KR20180136494A - Epoxy resin composition and electronic component device - Google Patents

Abstract

R₁은 각각 독립적으로, 수소 원자 또는 탄소수 1 내지 6의 1가 탄화수소기를 나타내고, R₂는 식 (a)로 나타나는 치환기를 나타내고, m은 0 내지 20의 수를 나타내고, p는 0.5 내지 2.0을 나타내고, R₃은 각각 독립적으로, 수소 원자 또는 탄소수 1 내지 6의 1가 탄화수소기를 나타낸다.An epoxy resin composition comprising an epoxy resin containing a compound represented by the following general formula (1) and a curing agent containing at least one selected from the group consisting of biphenylene type phenol aralkyl resins, phenol aralkyl resins and triphenylmethane type phenol resins .

R ₁ represents, independently of each other, a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms; R ₂ represents a substituent represented by the formula (a); m represents a number of 0 to 20; And each R ₃ independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms.

Description

Epoxy resin composition and electronic component device

The present invention relates to an epoxy resin composition and an electronic component device.

2. Description of the Related Art In recent years, high density mounting of semiconductor devices has been progressing. In the meantime, a resin-encapsulated semiconductor device has become a mainstream from a conventional pin insertion type package to a surface mounting type package. A surface-mount type IC (Integrated Circuit), an LSI (Large Scale Integration), and the like are formed in a thin and compact package in order to increase the mounting density and reduce the mounting height. Therefore, the occupied area of the device with respect to the package becomes large, and the thickness of the package becomes extremely thin.

In addition, these packages are different from conventional pin insertion type packaging methods. That is, since the pins are soldered from the back surface of the wiring board after the pins are inserted into the wiring board, the package is not directly exposed to high temperatures. However, since the surface mount type IC is temporarily fixed on the surface of the wiring board and is processed in a solder bath, a reflow apparatus or the like, it is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture is evaporated at the time of reflow, and the resulting vapor pressure acts as a peeling stress, causing peeling between the insert and the sealing material such as the element or the lead frame, And cause defective electrical characteristics. Therefore, development of a sealing material having excellent solder heat resistance (downflow resistance) has been desired.

As the sealing material, in addition to low moisture absorption, it is strongly desired to improve adhesion or adhesiveness to dissimilar materials such as lead frames (Cu, Ag, Au, Pd as a material) and chip interfaces. In order to respond to these demands, various studies have been made on the epoxy resin as a main material, and for example, a method using a biphenyl type epoxy resin has been studied (see, for example, Patent Document 1). Various types of epoxy resin modifiers have been studied from the background. Examples of such modifiers include sulfur atom-containing compounds (for example, see Patent Documents 2 and 3) and sulfur atom-containing silane coupling agents (for example, 4).

Japanese Patent Application Laid-Open No. 64-65116 Japanese Patent Laid-Open No. 11-12442 Japanese Patent Application Laid-Open No. 2002-3704 Japanese Patent Laid-Open No. 2000-103940

However, in the case of using a sulfur atom-containing silane coupling agent (see, for example, Patent Document 4), the effect of improving adhesion with noble metals such as Ag and Au is insufficient, 2 and 3) in the amounts described in the literature, the adhesion to the noble metal is not sufficiently improved, and the flowability is not satisfied.

An aspect of the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an electronic component device having an excellent flow property, an epoxy resin composition having good flame retardancy without deteriorating fluidity, and an element sealed by the epoxy resin composition .

As a result of intensive investigations to solve the above problems, the present inventors have found that the above object can be achieved by an epoxy resin composition containing a specific epoxy resin.

≪ 1 > An epoxy resin composition comprising an epoxy resin containing a compound represented by the following general formula (1)

A curing agent comprising at least one member selected from the group consisting of a biphenylene type phenol aralkyl resin, a phenol aralkyl resin and a triphenylmethane type phenol resin

And an epoxy resin.

R ₁ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms, R ₂ represents a substituent represented by the formula (a), m represents a number of 0 to 20, and p represents an integer of 0.5 to 2.0 And each R ₃ independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms.

<2> The epoxy resin composition according to <1>, further comprising a curing accelerator.

&Lt; 3 > The epoxy resin composition according to < 2 >, wherein the curing accelerator comprises an adduct of a third phosphine compound and a quinone compound.

<4> The epoxy resin composition according to any one of <1> to <3>, which further contains an inorganic filler.

