JP2022016887A - Epoxy resin composition and cured product - Google Patents

Abstract

To provide an epoxy resin composition for an electric material which is excellent in low viscosity and moldability, is excellent in heat resistance, especially, thermal decomposition stability in the presence of oxygen from the viewpoint of practicability, and has excellent performances such as moisture resistance, low thermal expansibility and thermal conductivity, and a cured product of the same.SOLUTION: There are provided an epoxy resin composition that is composed of an epoxy resin, a curing agent and an inorganic filler, in which a diketone-based epoxy resin is used as the epoxy resin component, a phenol compound having the number of hydroxyl groups in one molecule of 2 or larger and melt viscosity at 150°C of 50 mPa s to 500 mPa s is used as the curing agent component, and 50-96 wt.% of the inorganic filler is contained in the composition; and a cured product of the same.SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin composition and a cured product that provide a cured product having excellent thermal decomposition stability, low thermal expansion, low hygroscopicity, and the like.

In recent years, with the progress in the field of electronic materials, the development of higher performance resin materials is required. For example, in the field of semiconductor encapsulation, with the development of in-vehicle semiconductors, there is a demand for a resin composition having high heat resistance, particularly excellent thermal decomposition stability. On the other hand, since high-density mounting is also progressing, a resin composition having a low viscosity and excellent moldability is strongly demanded because a high filling rate of the inorganic filler is aimed at. Further, from the viewpoint of improving reliability as a sealing material, improvement of low hygroscopicity, low thermal expansion, adhesion and the like is also required.

However, an epoxy resin composition satisfying these requirements has not yet been proposed. For example, Patent Document 1 describes a naphthol aralkyl type epoxy resin composition having improved heat resistance and moisture resistance, and Patent Document 2 describes an aralkyl type epoxy in which 4,4'-dihydroxybiphenyl is linked with a p-xylylene group. A resin composition and Patent Document 3 disclose a biphenylaralkyl type epoxy resin composition having a structure in which a bisphenol compound is linked by a biphenylene group, both of which are sufficient from the viewpoint of thermal decomposition stability and low thermal expansion. It wasn't.

Patent Document 4 proposes an epoxy resin having a diketone structure. However, the resin composition disclosed as an example uses an aromatic diamine as a curing agent, has a high viscosity, is inferior in handleability and moldability, and is a resin composition for electronic parts from the viewpoint of reliability. Was unsuitable, and the thermal decomposition stability of the cured product was not sufficient.

Japanese Unexamined Patent Publication No. 1-252624 Japanese Unexamined Patent Publication No. 4-255714 Japanese Unexamined Patent Publication No. 8-239454 Japanese Unexamined Patent Publication No. 60-226869

Therefore, an object of the present invention is excellent in low viscosity and moldability, heat resistance, particularly excellent thermal decomposition stability in the presence of oxygen from the viewpoint of practicality, and further, moisture resistance, low thermal expansion, and heat. It is an object of the present invention to provide an epoxy resin composition for an electronic material having excellent performance in conductivity and a cured product thereof.

（但し、Ｒ_１およびＲ_２はそれぞれ独立して水素原子、炭素数１～８の炭化水素基、炭素数１～６のアルコキシ基またはグリシジルオキシ基を表す。また、Ｇはグリシジル基を示し、ｎは０～５の数を示す。） That is, in the present invention, in an epoxy resin composition composed of an epoxy resin and a curing agent, the epoxy resin component is a diketone-based epoxy resin represented by the following general formula (1), and the curing agent component is a phenolic hydroxyl group in one molecule. The epoxy resin composition is characterized by using a phenolic compound having a number of 2 or more.

(However, R ₁ and R ₂ independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a glycidyloxy group, and G represents a glycidyl group. n indicates a number from 0 to 5.)

The phenolic compound preferably has a melt viscosity at 150 ° C. of 50 mPa · s to 500 mPa · s.

The epoxy resin composition of the present invention may contain an inorganic filler, and in this case, it is preferable that the epoxy resin composition contains 50 to 96 wt% of the inorganic filler.

The epoxy resin composition of the present invention is suitable as an epoxy resin composition for electronic materials, particularly for encapsulants for electronic components or for electrically insulating substrates as described later.

Further, the present invention is a cured product obtained by curing the above epoxy resin composition.

The epoxy resin composition of the present invention provides a cured product having excellent moldability with low viscosity, excellent heat resistance, thermal decomposition stability, and low moisture absorption, and seals electrical and electronic parts. It can be suitably used for electronic material applications such as stops and circuit board materials.

