JP2012153814A - Epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve dielectric characteristics, and to maintain the other characteristics at the same time.SOLUTION: An epoxy resin composition includes epoxy resin having two or more epoxy groups in one molecule, and tertiary amine compound. The ratio ((B)/(A)) of the number of moles (B) of the tertiary amine compound to the number of moles (A) of the epoxy group of the epoxy resin is 0.05 to 0.65.

Description

  The present invention relates to an epoxy resin composition.

  In recent years, information processing devices such as notebook personal computers and mobile phones have been required to be faster, and the CPU clock frequency has been increased. Therefore, a high signal propagation speed is required, and a printed wiring board with high dielectric characteristics is required.

  An epoxy resin composition is used as an insulating material for the printed wiring board. Curing of the epoxy resin composition is generally performed by reacting an epoxy resin with a curing agent having active hydrogen such as a primary amine, secondary amine, polyfunctional carboxylic acid, or phenol resin. is there. However, in such a curing reaction, a highly polar alcoholic hydroxyl group is generated by a reaction between an epoxy group and active hydrogen, so that dielectric characteristics are deteriorated. Further, when the crosslink density is increased in order to impart heat resistance, the concentration of alcoholic hydroxyl groups in the cured product is further increased, and the dielectric properties are further decreased.

  Therefore, for example, in Patent Document 1, an epoxy resin having a β-methyl group-substituted epoxy group and a curing agent are essential components, and the dielectric constant of the obtained cured product at a frequency of 1 GHz is 3.0 or less. An epoxy resin composition suitable as a resin component for circuit boards and semiconductor devices that does not impair moldability, has excellent heat resistance and moisture resistance, and requires electrical characteristics such as low dielectric constant and low dielectric loss tangent has been obtained. .

  In Patent Document 2, a polycondensate of an aromatic polyvalent carboxylic acid and an aromatic polyvalent hydroxy compound having an aryloxycarbonyl group at the chain end is used as a curing agent for an epoxy resin, thereby reducing the crosslink density. A cured product of an epoxy resin composition used as a curing agent having a high heat resistance and a low dielectric loss tangent is obtained.

Japanese Patent Laying-Open No. 2005-307031 JP 2008-291279 A

  However, in order to meet the demand for further increasing the signal propagation speed of information processing equipment, there is a need for an epoxy resin composition having a further improved dielectric property compared to Patent Document 1.

  Moreover, in the technique of patent document 2, while improving a dielectric characteristic, about other characteristics, it will fall rather than the conventional epoxy resin composition. For example, in the example of Patent Document 2, it is described that as a curing condition, pressure curing is performed for 1 hour under conditions of 170 ° C. and 3 MPa, and then heat curing is performed in a vacuum dryer for 10 hours under conditions of 190 ° C. and 133 Pa. In comparison with the conventional epoxy resin composition using a curing agent, there is a problem in that it takes time to cure. In addition, the wiring board formed from the resin composition of Patent Document 2 is hydrolyzed by ester bonds contained in the curing agent under process conditions (for example, etching), resulting in a decrease in mechanical strength or a smooth surface. There is also a problem of not becoming.

  This invention is made | formed in view of the said situation, and it is providing the epoxy resin composition which can maintain another characteristic, improving a dielectric characteristic.

  According to the present invention, the tertiary amine compound with respect to the number of moles (A) of epoxy groups contained in the epoxy resin, including an epoxy resin having two or more epoxy groups in one molecule and a tertiary amine compound. An epoxy resin composition is provided in which the ratio (B) / (A)) of the number of moles (B) is 0.05 to 0.65.

  Moreover, according to this invention, the prepreg which has a resin layer which consists of said epoxy resin composition, and a fiber base material is provided.

  Moreover, according to this invention, the laminated board formed by forming a metal layer in the one side or both surfaces of said prepreg is provided.

  Moreover, according to this invention, the hardening body of said epoxy resin composition is provided.

  Moreover, according to this invention, the printed wiring board which has a circuit formation surface in the single side | surface or both surfaces of said laminated board is provided.

  Furthermore, according to this invention, a semiconductor device provided with the semiconductor element mounted in said printed wiring board is provided.

