JP2001146546A - Epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition excellent in heat resistance and low water absorption while keeping excellent electrical properties. SOLUTION: This epoxy resin composition comprises as its main components a compound (A) having two epoxy compounds in the molecule and a polyamide (B) represented general formula (1) (wherein X and Y are each an aromatic residue, amino group and hydroxyl group are mutually in ortho positions and (n) is an integer of 2-100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition having excellent heat resistance, low water absorption, and excellent electrical properties.

[0002]

2. Description of the Related Art Epoxy resins are excellent in electrical insulating properties, mechanical properties, chemical resistance, adhesiveness, etc., and are used in many fields such as electrical insulating fields, electronic material fields, adhesives for structural materials, and paints. Used in the field. In recent years, in these fields, materials having various high-performance characteristics have been required. For example, in the field of electric insulation, high heat resistance, low water absorption, and low dielectric constant are required. However, a material that can sufficiently satisfy these demands for high performance has not been obtained so far.

[0003] As a means of obtaining a resin satisfying such requirements, an epoxy resin has been improved with bismaleimide. However, although it is possible to improve the heat resistance, since it has two carbonyl groups of the imide ring, there is a problem in electric characteristics and water absorption, and it has not yet reached a level satisfying all requirements. . Many attempts have been made to improve water absorption and electrical properties by introducing a substituent containing a fluorine atom into the molecular structure.However, the generation of a gas containing fluorine corrodes metal materials. In some cases, heat resistance is a concern.

[0004] Epoxy resins have been modified by modifying them with polyimide resins instead of bismaleimide resins, but the required levels can be cleared due to their excellent heat resistance and mechanical properties. However, on the contrary, it also has a drawback that the electrical characteristics and the water absorption are reduced. To solve these problems, by introducing fluorine and trifluoromethyl groups into the polymer,
Attempts have also been made to improve electrical properties, water absorption and heat resistance. On the other hand, polybenzoxazole resins, which are superior in electrical properties and water absorption to polyimide resins and exhibit performance comparable to heat resistance, have been actively studied and are being developed for various applications. Under such circumstances, in recent years, requirements for use in electronic components have become even more severe, and it is required to satisfy all the above-mentioned required characteristics.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of intensive studies in order to solve such problems of the conventional epoxy resin composition, and it has been found that heat resistance, low water absorption,
Another object of the present invention is to provide an epoxy resin composition having excellent electrical characteristics.

[0006]

That is, the present invention relates to a compound (A) having at least two epoxy groups in one molecule.
And a polyamide (B) represented by the general formula (1) as an essential component.

[0007]

Embedded image In the formula, X and Y are aromatic residues, and the amino group and the hydroxy group have an ortho-position with each other. N is 2 to 1
Indicates an integer of 00.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (A) having at least two epoxy groups in one molecule of the present invention is specifically exemplified by 4,4′-bis (2,3-epoxypropoxy) biphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl
4'-bis (2,3-epoxypropoxy) -3,3'-5,5 '
Bifunctional epoxy compounds such as -tetraethylbiphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetrabutylbiphenyl, or trifunctional epoxy compounds
Polyfunctional epoxy resin such as functional glycidylamine type epoxy resin, polyglycidyl ester of polycarboxylic acid, polyglycidyl ester of aliphatic polyhydroxy compound, silicone modified epoxy resin, rubber modified epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,
There are phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, epoxy resin with naphthalene skeleton, epoxy resin with dicyclopentadiene skeleton, epoxy resin with limonene skeleton, etc. It may be halogenated or hydrogenated.
Alternatively, two or more types are used in combination.

Further, the polyamide (B) represented by the general formula (1) is obtained by mixing a bisaminophenol compound represented by the general formula (3) or a derivative thereof such as an esterified product or an etherified product thereof with the general formula (4). ) Can be produced by a method such as an acid chloride method or a condensation reaction in the presence of a dehydrating condensing agent such as polyphosphoric acid and dicyclohexylcarbodiimide.

[0010]

Embedded image Wherein X is an aromatic residue.

[0011]

Embedded image Wherein Y is an aromatic residue.

The above bisaminophenol compound is represented by the general formula (3), and more preferably the one represented by the general formula (5). -Diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) Sulfide, bis (3-amino-4-hydroxyphenyl) ketone, bis (3-amino-4-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl)
Propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and the like are preferably used. These may be used alone or in combination of two or more.