Hereinafter, the present invention will be described in detail.
The epoxy resin used in the epoxy resin composition of the present invention contains a diketone-based epoxy resin represented by the general formula (1) as a main component thereof.

n is a repeat number, representing a number from 0 to 5, but the preferred value of n will vary depending on the application. For example, for applications of semiconductor encapsulants that require a high filling rate of fillers, those having a low viscosity are desirable, and the value of n is 0 to 3, preferably 0 to 2, and more preferably n is 0. Those containing 50 wt% or more. When the epoxy resin of the present invention is a mixture having different values of n, the number average value of n is 0 to 5.0, preferably 0.1 to 2.0, and more preferably 0. It contains 50 wt% or more, and the number average value of n is 0.1 to 1.0. These low molecular weight epoxy resins are optionally crystallized and used as solids at room temperature. Further, a high molecular weight epoxy resin is preferably used for applications such as printed wiring boards, and in this case, a molecule having a value of n larger than 5 may be contained.

R ₁ and R ₂ independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a glycidyloxy group, respectively. From the viewpoint of low viscosity, a hydrogen atom or a methyl group is preferable, and from the viewpoint of moisture resistance, flame retardancy, and high adhesion, a phenyl group, a benzyl group, a styryl group, and a glycidyloxy group are preferable. From the viewpoint of the balance of the physical properties of the cured product, a hydrogen atom or a methyl group is most preferable. R ₁ and R ₂ may be the same or different, and a plurality of R ₁ or R ₂ may be the same or different. G represents a glycidyl group.

The diketone-based epoxy resin represented by the general formula (1) used as the epoxy resin of the present invention is preferably crystalline, and has a melting point or a softening point of preferably 50 to 200 ° C, more preferably 70 to 150 ° C. be. The melt viscosity at 150 ° C. is preferably 10 to 500 mPa · s, more preferably 15 to 300 mPa · s, and even more preferably 20 to 100 mPa · s. The epoxy equivalent is preferably about 180 to 300 g / eq.

ここで、Ｒ₃及びＲ₄は、それぞれ独立して水素原子、炭素数１～８の炭化水素基、炭素数１～６のアルコキシ基または水酸基を表す。 The method for producing the epoxy resin used in the present invention is not particularly limited, but it can be produced by reacting a phenolic compound having a diketone structure of the following formula (2) with epichlorohydrin. This reaction can be carried out in the same manner as a normal epoxidation reaction.

Here, R ₃ and R ₄ independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group, respectively.

The reaction between the phenolic compound and epichlorohydrin is, for example, after dissolving the phenolic compound in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, preferably at 50 to 150 ° C. , A method of reacting in the range of 60 to 100 ° C. for 1 to 10 hours can be mentioned. The amount of the alkali metal hydroxide used at this time is in the range of 0.8 to 2.0 mol, preferably 0.9 to 1.5 mol, with respect to 1 mol of the hydroxyl group in the phenolic compound. An excess amount of epichlorohydrin is used for the hydroxyl group in the phenolic compound, and usually 1.5 to 15 mol with respect to 1 mol of the hydroxyl group in the phenolic compound. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene and methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off to obtain the desired epoxy. Resin can be obtained.

The epoxy resin used in the epoxy resin composition of the present invention may be synthesized by using a mixture of a phenolic compound having the diketone structure of the above formula (2) and another phenolic compound having no diketone structure. can. In this case, the mixing ratio of the phenolic compound of the formula (2) is preferably 50 wt% or more. The other phenolic compounds are not particularly limited, and are selected from those having two or more hydroxyl groups in one molecule.

The purity of the epoxy resin, particularly the amount of hydrolyzable chlorine, should be small from the viewpoint of improving the reliability of electronic components. Although not particularly limited, 1000 ppm or less is preferable. The hydrolyzable chlorine in the present invention means a value measured by the following method. That is, after dissolving 0.5 g of the sample in 30 ml of dioxane, adding 1N KOH and 10 ml, boiling and refluxing for 30 minutes, cooling to room temperature, further adding 100 ml of 80% acetone water, and potentiometric titration with 0.002N AgNO ₃ aqueous solution. It is a value that can be done.