  According to the present invention, the tertiary amine compound is included in a molar ratio of 0.05 to 0.65 with respect to the number of moles of the epoxy group contained in the epoxy resin having two or more epoxy groups in one molecule. Epoxy resins can be polymerized through an ether bond using a tertiary amine compound as a catalyst. Therefore, generation of hydroxyl groups is suppressed, and the dielectric loss tangent can be improved without increasing the dielectric constant. In addition, these tertiary amine compounds have low reactivity with respect to other components except that they react catalytically with respect to other than epoxy groups, and are affected by severe process conditions such as etching before and after curing. Hateful. Therefore, an epoxy resin composition capable of maintaining other characteristics while improving dielectric characteristics can be realized.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which can maintain another characteristic is improved, improving a dielectric characteristic.

  Hereinafter, embodiments of the present invention will be described.

  The epoxy resin is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, alkyl substituted bisphenol A type epoxy resin, halogen substituted bisphenol A type Epoxy resin, bisphenol F type epoxy resin, alkyl substituted bisphenol F type epoxy resin, halogen substituted bisphenol F type epoxy resin, bisphenol S type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin , Biphenyl type epoxy resin, naphthalene type epoxy resin, and cyclopentadiene type epoxy resin. One of these can be used alone, or two or more can be used in combination.

  It is preferable that an epoxy resin contains 30 weight% or more in an epoxy resin composition. The prepreg obtained using such an epoxy resin composition can exhibit high peel strength when laminated on a metal foil. Moreover, it is preferable that the epoxy resin in an epoxy resin composition shall be 90 weight% or less from a viewpoint of fully reducing a dielectric loss tangent.

  The tertiary amine compound used in the present invention is not particularly limited as long as it is an amine compound having at least one nitrogen atom bonded to three carbon atoms in the molecule, but does not volatilize under the curing conditions of the epoxy resin composition. Is preferred. Tertiary amine compounds include aliphatic tertiary amines such as trimethylamine, triethylamine and tribenzylamine, aromatic tertiary amines such as triphenylamine and tri-p-toluylamine, imidazole, pyridine, p-dimethylaminopyridine, N -Nitrogen-containing heterocyclic compounds such as methylmorpholine, quinoline, isoquinoline, pyrimidine, piperazine, and derivatives thereof.

  Of these, nitrogen-containing heterocyclic compounds are preferable, and imidazole or a derivative thereof is particularly preferable. Any imidazole derivative may be used as long as it has an imidazole skeleton, such as 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 1-isobutyl. 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole (1B2PZ), 1-benzyl-2-methylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4 -Diamino-6 (2'-U Decylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl-4-methylimidazole (1')) ethyl-s-triazine, 2-phenyl-3,5-dihydroxy Methylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] And triazine duct imidazoles such as benzimidazole (TBZ) and 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine) (C11Z-A).

  The ratio of the number of moles (B) of the tertiary amine compound to the number of moles (A) of the epoxy groups of the epoxy resin ((B) / (A)) is 0.05 to 0.65, but the heat resistance (glass From the viewpoint of improving the transition point, it is preferably 0.1 to 0.25.

  Further, the content of the tertiary amine compound is preferably 5 to 50 parts by weight of the tertiary amine with respect to 100 parts by weight of the epoxy resin, but from the viewpoint of heat resistance (glass transition point), 5 to 20 is preferable. More preferred are parts by weight. By setting the content of the tertiary amine compound to the lower limit value or more, good dielectric properties can be obtained. Moreover, high glass transition temperature can be obtained by making the content of a tertiary amine compound below an upper limit.

  The epoxy resin composition of the present invention may contain a thermosetting resin other than the epoxy resin. Examples of thermosetting resins other than epoxy resins include urea (urea) resins, melamine resins and other triazine ring resins, unsaturated polyester resins, bismaleimide resins, polyurethane resins, diallyl phthalate resins, silicone resins, and benzoxazine rings. And the like.

  Moreover, you may add the resin component for improving the adhesiveness with a conductor layer to the epoxy resin composition of this invention. For example, phenoxy resin, polyamide resin, polyvinyl alcohol resin, and the like can be given.

  The epoxy resin composition of the present invention may contain an inorganic filler such as talc, alumina, glass, silica, mica, aluminum hydroxide, magnesium hydroxide, etc. Among them, fused silica excellent in low thermal expansion is preferable. The shape is crushed and spherical, but in order to lower the melt viscosity of the resin composition, a usage method suitable for the purpose such as using spherical silica is adopted. It is preferable that the inorganic filler has a lower limit contained in the epoxy resin composition of 50% by weight or more because thermal expansion and water absorption are reduced. Further, when the upper limit contained in the epoxy resin composition is 90% by weight or less, there is no concern that the operability such as impregnation is lowered.