&Lt; 5 > The epoxy resin composition according to < 4 >, wherein the content of the inorganic filler is 60% by mass to 95% by mass.

<6> The epoxy resin composition according to any one of <1> to <5>, further comprising a coupling agent.

<7> The epoxy resin composition according to <6>, wherein the coupling agent comprises a silane coupling agent having a secondary amino group.

&Lt; 8 >

A cured product of the epoxy resin composition according to any one of < 1 > to < 7 >

And an electronic component device.

According to one aspect of the present invention, there can be obtained an epoxy resin composition which is excellent in fl ow flowability, does not deteriorate fluidity, and has excellent flame retardancy, and an electronic component device having the element sealed by the composition.

In the present specification, the numerical range indicated by using &quot; to &quot; indicates a range including the numerical values before and after "to" as the minimum value and the maximum value, respectively.

In the present specification, the content of each component in the composition means the total content of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition .

In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range of the other stepwise description. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment.

In the present specification, the particle diameter of each component in the composition means a value for a mixture of plural kinds of particles present in the composition, unless otherwise specified, when a plurality of particles corresponding to each component exist in the composition do.

&Lt; Epoxy resin composition &

The epoxy resin composition according to one embodiment of the present invention comprises an epoxy resin containing a compound represented by the following general formula (1) (hereinafter also referred to as a "specific epoxy resin"), a biphenylene type phenol aralkyl resin, (Hereinafter, also referred to as &quot; specific curing agent &quot;) containing at least one member selected from the group consisting of an alkyl resin and a triphenylmethane type phenol resin.

R ₁ represents, independently of each other, a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms; R ₂ represents a substituent represented by the formula (a); m represents a number of 0 to 20; And each R ₃ independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms.

When the epoxy resin composition has such a constitution, the adhesiveness with metals such as Cu, Ag, Au, Pd and the like is excellent, and therefore the flow resistance is excellent, the flowability is not deteriorated, and the flame retardancy is improved. This reason is not clear, but it can be thought as follows.

By introducing a specific amount of a benzyl group into an epoxy resin which is an epoxy resin of a novolak type phenol resin, the interaction with the adherend is enhanced and the adhesiveness is improved. Further, the moisture resistance is improved, the occurrence of peeling from the insert such as the lead frame due to the moisture moisture is suppressed, the adhesiveness is maintained even when the reflow is exposed to high temperature heat, and the flowability is improved do. Particularly, by combining a specific curing agent, the adhesiveness with Ag which can be used as a material for the lead frame is enhanced, so that the flow property can be increased synergistically.

Further, it is considered that the lower the melt viscosity, the higher the fluidity and the better the moldability.

(Epoxy resin)

The epoxy resin composition contains an epoxy resin. The epoxy resin includes a compound represented by the following general formula (1).

R ₁ represents, independently of each other, a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms; R ₂ represents a substituent represented by the formula (a); m represents a number of 0 to 20; And each R ₃ independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms.

In the general formula (1), R ₂ represents a substituent represented by the formula (a) (hereinafter also referred to as "benzyl group"). p represents a number of 0.5 to 2.0, which means the average number of benzyl groups (number average) substituted with one benzene ring. p is 0.5 to 2.0, preferably 0.7 to 1.5. When p is 0.7 or more, flowability is further improved, and when p is 1.5 or less, curability is further improved.

Here, p is described. Up to three benzyl groups may be substituted for the benzene rings at both terminals in the compound represented by the general formula (1). The maximum total number of benzyl groups is 8, and the maximum value of p in this case is 2.7 (8/3? 2.7 ). However, in the present embodiment, p in the general formula (1) is 0.5 to 2.0. In the present embodiment, p is a number average value, so that the benzene ring in the general formula (1) may not have a hydrogen atom substituted with a benzyl group.

In formula (a), each R ₃ independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

In the general formula (1), each R ₁ independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group desirable. R ₁ may be located at any of the ortho, meta, and para positions of the benzene ring, but is preferably located at the ortho position of the benzene ring.

In the general formula (1), m is an average value, and m represents a number of 0 to 20, preferably 1.0 to 5.0.

The specific viscosity of the specific epoxy resin at 150 캜 is preferably 0.01 Pa · s to 0.30 Pa · s, more preferably 0.01 Pa · s to 0.20 Pa · s. In terms of workability, the lower the melt viscosity in the above range, the more preferable.