In the epoxy resin composition of the present invention, in addition to the epoxy resin having a diketone structure used as an essential component, another epoxy resin having two or more epoxy groups in the molecule may be used in combination as the epoxy resin component. For example, bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, Divalent phenols such as fluorenbisphenol, 2,2'-biphenol, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, or phenol novolak , Bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis ( 4-Hydroxyphenyl) ethane, fluoroglycinol, pyrogallol, t-butylpyrogalol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol There are trivalent or higher phenols such as aralkyl resin and dicyclopentadiene resin, and glycidyl etherified products derived from halogenated bisphenols such as tetrabromobisphenol A. One type or two or more types of these epoxy resins can be used.

The epoxy resin composition of the present invention preferably contains the epoxy resin of the above formula (1) as an epoxy resin in an amount of 50 wt% or more of the epoxy resin component. More preferably, it is 70 wt% or more, and more preferably 80 wt% or more of the total epoxy resin. If the ratio of use is less than this, the moldability of the epoxy resin composition deteriorates, and the heat resistance of the cured product, the thermal decomposition stability in the presence of oxygen, the moisture resistance, the low thermal expansion property, etc. The improvement effect is small.

As the curing agent used in the present invention, a phenolic compound (including a resin) having two or more phenolic hydroxyl groups in one molecule is used, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4. Divalent phenols such as'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol, or tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl). ) Polyphenols such as ethane, phenol novolac, o-cresol novolak, naphthol novolak, trivalent or higher phenols typified by polyvinylphenol, and further phenols, naphthols, or bisphenol A, bisphenol F, bisphenol. Divalent phenols such as S, fluorenebisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, Polyhydric phenol synthesized by reaction with a cross-linking agent such as p-xylylene glycol dimethyl ether, 4,4'-dimethoxymethylbiphenyl, 4,4'-dimethoxymethyldiphenyl ether, divinylbenzene, divinylbiphenyl, divinylnaphthalene, etc. There are sex compounds and the like.

ここで、Ａはベンゼン環、ナフタレン環、又はビフェニル環を示し、ｍおよびpは独立に１または２の数を示す。ここで、ベンゼン環、ナフタレン環、又はビフェニル環は、置換基を有するものであってもよく、好ましい置換基はＣ１～６の炭化水素基である。ｋは繰り返し数であり１～１５の数であるが、その平均は１．０～５．０の範囲であることが好ましい。 The phenol compound is not particularly limited in its structure, but is preferably an aralkyl-type phenol resin represented by the following general formula (3).

Here, A represents a benzene ring, a naphthalene ring, or a biphenyl ring, and m and p independently represent numbers of 1 or 2. Here, the benzene ring, the naphthalene ring, or the biphenyl ring may have a substituent, and the preferred substituent is a hydrocarbon group of C1 to 6. k is a repetition number and is a number of 1 to 15, but the average thereof is preferably in the range of 1.0 to 5.0.

The phenol resin having an aralkyl structure can be produced by reacting a phenolic hydroxyl group-containing compound having a benzene ring or a naphthalene ring with an aromatic cross-linking agent.

Examples of the phenolic hydroxyl group-containing compound include phenol, hydroquinone, resorcin, catechol, pyrogallol, fluoroglucolcinol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, and 1,7-naphthalenediol. , 2,6-Naphthalenediol, 2,7-naphthalenediol, 2,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl and the like.

As the aromatic cross-linking agent, there are those having a benzene skeleton and those having a biphenyl skeleton. As the substance having a benzene skeleton, any of o-form, m-form and p-form may be used, but m-form and p-form are preferable. Specifically, p-xylene glycol, α, α'-dimethoxy-p-xylene, α, α'-diethoxy-p-xylene, α, α'-diisopropyl-p-xylene, α, α'-dibutoxy. -P-xylene, m-xylene glycol, α, α'-dimethoxy-m-xylene, α, α'-diethoxy-m-xylene, α, α'-diisopropoxy-m-xylene, α, α' -Dibutoxy-m-xylene and the like can be mentioned. Those having a biphenyl skeleton include 4,4'-dihydroxymethylbiphenyl, 2,4'-dihydroxymethylbiphenyl, 2,2'-dihydroxymethylbiphenyl, 4,4'-dimethoxymethylbiphenyl, 2,4'. -Dimethoxymethylbiphenyl, 2,2'-dimethoxymethylbiphenyl, 4,4'-diisopropoxymethylbiphenyl, 2,4'-diisopropoxymethylbiphenyl, 2,2'-diisopropoxymethylbiphenyl, 4,4 '-Dibutoxymethylbiphenyl, 2,4'-dibutoxymethylbiphenyl, 2,2'-dibutoxymethylbiphenyl and the like can be mentioned. The substitution position of the functional group such as the methylol group with respect to biphenyl may be any of the 4,4'-position, the 2,4'-position and the 2,2'-position, but the compound desirable as the condensing agent is 4,4'-. It is particularly preferable that the total cross-linking agent contains 50 wt% or more of 4,4'-form. If it is less than this, the curing speed as an epoxy resin curing agent is lowered, and the obtained cured product tends to be brittle.