  Since the epoxy resin composition of the present invention improves the wettability of the interface between the resin and the filler, a silane coupling agent can also be used. Examples of the silane coupling agent include an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, and a silicone oil type coupling agent, and one or more of these are used. May be. The pigment of the silane coupling agent is preferably 0.1 to 5% by weight with respect to the entire epoxy resin composition. By setting it as 0.1 weight% or more, a coupling agent can be disperse | distributed to the whole surface of a filler. Moreover, the fall of glass transition temperature can be prevented by setting it as 5 weight% or less.

  The epoxy resin composition of the present invention is within the range not impairing its properties, other than the above components such as pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, etc. Additives can be added.

  Next, the prepreg will be described. This prepreg has a resin layer made of the above-described epoxy resin composition and a fiber base material. Thereby, the prepreg suitable for manufacturing the printed wiring board excellent in the dielectric property and heat resistance can be obtained.

  Although it does not specifically limit as a fiber base material, Glass fiber base materials, such as a glass woven fabric and a glass nonwoven fabric, Polyamide-type resin fibers, such as a polyamide resin fiber, an aromatic polyamide resin fiber, and a wholly aromatic polyamide resin fiber, A polyester resin fiber Synthetic fiber base materials composed of woven or non-woven fabrics mainly composed of polyester resin fibers such as aromatic polyester resin fibers and wholly aromatic polyester resin fibers, polyimide resin fibers and fluororesin fibers, kraft paper, cotton Examples thereof include organic fiber base materials such as linter paper and paper base materials mainly composed of linter paper and kraft pulp mixed paper. Among these, a glass fiber base material is preferable. Thereby, the intensity | strength of a prepreg can improve, a water absorption can be lowered | hung, and a thermal expansion coefficient can be made small.

  Although the glass which comprises a glass fiber base material is not specifically limited, For example, E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass etc. are mentioned. Among these, E glass, T glass, or S glass is preferable. Thereby, the high elasticity of a glass fiber base material can be achieved and a thermal expansion coefficient can also be made small.

  Although the method for producing the prepreg is not particularly limited, for example, a resin varnish is prepared using the above-described epoxy resin composition, a method of immersing a fiber substrate in the resin varnish, a method of applying with various coaters, and spraying by spraying Methods and the like. Among these, the method of immersing the fiber base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to the fiber base material can be improved. In addition, when a fiber base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.

  The solvent used for the resin varnish desirably has good solubility in the resin component in the epoxy resin composition, but a poor solvent may be used as long as it does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, and carbitol. It is done.

  The solid content of the resin varnish is not particularly limited, but the solid content of the epoxy resin composition is preferably 50 to 80% by weight, and particularly preferably 60 to 78% by weight. Thereby, the impregnation property to the base material of a resin varnish can further be improved. After impregnating the fiber base material with the epoxy resin composition, it can be heated to a predetermined temperature and dried to obtain a prepreg. Although a drying temperature is not specifically limited, For example, it can be 90-220 degreeC.

  A laminate may be produced by forming a metal layer on one or both sides of the prepreg. Specifically, this laminated plate can be produced by stacking at least one or a plurality of the above-described prepregs on top and bottom surfaces of metal foil, and heating and pressing. Although the temperature to heat is not specifically limited, 120-230 degreeC is preferable and especially 150-210 degreeC is preferable. Moreover, the pressure to pressurize is not particularly limited, but is preferably 1 to 5 MPa, and particularly preferably 2 to 4 MPa. Thereby, the laminated board excellent in the dielectric property and the mechanical and electrical connection reliability in high temperature and high humidity can be obtained.

  The metal foil is not particularly limited, but, for example, copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys Metal foils, such as an alloy, iron, and an iron-type alloy, are mentioned.

  Although the thickness of metal foil is not specifically limited, It is preferable that they are 0.1 micrometer or more and 70 micrometers or less. By setting the thickness of the metal foil to 0.1 μm or more, the metal foil is damaged and the generation of pinholes is suppressed. In addition, when the metal foil is etched and used as a conductor circuit, there is no fear of plating variations during circuit pattern formation, circuit disconnection, or infiltration of a chemical solution such as an etching solution or a desmear solution. Further, by setting the upper limit to 70 μm or less, variations in the thickness of the metal foil and the surface roughness of the metal foil roughened surface can be minimized.