[0013]

Embedded image

The dicarboxylic acid is represented by the general formula (4)
And further preferably those represented by the general formula (6), and specific examples include terephthalic acid, isophthalic acid, 4,4′-dicarboxybiphenyl,
3,3′-dicarboxybiphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxydiphenyl ketone, 4,4′-dicarboxydiphenyl sulfide,
4,4'-dicarboxydiphenylsulfone, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (4-
(Carboxyphenyl) hexafluoropropane is preferably used. These may be used alone, or 2
Combinations of more than one type can also be used.

[0015]

Embedded image

That is, the preferred polyamide (B) in the present invention is synthesized from a bisaminophenol compound represented by the general formula (5) and a dicarboxylic acid represented by the general formula (6). ).

[0017]

Embedded image

The polyamide (B) is synthesized according to a known method. As an example of a specific synthesis method, an acid chloride method may be used. The dicarboxylic acid is converted to N-methyl-2-
It is dissolved in a polar solvent such as pyrrolidone and reacted at room temperature to 75 ° C. in the presence of excess thionyl chloride, and then excess thionyl chloride is distilled off under reduced pressure. Thereafter, the precipitate is recrystallized with a solvent such as hexane to obtain dicarboxylic acid chloride. Next, the bisaminophenol compound is dissolved in a polar solvent such as N-methyl-2-pyrrolidone and reacted with dicarboxylic acid chloride at -30 ° C. to room temperature in the presence of an acid acceptor such as pyridine. A polyamide can be obtained.

In the present invention, the epoxy group compound (A)
And polyamide (B) are essential components, and their ratio is important. The content of the polyamide is preferably 10 to 40% by weight, more preferably 10 to 30% by weight, based on the total solid content of both the epoxy compound and the polyamide. When the amount of the polyamide to be blended is less than 10% by weight, the improvement in heat resistance by the addition of the polyamide cannot be sufficiently exhibited. On the other hand, if it exceeds 40% by weight, the excellent mechanical properties of the epoxy resin are undesirably reduced.

The epoxy resin composition of the present invention preferably contains a curing agent for epoxy resin. As the curing agent, any one may be used as long as it is generally used as a curing agent for an epoxy resin, for example, an amine compound, an acid anhydride, an imidazole, a polyhydric phenol compound, a phenol resin, dicyandiamide or a derivative thereof. Can be used. The compounding amount is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy compound (A). The amount is determined according to the purpose of use, and does not necessarily have to be equivalent to the epoxy compound.

A curing accelerator may be used to accelerate the curing reaction, for example, 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine,
Benzyldiamine, α-methylbenzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,
Tertiary amines such as 6-tris (dimethylaminomethyl) phenol, triethanolamine, diethylaminoethanol, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazoles such as -phenyl-4-methylimidazole, organic phosphine compounds such as triphenylphosphine, trimethylphosphine, triethylphosphine and tributylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, and tetrabutylphosphonium Tetra-substituted phosphonium such as tetrabutyl borate, tetra-substituted borate, 2-ethyl-4-methylimidazole tetramethyl borate, N
Tetraphenylboron salts such as -methylmorpholine / tetraphenylborate, and the like;
More than one species may be used in combination. The addition amount is preferably in the range of 0.01 to 1 part by weight based on 100 parts by weight of the epoxy compound (A).

The epoxy resin composition of the present invention may contain additives such as an antioxidant, a flame retardant, a flame retardant auxiliary, a lubricant, a coloring agent, and a filler as long as the desired performance is not impaired. it can.

The epoxy resin composition of the present invention can be used in a solid form as an epoxy resin molding material or a phenol resin molding material, or as a modifier thereof, by a compression molding method or a transfer molding method. ,
It is molded by a known molding method such as an extrusion molding method or an injection molding method, and is put to practical use. It is also possible to dissolve in an organic solvent and use it as an insulating material such as a laminate. More specifically, the resin composition is dissolved in the above-mentioned organic solvent and applied to a suitable support, for example, glass, fiber, metal, silicon wafer, ceramic substrate, or the like. Examples of the application method include dipping, screen printing, spraying, spin coating, roll coating, and the like. After application, the coating is heated and dried to volatilize the solvent, and a tack-free coating film can be obtained.

