , Chlorinated paraffin, bromotoluene, hexabromobenzene, antimony trioxide and other flame retardants, silane coupling agents, titanate coupling agents, aluminum coupling agents and other coupling agents, fused silica, crystalline silica, Glass flakes, glass beads, glass balloons, talc, alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, zinc, lead,
Metal powders such as iron powder, iron oxide, iron sand, inorganic fillers such as graphite and carbon, or conductive particles, coloring agents such as dyes and pigments, oxidation stabilizers, light stabilizers, moisture resistance improvers, thixotropic agents, and dilution Agents, antifoaming agents, other resins, and the like.

Further, the heat-resistant resin composition of the present invention exhibits its usefulness by using it as a surface protective agent, a coating agent, an adhesive, a binder, a sealant, etc. due to its properties. Particularly, for electronic devices, coating agents for semiconductor devices, resin sealing agents, die bonding agents for devices and supporting substrates, materials for LSI mounting substrates, etc., and for electrical devices, impregnated varnishes, binder resins for prepregs , Housing agent and the like.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Synthesis example (Synthesis of aromatic polyamide having phenolic hydroxyl group)
In a 200 ml three-necked round-bottomed flask equipped with a mechanical stirrer, a cooling tube, a calcium chloride tube, and a nitrogen inlet tube, 3.642 g of 5-hydroxyisophthalic acid (2.
0 mmol), 3,3 ', 5,5'-tetraethyl-
6.209 g of 4,4'-diaminodiphenylmethane (2
0 mmol), calcium chloride 2.02 g, lithium chloride 0.66 g, N-methyl-2-pyrrolidone 120 m
1, pyridine 6 ml, triphenyl phosphite 12.41
g (40 mmol) at 120 ° C. under a nitrogen atmosphere.
For 4 hours with stirring. After completion of the reaction, the reaction solution was introduced into a mixed solution having a water: methanol ratio of 8: 2 to precipitate a resin. The produced resin was repeatedly washed twice using a mixed solution of methanol and water as a washing solvent, and dried to obtain 9.05 g of an aromatic polyamide resin. The intrinsic viscosity value of this resin was 0.60 dl / g (calculated from viscosity measurement of a dimethylacetamide solution having a concentration of 0.5 g / dl at 30 ° C.), and this resin was soluble in ethanol.

Example 1 1.00 g of the aromatic polyamide having a phenolic hydroxyl group obtained in the above synthesis example, bisphenol A type epoxy compound (Epicoat 828, manufactured by Yuka Shell Epoxy)
After dissolving 0.80 g and triphenylphosphine 0.02 g as a reaction accelerator in a mixed solvent consisting of 3.5 g of ethanol, 0.5 g of tetrahydrofuran and 0.6 g of methyl ethyl ketone, this solution is applied on a glass substrate. Then, the resultant was heated at 120 ° C. for 2 hours, and then heated at 180 ° C. for 2 hours to form a transparent resin composition film. For the obtained film, the maximum stress of the film was measured using a dynamic viscoelasticity measuring device (Rheospectral DVE-3, manufactured by Rheology) and a tensile strength measuring device (AGS-100A, manufactured by Shimadzu Corporation). It was measured. Table 1 shows the results.

Example 2 The bisphenol A type epoxy compound of Example 1 was 0.66 g of a biphenyl type epoxy compound (YX-4000IT, manufactured by Yuka Shell Epoxy), and the mixed solvent was 2.0 g of methanol and 3.65 g of tetrahydrofuran. A film of the resin composition was prepared in the same manner as in Example 1 except that the mixed solvent was replaced with a mixed solvent consisting of the following. Table 1 shows the results.

Comparative Example 1 Bisphenol A type epoxy compound (Epicoat 82)
8, 1.00 g of Yuka Shell Epoxy Co., Ltd.) was heated to 120 ° C., and 0.345 g of bis (4-aminophenyl) sulfone was dissolved therein. Then, this solution was applied to a glass substrate and heated at 150 ° C. By heating at 180 ° C. for 2 hours and then at 180 ° C., a resin film was formed. The same measurement as in Example 1 was performed on the obtained film. Table 1 shows the results.

Comparative Example 2 1.00 g of biphenyl type epoxy compound (YX-4000IT, manufactured by Yuka Shell Epoxy) and 0.70 g of phenol novolak resin (trade name: D-5, manufactured by Toto Kasei)
And triphenylphosphine 0.01 as a reaction accelerator
7 g was dissolved in 6.8 g of dimethylformamide, this solution was applied on a glass substrate, dried at 80 ° C., and then heated at 150 ° C. for 2 hours and then at 180 ° C. for 2 hours to obtain a resin film. It was created. The same measurement as in Example 1 was performed on the obtained film. Table 1 shows the results.

[0031]

[Table 1]

[0032]

The heat-resistant composition obtained by the present invention comprises a specific aromatic polyamide resin and a polyfunctional epoxy compound, and as shown in Table 1, has excellent thermal properties and mechanical properties. It has characteristics and can be used in a wide range of fields as surface protection, coating, adhesion, binding, sealing, etc. of various materials and various articles, especially electronic equipment and electric equipment, etc. Can be.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 63/00-63/10 C08L 77/10 C08G 59/62

Claims (1)

(57) [Claims] 1. A phenolic hydroxyl group-containing aromatic polyamide resin or a copolymer thereof containing a repeating unit represented by the following general formula (1) in an amount of 90 mol% or more, and a polyfunctional epoxy compound. Heat resistant resin composition. Embedded image (In the formula, R ¹ and R ² each represent a group selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group, but they are not hydrogen atoms at the same time.)