  Moreover, you may produce the adhesive sheet by forming the resin layer which consists of an epoxy resin composition of this invention on a carrier film or metal foil. In this case, first, the epoxy resin composition of the present invention is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve type. In various organic solvents such as carbitol and anisole, various mixing machines such as ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation and revolution dispersion method are used. Dissolve, mix and stir to make a resin varnish.

  Although content of the epoxy resin composition in a resin varnish is not specifically limited, 45 to 85 weight% is preferable and 55 to 75 weight% is especially preferable.

  Next, the resin varnish is coated on a carrier film or a metal foil using various coating apparatuses, and then dried. Or after spray-coating a resin varnish on a carrier film or metal foil with a spray apparatus, this is dried. By these methods, an adhesive sheet can be produced.

  Although a coating apparatus is not specifically limited, For example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, etc. can be used. Among these, a method using a die coater, a knife coater, and a comma coater is preferable. Thereby, the adhesive sheet which does not have a void and has the thickness of the uniform resin layer can be manufactured efficiently.

  Since the carrier film forms a resin layer on the carrier film, it is preferable to select a carrier film that is easy to handle. Further, since the carrier film is peeled off after laminating the resin layer of the adhesive sheet on the circuit forming surface of the laminated plate having the circuit forming surface, it is preferable that the carrier film be easily peeled off after being laminated on the laminated plate. For example, it is preferable to use a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a thermoplastic resin film having heat resistance such as a fluorine resin, or a polyimide resin. Among these, a film made of polyester is particularly preferable from the viewpoint of easy peeling.

  Although the thickness of a carrier film is not specifically limited, 1-100 micrometers is preferable and 3-50 micrometers is especially preferable. By carrying out like this, it can be set as the adhesive sheet which is easy to handle and excellent in the flatness of the surface of a resin layer.

  After laminating the adhesive sheet on the circuit forming surface of the laminate, the metal foil may be peeled off or etched to form a conductor circuit. The same metal foil that can be used for the above-described laminated plate can be used as the metal foil, but the thickness of the metal foil is further preferably 1 μm or more and 35 μm or less, and more preferably 1.5 μm or more and 18 μm or less.

  The metal foil can also be an ultrathin metal foil with a carrier foil. The ultrathin metal foil with a carrier foil is a metal foil obtained by laminating a peelable carrier foil and an ultrathin metal foil. An ultrathin metal foil layer can be formed on both surfaces of the resin layer by using an ultrathin metal foil with a carrier foil. Therefore, for example, when forming a circuit by the semi-additive method, etc., without performing electroless plating, electrolytic plating is performed by using an ultrathin metal foil as a direct feed layer, and after the circuit is formed, the ultrathin copper foil is flash etched. can do. By using an ultra-thin metal foil with a carrier foil, even with an ultra-thin metal foil having a thickness of 10 μm or less, for example, a reduction in handling properties of the ultra-thin metal foil in a pressing process, and cracking or cutting of the ultra-thin copper foil are prevented. Can do.

  The thickness of the ultrathin metal foil is preferably 0.1 μm or more and 10 μm or less. By setting the lower limit of the thickness of the thin metal foil to 0.1 μm or more, damage to the ultrathin metal foil after peeling the carrier foil and generation of pinholes in the ultrathin metal foil are suppressed. In addition, there is no risk of plating variations, circuit wiring disconnection, or infiltration of chemicals such as an etching solution or a desmear solution during circuit pattern formation due to pinholes. Further, by setting the upper limit to 10 μm or less, variations in the thickness of the ultrathin metal foil and the surface roughness of the roughened surface can be reduced. Furthermore, 0.5 to 5 μm is preferable, and 1 to 3 μm is more preferable. Usually, an ultrathin metal foil with a carrier foil peels off the carrier foil before forming a circuit pattern on the press-molded laminate.

  Next, the printed wiring board will be described. This printed wiring board has a circuit forming surface on one side or both sides of the above-mentioned laminated board.

  Specifically, a laminated board having copper foil on both sides is prepared, a through hole is formed by a drill or the like, and after filling the through hole by plating, a predetermined conductor circuit ( Inner layer circuit) is formed, and the conductor circuit is roughened such as blackening to produce a circuit formation surface.

  Next, the above-mentioned adhesive sheet or the above-mentioned prepreg is formed on the circuit forming surface of the laminated board, and is heated and pressed using a vacuum pressure laminator or the like. Although it does not specifically limit as conditions to heat-press-mold, If an example is given, it can implement at the temperature of 60-160 degreeC, and the pressure of 0.2-3 MPa.