In the above general formula (3), k is a number from 1 to 15. The value of k can be easily prepared by changing the molar ratio of the phenolic hydroxyl group-containing compound and the cross-linking agent. That is, the value of k can be controlled to be smaller as the phenolic hydroxyl group-containing compound is used excessively with respect to the cross-linking agent. The larger the value of k, the higher the softening point and viscosity of the obtained resin. Further, the smaller the value of k, the lower the viscosity, but the number of unreacted phenolic hydroxyl group-containing compounds at the time of synthesis increases, and the production efficiency of the resin decreases. Practically, the molar ratio of both must be 1 mol or less of the cross-linking agent with respect to 1 mol of the phenolic hydroxyl group-containing compound, and is preferably in the range of 0.1 to 0.9 mol. If it is less than 0.1 mol, the amount of the unreacted phenolic hydroxyl group-containing compound increases, which is not industrially preferable.

The melt viscosity of the phenol compound used as the curing agent of the present invention at 150 ° C. is 10 mPa · s to 500 mPa · s, preferably 15 mPa · s to 300 mPa · s, and more preferably 20 mPa · s to 200 mPa · s. Is. The softening point is preferably 50 to 110 ° C, more preferably 50 to 90 ° C. If it is lower than this, there is a problem of blocking during storage, and if it is higher than this, there is a problem of kneadability and moldability at the time of preparing the epoxy resin composition. As the phenolic hydroxyl group equivalent (OH equivalent), for example, one having 100 to 250 g / eq can be preferably used. These phenol resins may be used alone or in combination of two or more.

The epoxy resin composition of the present invention preferably contains, as a curing agent component, a phenol compound having a melt viscosity in the above range in an amount of 50 wt% or more of the curing agent component. More preferably, it is 60 wt% or more, and more preferably 70 wt% or more of the total curing agent. If the ratio of use is less than this, the moldability of the epoxy resin composition deteriorates, and the heat resistance of the cured product, the thermal decomposition stability in the presence of oxygen, the moisture resistance, the low thermal expansion property, etc. The improvement effect is small. The phenol compound having a predetermined melt viscosity is preferably the aralkyl-type phenol resin of the above general formula (3).

The curing agent component is preferably composed of only the aralkyl type phenol resin of the general formula (3), but if it is less than 50 wt%, other curing agents can be contained. As the other curing agent, a phenol-based curing agent is preferable, but a known epoxy resin curing agent such as an acid anhydride-based or amine-based curing agent can be used. When the phenol compound contains the aralkyl type phenol resin of the general formula (3) and other phenol compounds, it is preferable that the melt viscosity as a whole is within the above range. Even when the curing agent component contains a known epoxy resin curing agent such as an acid anhydride type or an amine type in addition to the phenol compound, it is preferable that the melt viscosity of the entire curing agent component is within the above range.

In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the phenolic compound as a curing agent may be within the range usually adopted, but preferably 0.8 phenolic hydroxyl group is used for 1 mol of the epoxy group. It may be blended so as to be ~ 1.2 mol, preferably 0.9 to 1.1 mol. Even when other curing agents are included, the total curing functional groups may be in the above molar ratio range. Outside this range, unreacted epoxy groups or functional groups in the curing agent remain even after curing, and the reliability of the insulating material for electronic components such as electrical insulation is lowered.

It is preferable that the epoxy resin composition of the present invention contains an inorganic filler. In this case, the amount of the inorganic filler added is usually 50 to 96 wt% with respect to the epoxy resin composition, preferably 75 to 96 wt%, and more preferably 85 to 96 wt%. If it is less than this, the effects of low thermal expansion, high heat resistance, high thermal conductivity and the like will not be sufficiently exhibited. On the other hand, if it is more than this, the viscosity becomes high and the moldability deteriorates.

Examples of the inorganic filler include one or more of silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, mulite, titania and the like. Examples thereof include powder, spherical beads and the like. Of these, spherical fused silica is preferable from the viewpoint of increasing the filling of the inorganic filler. Usually, silica is used in combination with several kinds of particle size distributions. The range of the average particle size of the silica to be combined is preferably 0.5 to 100 μm.