At this time, it is possible to convert the polyamide into a polybenzoxazole by ring closure, or to cause a crosslinking reaction of the epoxy compound. Depending on the intended use, it is also possible to carry out ring closure and curing after performing a predetermined step, only volatilization of the solvent. In addition, impregnated into a substrate such as glass fiber cloth or other cloth, paper and dried,
It can be a prepreg. As the impregnation method, brushing, spraying, dipping, or the like can be used, and a method in which the solvent is removed by heating and drying or a method in which the solvent is partially cured can be obtained.

As the organic solvent for dissolving the above-mentioned epoxy resin composition, a solvent which completely dissolves the solid content is preferable. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl Sulfoxide, cellosolve, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, 1,
3-butylene glycol-3-monomethyl ether, methyl-1,3-butylene glycol acetate, ethyl lactate, butyl lactate, methyl pyruvate, ethyl pyruvate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydroxyfuran, etc. These can be used alone or in combination of two or more. As the usage amount,
There is no problem as long as the amount can completely dissolve the epoxy compound and the polyamide, and it can be adjusted according to the intended use.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. First, an acid chloride is synthesized, a polyamide is synthesized using the acid chloride, and further, an epoxy resin composition is prepared, and a cured film is prepared.For property evaluation, a glass transition temperature, a water absorption, and The electrical characteristics were measured. The measurement method was as described below, and the evaluation results were summarized in Table 1.

1. Glass transition temperature (Tg) Viscoelasticity measurement device (DM manufactured by Seiko Instruments Inc.)
S210), using a frequency of 10 Hz and a heating rate of 3 ° C. /
Minute, measured in tensile mode, and t in the dynamic viscoelastic curve
The peak temperature of an δ was defined as the glass transition temperature (° C.).

2. The weight change rate after immersing a test film having a water absorption of 5 cm square and a thickness of 20 μm in pure water at 23 ° C. for 24 hours was calculated.

3. Electrical properties According to the method of JIS-C-6481, volume resistivity and 1M
The value of the relative dielectric constant at room temperature in Hz was measured.

[Synthesis of Acid Chloride] Synthesis Example 1 6 g of 4,4′-dicarboxydiphenyl ether, 24 g of thionyl chloride and 0.1 g of dry N, N-dimethylformamide (DMF) were placed in a reaction vessel and reacted at 60 ° C. for 2 hours. Allowed to react for hours. After completion of the reaction, unreacted thionyl chloride was distilled off by heating and reduced pressure. The precipitate in the reaction vessel was recrystallized using hexane to obtain 6.2 g of carboxylic acid chloride.

Synthetic Example 2 The same procedure as in Synthetic Example 1 was carried out to obtain 2,2′-bis (4-carboxyphenyl) hexafluoropropane acid chloride.

[Synthesis of Polyamide] Synthesis Example 3 To a flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel, 7.33 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ( 0.02 mol)
Was dissolved in 30 g of dimethylacetamide, and 3.0 g of pyridine was added. Then, under dry nitrogen introduction, 4.9 g of the acid chloride obtained in Synthesis Example 1 was added to 24 g of dimethylacetamide.
A solution having 0 g (0.02 mol) dissolved therein was added dropwise over 30 minutes while maintaining the system temperature at -15 ° C. After completion of the dropwise addition, the temperature was returned to room temperature, and the stirring was further continued for 4 hours. Then, the reaction solution was dropped into 1 L of distilled water, and the precipitate was filtered, washed, and dried at 50 ° C./24 hr to obtain 10.1 g of polyamide.

(Synthesis example 4) 2,2'-bis (3-amino-4-
Hydroxyphenyl) hexafluoropropane7.33
Except for using 7.85 g (0.02 mol) of the acid chloride obtained in Synthesis Example 2 with respect to g (0.02 mol), all operations were performed in the same manner as in Synthesis Example 3 to obtain 12.4 g of polyamide. Obtained.

[Preparation of Epoxy Resin Composition] Example 1 Bisphenol A type epoxy resin (epoxy equivalent 92
5) 80 g, 20 g of the polyamide obtained in Synthesis Example 3,
A varnish was obtained by dissolving 5 g of 4,4′-diaminodiphenylmethane and 1 g of dicyandiamide in a mixed solvent of 80% by weight of N, N-dimethylformamide and 20% by weight of methyl isobutyl ketone at room temperature. The varnish was applied on a glass plate using a doctor blade having a gap of 300 μm. After that, in an oven at 70 ° C for 1 hour,
After drying at 100 ° C./30 minutes and peeling, a resin composition film having a thickness of 20 μm was obtained. Fix the film with a metal frame,
150 ° C / 30 minutes, 250 ° C / 30 minutes, 350 ° C / 30
The mixture was heated under a nitrogen atmosphere in the order of minutes to obtain a cured film of the resin composition.