  Then, you may heat-press-mold using a flat plate press apparatus etc. Although it does not specifically limit as conditions to heat-press-mold, If an example is given, it can implement at the temperature of 140-240 degreeC, and the pressure of 1-4 MPa.

  Next, the epoxy resin composition of the present invention is cured to form a build-up layer that is laminated on the circuit forming surface of the laminate. Although it does not specifically limit as hardening conditions, If an example is given, it can implement at the temperature of 100 to 250 degreeC, and 30 to 180 minutes. Although it may be pressurized, it is preferably cured under atmospheric pressure.

  Thereafter, the surface of the build-up layer can be roughened with an oxidizing agent such as permanganate or dichromate, and a new conductive wiring circuit can be formed by metal plating. Further, this may be used as a core material to further form a buildup layer.

  Next, an opening is provided in the build-up layer using a carbonic acid laser device, and an outer layer circuit is formed on the surface of the build-up layer by electrolytic copper plating to achieve conduction between the outer layer circuit and the inner layer circuit. The outer layer circuit is provided with a connection electrode portion for mounting a semiconductor element. Thereafter, a solder resist is formed on the outermost layer, the connection electrode portion is exposed so that a semiconductor element can be mounted by exposure and development, nickel gold plating is performed, and the printed wiring board is cut to a predetermined size.

  Next, the semiconductor device will be described. A semiconductor device can be manufactured by mounting a semiconductor element on a printed wiring board manufactured by the method described above. The mounting method and the sealing method of the semiconductor element are not particularly limited. For example, a semiconductor element and a printed wiring board are used, and a flip-chip bonder or the like is used to align the connection electrode portions on the printed wiring board and the solder bumps of the semiconductor element. Thereafter, the solder bump is heated to the melting point or higher by using an IR reflow device, a hot plate, or other heating device, and the printed wiring board and the solder bump are connected by fusion bonding. And a semiconductor device can be obtained by filling and hardening a liquid sealing resin between a printed wiring board and a semiconductor element.

It continues and demonstrates the effect of the epoxy resin composition of this invention concretely.
According to the present invention, the tertiary amine compound is contained in a molar ratio of 0.05 to 0.65 with respect to the number of moles of epoxy groups of the epoxy resin having two or more epoxy groups in one molecule. Epoxy resins can be polymerized via an ether bond using an amine compound as a catalyst. A prediction of the polymerization mechanism of the present invention is shown in Formula (1).

  Conventionally, in a method of reacting an epoxy resin with a curing agent such as a primary amine or a secondary amine, a reaction has occurred as shown by the following formula (2). For this reason, hydroxyl groups are generated and the dielectric properties are degraded.

  On the other hand, in the case of the present invention, as shown by the formula (1), an anion generated by the ring opening of the epoxy group reacts with the epoxy group by the action of the tertiary amine, and an ether bond is formed. Self-polymerization occurs. Therefore, the generation of alcoholic hydroxyl groups can be suppressed, the dielectric loss tangent can be improved and the crosslinking density can be improved without increasing the dielectric constant.

Moreover, the epoxy resin composition of this invention is maintaining the characteristic of the conventional epoxy resin composition using the hardening | curing agent favorably. For example, an insulating layer of a laminated board or a printed wiring board formed from the epoxy resin composition of the present invention has a gel time at 140 ° C. within 10 minutes and has a sufficient curing rate even at a low temperature. The glass transition temperature can be 100 to 200 ° C., the water absorption can be 0.1 to 0.2%, and the thermal expansion coefficient can be 10 to 30 K ^{−1 in} the thickness direction. Moreover, the peel strength of the laminated board and printed wiring board formed from the epoxy resin composition of the present invention is better than that of a conventional epoxy resin composition using a curing agent, and is 0.5 to 1.5 kN / m. Therefore, in the present invention, it is possible to realize an epoxy resin composition that further improves the dielectric characteristics while maintaining the characteristics of the conventional epoxy resin composition using a curing agent. In addition, evaluation of the epoxy resin composition of this invention can be performed based on JIS-C-6481 (copper-clad laminated board test method for printed wiring boards).

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

Examples 1-10, Comparative Examples 1-5
In the formulation shown in Table 1, an epoxy resin and a tertiary amine compound were mixed on an aluminum cup, placed on a hot plate at 180 ° C. and dissolved. When 80% of the gel time measured in advance passed, the gel plate was removed from the hot plate, allowed to cool to room temperature (23 ° C.), and solidified. Thereafter, the solidified material was pulverized, spread on an aluminum foil, pressed at a pressure of 4 MPa and a temperature of 220 ° C. for 180 minutes, and then peeled off the aluminum foil to obtain a resin plate.