Conventionally known curing accelerators such as amines, imidazoles, organic phosphines, and Lewis acids may be added to the epoxy resin composition of the present invention. Specifically, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc. Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, and organics such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine. Tetra-substituted phosphonium-tetra-substituted borates such as phosphines, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, Examples thereof include tetraphenylboron salts such as N-methylmorpholin and tetraphenylborate. The amount to be added is usually 0.2 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.

In the epoxy resin composition of the present invention, in addition to the above components, a mold release agent, a coupling agent, a thermoplastic oligomer, and other substances generally usable for the epoxy resin composition are appropriately blended and used. be able to. For example, a phosphorus-based flame retardant, a flame retardant such as a brom compound or antimony trioxide, a colorant such as carbon black or an organic dye, or the like can be used.

Wax can be used as the release agent. As the wax, for example, stearic acid, montanic acid, montanic acid ester, phosphoric acid ester and the like can be used.

As the coupling agent, for example, epoxysilane can be used. The amount of the coupling agent added is preferably 0.1 to 2.0 wt% with respect to the epoxy resin composition. If it is less than 0.1 wt%, the resin and the base material do not fit well and the moldability deteriorates. On the contrary, if it exceeds 2.0 wt%, the molded product is contaminated due to continuous moldability. Coupling agents are used to improve the adhesive strength between the inorganic filler and the resin component.

The epoxy resin composition of the present invention contains an epoxy resin and a curing agent as essential components, and a compounding component (excluding the coupling agent) containing a component such as an inorganic filler is uniformly mixed by a mixer or the like, and then the coupling agent is used. Can be added and kneaded with a heating roll, kneader or the like to produce the product. The order of blending these components is not particularly limited except for the coupling agent. Further, after kneading, the melt-kneaded product can be crushed into a powder or a tablet.

Since the epoxy resin composition of the present invention is particularly excellent for encapsulating electronic components and mounting substrates, it is suitable as an epoxy resin composition for electronic materials.

The epoxy resin composition of the present invention can be combined with a fibrous base material such as glass fiber to form a composite material. For example, an epoxy resin composition containing an epoxy resin and a curing agent as main components is dissolved in an organic solvent, impregnated into a sheet-like fiber base material, heated and dried, and the epoxy resin is partially reacted to obtain a prepreg. be able to.

In order to obtain a cured molded product using the epoxy resin composition of the present invention, for example, heat molding methods such as transfer molding, press molding, casting molding, injection molding, extrusion molding, etc. are applied, but mass productivity is applicable. From the viewpoint, transfer molding is preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples.
Reference example 1
30 g of 1,3-bis (4-hydroxybenzoyl) benzene was dissolved in 180 g of epichlorohydrin, and 15.4 g of a 48% sodium hydroxide aqueous solution was added dropwise at 60 ° C. under reduced pressure (about 130 Torr) over 3 hours. During this period, the generated water was removed from the system by azeotropic boiling with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 1 hour to dehydrate, epichlorohydrin was distilled off, 250 g of methyl isobutyl ketone was added, and the mixture was washed with water to remove salts. Then, 3 g of 20% sodium hydroxide was added at 80 ° C., the mixture was stirred for 2 hours, and washed with 300 mL of warm water. Then, after removing water by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure to obtain 36.5 g of a pale yellow transparent solid epoxy resin. This epoxy resin was crystallized by being left at room temperature (epoxy resin A). The melting point was 88.4 ° C. The melting point was measured using a DSC7020 differential scanning calorimetry device manufactured by Hitachi High-Tech Science, and the peak temperature of endotherm obtained at a heating rate of 10 ° C./min was taken as the melting point.

The viscosity of the epoxy resin A at 150 ° C. was 36.5 mPa · s. The epoxy equivalent is 232 g / eq., The hydrolyzable chlorine is 370 ppm, and the component ratios in the general formula (1) obtained from the GPC measurement of the obtained resin are 91.3% for n = 0 and n =. 1 was 6.8%. Here, the melting point is a value obtained by the capillary method at a heating rate of 2 ° C./min. The viscosity was measured with CAP2000H manufactured by BROOKFIELD. In addition, GPC measurement is performed by equipment; 515A type manufactured by Japan Waters Corp., column; TSK-GEL2000 x 3 and TSK-GEL4000 x 1 (both manufactured by Tosoh Corporation), solvent; tetrahydrofuran, flow rate; 1 ml / min, temperature; 38 ° C., detector; RI conditions were followed.