The melt viscosity was measured by the following method using a rotating viscoelasticity measuring apparatus (for example, Shimadzu Corporation, product name: CFD-100D).

(1) Set the temperature range to 150 ° C, (2) melt 0.15 g to 0.25 g of the sample on the plate, lower the cone and leave it until the temperature control lamp flashes five times. (3) The top and bottom agitation of the cone is performed for about 20 seconds, and then the temperature control lamp is kept blinking until it is repeated five times. (4) Read the value after about 15 seconds after the cone rotation. (5) Repeat the operations (3) to (4) until the values become equal, and record the values. (6) The operations of (2) to (5) are repeated three or more times in the same lot, and the average value is determined as the viscosity.

The epoxy equivalent of the specific epoxy resin is preferably 240 g / eq to 270 g / eq, more preferably 255 g / eq to 270 g / eq, still more preferably 257 g / eq to 270 g / / eq is particularly preferable.

The epoxy equivalent is determined by the following method.

An epoxy resin was weighed to a solid content of 3 g to 4 g, and 20 mL of acetic acid, 10 mL of a tetraethylammonium bromide solution (a mixture of 100 g of tetraethylammonium bromide and 400 mL of acetic acid) and 4 to 5 drops of crystal violet . Titrate this solution with a 0.1 mol / L perchloric acid acetic acid solution. Likewise titrate the blank. The epoxy equivalence is calculated by the following formula.

Epoxy equivalence = 1,000 x mass of epoxy resin actually weighed x solid content concentration of epoxy resin [mass%] / ((titrant [mL] - blank titration [mL]) x 0.1 mol / L x factor of perchloric acid acetic acid solution f)

The softening point of a specific epoxy resin is preferably 50 占 폚 to 80 占 폚, more preferably 55 占 폚 to 70 占 폚, and still more preferably 56 占 폚 to 65 占 폚, from the viewpoint of moldability and flowability. The softening point of a specific epoxy resin is measured by the ring method. In the ring method, a resin was set in a support ring in a water bath, 3.5 ± 0.05 g of a sphere was placed in the center of the ring, the bath was raised at a rate of 5 ± 0.5 ° C per minute, And the temperature is measured. The details are measured in accordance with JIS K7234: 1986.

The specific epoxy resin can be obtained by reacting a phenol novolac resin corresponding to the general formula (1) (hereinafter also referred to as "raw phenol novolac resin") with a compound containing a benzyl group corresponding to the formula (a) Containing compound ") in the presence of an acid catalyst to obtain a specific phenol novolac resin, and epoxidizing the specific phenol novolac resin.

The blending ratio of the raw material phenol novolak resin and the raw material benzyl group-containing compound is adjusted according to the desired value of p in the general formula (1). Therefore, the raw material phenol novolak resin and the starting benzyl group are preferably added so that the raw material benzyl group-containing compound is preferably added in the range of 0.5 to 2.0, more preferably 0.7 to 1.5 in one benzene ring of the starting phenol novolac resin. Containing compound is preferably blended. Here, the benzene ring of the raw material phenol novolak resin has one hydroxyl group, and the compounding ratio of the raw material benzyl group-containing compound to one mole of the hydroxyl group in the raw material phenol novolak resin is preferably 0.5 mol to 2.0 mol, More preferably from 0.7 mol to 1.5 mol.

The raw material phenol novolac resin has a structure in which a phenol compound having R ₁ (a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) is linked with a methylene group. Examples of the phenol compound include phenol, cresol, ethylphenol, isopropylphenol, n-propylphenol, isobutylphenol, t-butylphenol, n-pentylphenol and n-hexylphenol. Among them, the phenol compound is preferably cresol having o-cresol or o-cresol as a main component. When cresol having o-cresol as a main component is used, the content of o-cresol in the entire cresol is preferably 50 mass% or more, and more preferably 70 mass% or more. When cresol containing o-cresol as a main component is used, cresol containing o-cresol as a main component may include m-cresol and p-cresol.