[Evaluation 1]
1. Dielectric properties (dielectric constant, dielectric loss tangent)
The dielectric characteristics of the resin plate at 1 GHz were measured by the triplate resonator method. The results are shown in Table 1.
2. Glass transition temperature The thermal expansion coefficient was measured by TMA (thermal mechanical analysis, manufactured by TA Instruments, TMA Q400), and the transition point of the thermal expansion coefficient was taken as the glass transition temperature. The results are shown in Table 1.

[Evaluation 2]
Infrared spectroscopic apparatus in which an epoxy resin and a tertiary amine compound were mixed on an aluminum cup and placed in an oven at 200 ° C. for 2 hours with the formulation of Examples 1 to 3 and Comparative Examples 1 to 3 shown in Table 1. (Product name: AVATAE320 FT-IR, manufacturer: manufactured by ThermoNicolet). The peak showing the stretching vibration of the carbon-carbon double bond (C = C) in the absorption band near the wavelength of 1500 cm ^{−1 is} defined as a reference peak, and the ether bond (− in the absorption band near the wavelength of 1130 cm ^{−1 with} respect to the peak intensity of the reference peak) The ratio of the peak intensity showing the stretching vibration of O-) and the ratio of the peak intensity to the peak showing the stretching vibration of the epoxy group in the absorption band near the wavelength of 916 cm ⁻¹ were examined. The results are shown in Table 2.

  From the results shown in Table 2, it was shown that the amount of ether bonds generated increased as the amount of the tertiary amine compound increased with respect to the epoxy group content. Therefore, in the epoxy resin compound of this invention, since self-polymerization as shown by Formula (1) arises, it was guessed that the production | generation of an alcoholic hydroxyl group decreases and a dielectric property improves.

Examples 11-14, Comparative Examples 9-10
A resin varnish blended as shown in Table 3 was prepared, and after impregnating 80 parts by weight of the solid content with the resin varnish with respect to 100 parts by weight of glass cloth (1035E, manufactured by Nitto Boseki Co., Ltd., thickness 0.03 mm), 190 A prepreg having a resin content of 55% by weight was produced by drying in a drying oven at 5 ° C for 5 minutes. Four prepregs were stacked and both sides were sandwiched between copper foils having a thickness of 35 μm, and heat-press molding was performed at 220 ° C. and 4 MPa for 180 minutes to prepare a copper-clad laminate having a thickness of 0.5 mm.

[Evaluation 3]
1. Dielectric property Measured by the same method as in Evaluation 1.
2. Gel time 1 g of a sample was placed on a hot plate maintained at 140 ° C., and the time until the resin composition did not pull the yarn even when the spatula was lifted while stirring with a spatula was measured. The shorter this time, the faster the curing rate.
3. Peel strength Measured according to JIS C 6481.
4). Water absorption The copper foil was etched on the entire surface, and a 50 mm × 50 mm test piece was cut out and measured according to JIS C 6481.
5. Glass transition temperature It was measured by the same method as in Evaluation 1.
6). Thermal expansion coefficient The thermal expansion coefficient in the thickness direction was measured by TMA (thermomechanical analysis, manufactured by TA Instruments, TMA Q400), and an average value from 50 ° C to 150 ° C was shown.

Claims (9)

  An epoxy resin having two or more epoxy groups in one molecule and a tertiary amine compound, the number of moles of the tertiary amine compound (B) relative to the number of moles of epoxy groups (A) contained in the epoxy resin The epoxy resin composition whose ratio ((B) / (A)) is 0.05 to 0.65.   The epoxy resin composition according to claim 1, wherein a content of the tertiary amine compound is 5 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin.   The epoxy resin composition according to claim 1 or 2, wherein the tertiary amine compound is a nitrogen-containing aromatic heterocyclic compound.   The epoxy resin composition according to claim 3, wherein the tertiary amine compound is imidazole or a derivative thereof.   The prepreg which has a resin layer which consists of an epoxy resin composition of any one of Claims 1 thru | or 4, and a fiber base material.   The laminated board formed by forming a metal layer in the single side | surface or both surfaces of the prepreg of Claim 5.   The hardened | cured material of the epoxy resin composition of any one of Claims 1 thru | or 4.   The printed wiring board which has a circuit formation surface in the single side | surface or both surfaces of the laminated board of Claim 6.   A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to claim 8.