Examples 1 to 3, Comparative Examples 1 to 3
As the epoxy resin component, the epoxy resin A of Reference Example 1, the epoxy compound of 4,4'-dihydroxybenzophenone (epoxy resin B: manufactured by Nittetsu Chemical & Materials, epoxy equivalent 173), the biphenyl-based epoxy resin (epoxy resin C: Mitsubishi). Chemical, YX-4000H, epoxy equivalent 195) is used as a curing agent, and phenol novolac (curing agent A: manufactured by Gunei Chemical Co., Ltd., PSM-4261; OH equivalent 103, softening point 82 ° C., melt viscosity 160 mPa at 150 ° C.) -S), Phenol aralkyl resin (curing agent B: Meiwa Kasei, MEH-7800-4L, OH equivalent 162, softening point 50 ° C., melt viscosity at 150 ° C. 30 mPa · s), 1-naphthol aralkyl resin (curing agent) C: Nittetsu Chemical & Materials Co., Ltd., SN-475, OH equivalent 208, softening point 74 ° C., melt viscosity 35 mPa · s at 150 ° C.), bis (4-aminophenyl) methane (hardener D: manufactured by Tokyo Kasei Kogyo Co., Ltd.) )It was used. Further, triphenylphosphine was used as a curing accelerator, and crushed silica (average particle size 21.2 μm) was used as an inorganic filler. The components shown in Table 1 were blended, sufficiently mixed with a mixer, and then kneaded with a heating roll for about 5 minutes to obtain epoxy resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3. Using this epoxy resin composition, molding and post-cure were performed under the conditions shown in Table 1, and the physical characteristics of the molded product were evaluated.

The results are summarized in Table 1. The numbers of each formulation in Table 1 represent parts by weight. The evaluation was performed as follows.

(1) Spiral flow: An epoxy resin composition is injected into a spiral flow measuring mold conforming to the standard (EMMI-1-66) with a spiral flow injection pressure (150 kgf / cm ² ), a curing temperature of 175 ° C., and a curing time of 3 minutes. The flow length was examined by molding under the conditions of.
(2) Gel time: The epoxy resin composition is poured into the recess of a gelling tester (manufactured by Nissin Kagaku Co., Ltd.) that has been preheated to 175 ° C., and two rotations per second are performed using a stirring rod made of PTFE. The gelation time required for the epoxy resin composition to cure was examined by stirring at the speed of.
(3) The test piece immediately after molding at a hardness at heat of 175 ° C. was measured by a durometer type D.
(4) Glass transition temperature, linear expansion coefficient: Measured at a heating rate of 10 ° C./min using a TMA7100 type thermomechanical measuring device manufactured by Hitachi High-Tech Science.
(5) Bending strength and flexural modulus: A test piece having a width of 10 mm and a thickness of 4 mm was formed, post-cured, and then determined by a three-point bending method.
(6) Thermal decomposition temperature: Using a TG / DTA7300 type manufactured by Hitachi High-Tech Science, the temperature was set to the temperature at which only the resin component was reduced by 5% by weight when measured at a temperature rise rate of 10 ° C./min under an air flow.
(7) Residual coal ratio: Using a TG / DTA7300 type manufactured by Hitachi High-Tech Science, the residual ratio in the resin component at 700 ° C. when measured at a heating rate of 10 ° C./min under a nitrogen stream.
(8) Water absorption rate: A disk having a diameter of 50 mm and a thickness of 3 mm was formed, and the weight change rate was determined after post-curing and then absorbing moisture at 85 ° C. and a relative humidity of 85% for 100 hours.

Claims (6)

In an epoxy resin composition composed of an epoxy resin and a curing agent, a diketone-based epoxy resin represented by the following general formula (1) is used as the epoxy resin, and phenol having two or more phenolic hydroxyl groups in one molecule is used as the curing agent. An epoxy resin composition characterized by using a sex compound.

(However, R ₁ and R ₂ independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a glycidyloxy group, and G represents a glycidyl group. n indicates a number from 0 to 5.) The epoxy resin composition according to claim 1, wherein the phenolic compound has a melt viscosity at 150 ° C. of 50 mPa · s to 500 mPa · s. The epoxy resin composition according to claim 1 or 2, wherein the phenolic compound is an aralkyl-type phenol resin. The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin composition contains 50 to 96 wt% of an inorganic filler. The epoxy resin composition according to any one of claims 1 to 4, wherein the epoxy resin composition is for an electronic material. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 5.