Example 2 Bisphenol A type epoxy resin (epoxy equivalent 92
5) 60 g, 40 g of the polyamide obtained in Synthesis Example 4,
3 g of 4,4'-diaminodiphenylmethane and 0.3 g of 2-ethyl-4-methylimidazole were mixed with 80% by weight of N, N-dimethylformamide and 20 g of methyl isobutyl ketone.
A cured film was prepared in the same manner as in Example 1 by dissolving at room temperature in a mixed solvent of weight%.

Example 3 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 90 g, 10 g of the polyamide obtained in Synthesis Example 3,
4.5 g of a phenol novolak resin (hydroxyl equivalent: 108, softening point: 90 ° C.), and 0.4 g of tetraphenylphosphine.
1 g was dissolved in a mixed solvent of N, N-dimethylformamide 80% by weight and methyl isobutyl ketone 20% by weight at room temperature, and the same operation as in Example 1 was carried out to prepare a cured film.

Example 4 Cresol novolak type epoxy resin (epoxy equivalent 2
00), 20 g of a bisphenol A type epoxy resin (epoxy equivalent: 925), 30 g of the polyamide obtained in Synthesis Example 4, 5 g of methyltetrahydrophthalic anhydride, and 0.5 g of 2-ethyl-4-methylimidazole were added to N, N -
It was dissolved in a mixed solvent of 80% by weight of dimethylformamide and 20% by weight of methyl isobutyl ketone at room temperature, and the same operation as in Example 1 was performed to prepare a cured film.

Comparative Example 1 A varnish was prepared in the same manner as in Example 1, except that the polyamide obtained in Synthesis Example 3 was not blended. This varnish was applied on a glass plate using a doctor blade with a gap of 300 μm,
The film was dried in an oven at 70 ° C. for 1 hour and at 100 ° C. for 30 minutes, and peeled to obtain a resin composition film having a thickness of 20 μm. The film is fixed with a metal frame, 150 ° C./30 minutes,
Heating was performed at 200 ° C. for 30 minutes in a nitrogen atmosphere to obtain a cured film of the resin composition.

Comparative Example 2 A varnish was prepared in the same manner as in Example 3 except that the polyamide obtained in Synthetic Example 3 was not used, and a varnish was prepared. To obtain a cured film.

[0040]

[Table 1]

From the evaluation results of Examples and Comparative Examples summarized in Table 1, the epoxy resin composition of the present invention has excellent water absorption and heat resistance while maintaining excellent electrical properties. You can see that. From the above, it is shown that the present invention can provide an epoxy resin composition excellent in heat resistance, low water absorption, and electrical properties.

[0042]

Industrial Applicability The epoxy resin composition of the present invention has improved heat resistance and low water absorption while maintaining excellent electrical properties. It is useful as an insulating material for wiring boards, as an adhesive resin for flexible copper-clad boards, and as a resin for epoxy molding materials.

Continued on the front page F-term (reference) 4J001 DA01 DC05 DC08 DC14 EB36 EB37 EB44 EB56 EB57 EB58 EB60 EC23 EC44 EC54 EC66 EC67 EC68 EC70 FA01 FB03 FB05 FC03 FC05 GA13 GA16 HA01 HA02 HA05 JA17 JB07 JB17 JB18 CDB CD CD CD061 CD081 CD131 CD201 CL062 FD140 FD150 GQ00 4J036 AA01 DA01 DA02 DB05 DB15 DC02 DC12 DC13 DC31 DC41 DC46 DD07 FB07 FB13 FB14 GA23 JA05 JA08

Claims (3)

[Claims] 1. An epoxy resin comprising, as essential components, a compound (A) having at least two epoxy groups in one molecule and a polyamide (B) represented by the general formula (1). Resin composition. Embedded image In the formula, X and Y are aromatic residues, and the amino group and the hydroxy group have an ortho-position with each other. N is 2 to 1
Indicates an integer of 00. 2. The epoxy resin composition according to claim 1, wherein the polyamide (B) has a repeating unit represented by the general formula (2). Embedded image 3. The compounding ratio of the compound (A) having an epoxy group and the polyamide (B) is such that (A) is 90 to 60% by weight and (B) is 10 to 40% by weight based on the total solid content of both components. % By weight
The epoxy resin composition according to the above.