The raw phenol novolak resin may have a structure in which other phenol compounds are connected by a methylene group in addition to a structure in which a phenol compound having R ₁ is linked with a methylene group. Examples of other phenol compounds include allylphenol, phenylphenol, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcin, catechol, 1-naphthol, , 1,6-naphthalene diol, 1,7-naphthalene diol, 2,6-naphthalene diol, 2,7-naphthalene diol and the like. A part of the compound represented by the general formula (1) may contain a structural unit derived from another phenol compound, and the compound represented by the general formula (1) may contain a structural unit derived from another phenol compound, By mass, preferably not more than 10% by mass, more preferably not more than 5% by mass, and still more preferably not substantially.

The raw material benzyl group-containing compound is a compound having a benzyl group having R ₃ (a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms). Examples of the raw material benzyl group-containing compound include benzyl alcohol, benzyl chloride, benzyl bromide, and benzyl iodide. The starting benzyl group-containing compound such as benzyl alcohol, benzyl chloride, benzyl bromide or benzyl iodide may have a monovalent hydrocarbon group of 1 to 6 carbon atoms as R ₃ . Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, t-butyl, pentyl and hexyl.

The acid catalyst may be appropriately selected from well-known inorganic acids and organic acids. Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; Organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid, and diethylsulfuric acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; Ion exchange resins, activated clays, silica-alumina, and solid acids such as zeolite.

The reaction for synthesizing a specific phenol novolac resin is usually carried out at a temperature of 10 to 250 캜 for 1 to 20 hours. A solvent may be used in the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Ether solvents such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; And aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene.

This reaction can be carried out by, for example, feeding all raw materials of raw material phenol novolak resin and raw material benzyl group-containing compound in a batch, reacting the mixture at a predetermined temperature, introducing raw phenol novolak resin and catalyst, , While reacting the raw material benzyl group-containing compound while dropping the raw material benzyl group-containing compound. In this case, the dropping time is usually 1 hour to 10 hours, preferably 5 hours or less. After the reaction, if a solvent is used, the catalyst is removed if necessary, and then the solvent is distilled off to obtain a specific phenol novolac resin.

A method of epoxidizing a specific phenol novolak resin includes, for example, a method of reacting a specific phenol novolac resin with epichlorohydrin, a method of reacting a specific phenol novolac resin with allyl halide to obtain an allyl ether compound, And the like.

For example, a specific phenol novolac resin is dissolved in excess epichlorohydrin and then reacted in the presence of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like at a temperature in the range of 20 ° C to 150 ° C, preferably 30 ° C to 80 ° C For 1 hour to 10 hours. The amount of the alkali metal hydroxide to be used at this time is preferably from 0.8 mol to 1.5 mol, more preferably from 0.9 mol to 1.2 mol, per mol of the hydroxyl group of the specific phenol novolac resin. Although epichlorohydrin is used in excess to one mole of hydroxyl groups of a specific phenol novolac resin, it is usually used in an amount of 1.5 to 30 moles, preferably 2 to 15 moles per mole of hydroxyl group of a specific phenol novolac resin. It is a range of malls. After completion of the reaction, the excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, To obtain a specific epoxy resin.

The epoxy resin composition may further include a conventionally known epoxy resin in addition to the specific epoxy resin. Examples of the epoxy resin which can be used in combination include phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F, and at least a naphthol compound such as? -Naphthol,? -Naphthol and dihydroxynaphthalene Novolak type epoxy resin obtained by epoxidating a novolac resin obtained by condensing or co-condensing a compound having a hydroxyl group and an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in the presence of an acid catalyst , Phenol novolak type epoxy resins (excluding specific epoxy resins), orthocresol novolak type epoxy resins (excluding specific epoxy resins), and triphenylmethane type epoxy resins]; Epoxy resins such as bisphenol A, bisphenol F, bisphenol S, diglycidyl ether such as alkyl-substituted or unsubstituted biphenol; Stilbene type epoxy resin; Hydroquinone type epoxy resins; Glycidyl ester type epoxy resins obtained by reaction of polybasic acids such as phthalic acid and dimeric acid with epichlorohydrin; Glycidylamine type epoxy resins obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; A dicyclopentadiene type epoxy resin which is an epoxide of a cocondensation resin of dicyclopentadiene and a phenolic compound; A naphthalene type epoxy resin having a naphthalene ring; Phenol aralkyl type epoxy resins which are epoxides of phenol aralkyl resins; A biphenylene type epoxy resin containing a biphenylene skeleton; Naphthol aralkyl type epoxy resins which are epoxides of naphthol aralkyl resins; Trimethylol propane-type epoxy resin; Terpene-modified epoxy resins; A linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peroxide such as peracetic acid; Alicyclic epoxy resins; Sulfur atom-containing epoxy resins, and the like. These epoxy resins which can be used in combination may be used alone or in combination of two or more.

Among them, bisphenol F type epoxy resin, sulfur atom-containing epoxy resin and phenol aralkyl type epoxy resin are preferable from the viewpoint of flowability and bottoming property, and novolak type epoxy resin Epoxy resin is excluded). From the viewpoint of low hygroscopicity, dicyclopentadiene type epoxy resin is preferable, and from the viewpoint of heat resistance and low bending property, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferable, A biphenylene type epoxy resin and a naphthol aralkyl type epoxy resin are preferable. It is preferable to use an epoxy resin composition such as nonhalogen or nonantimony in combination with a good flame retardant epoxy resin from the viewpoint of improvement of the high temperature storage stability.

Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (III), and examples of the sulfur atom-containing epoxy resin include epoxy resins represented by the following general formula (IV) As the phenol aralkyl type epoxy resin, for example, an epoxy resin represented by the following general formula (V) can be mentioned.

In the general formula (III), R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, Alkyl group. n is an average value and represents a number of 0 to 3; The alkyl group, alkoxy group, aryl group and aralkyl group represented by R ¹ to R ⁸ may each independently have a substituent or may not have a substituent.

In the general formula (IV), R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. n is an average value and represents a number of 0 to 3; The alkyl group and the alkoxy group represented by R ¹ to R ⁸ may each independently have a substituent or may not have a substituent.

In the general formula (V), R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 2 carbon atoms. n is an average value and represents a number of 0 to 3; The alkyl group and the alkoxy group represented by R ¹ to R ⁵ may each independently have a substituent or may not have a substituent.

Examples of the bisphenol F type epoxy resin represented by the general formula (III) include those in which R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms, YSLV-80XY (Shin-Nitetsu Sumikin Kagaku Kogyo Co., Ltd.), whose main component is 0, is available as a commercial product.

Among the sulfur atom-containing epoxy resins represented by the general formula (IV), epoxy resins in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms and R ¹ , R ⁴ , R ⁵ and R ⁸ are alkyl groups, More preferred are epoxy resins in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are t-butyl groups, and R ⁴ and R ⁵ are methyl groups. As such a compound, for example, YSLV-120TE (trade name, Shin-Nettetsu Sekinigaku Kagaku Co., Ltd.) is available as a commercial product.

As the epoxy resin represented by the general formula (V), for example, NC-2000L (trade name, product of Nihon Kayaku Co., Ltd.) in which R ¹ to R ⁵ are hydrogen atoms is available as a commercial product. Any of these epoxy resins may be used singly or in combination of two or more.

As the novolak-type epoxy resin, for example, an epoxy resin represented by the following general formula (VI) can be mentioned.

In the general formula (VI), each R independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms (which is not a substituent represented by the formula (a) in the general formula (1)), n Is an average value and represents a number of 0 to 10. Each of the hydrocarbon groups represented by R may independently have a substituent or may not have a substituent.

The novolak type epoxy resin represented by the general formula (VI) is obtained by reacting novolak type phenolic resin with epichlorohydrin. Among them, R in the general formula (VI) is preferably an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or an isobutyl group or a methoxy group, And the like, and more preferably a hydrogen atom or a methyl group. n is preferably an integer of 0 to 3.

Among the novolak type epoxy resins represented by the general formula (VI), orthocresol novolak type epoxy resins are preferable. As such a compound, for example, EOCN-1020 (trade name, Nihon Kayaku Co., Ltd.) is available as a commercial product.

Examples of the dicyclopentadiene type epoxy resin include epoxy resins represented by the following general formula (VII).

In formula (VII), R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms, n is an average value, 0 to 10, and m represents 0 to 6 Represents an integer. Each of the hydrocarbon groups represented by R ¹ and R ² may independently have a substituent or may not have a substituent.

As R ¹ in the general formula (VII), a hydrogen atom; An alkyl group such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, and t-butyl group; Alkenyl groups such as a vinyl group, an allyl group and a butenyl group; And a monovalent hydrocarbon group having 1 to 5 carbon atoms and having a substituent such as a halogenated alkyl group, an amino group-substituted alkyl group and a mercapto group-substituted alkyl group. Of these, an alkyl group such as a methyl group or an ethyl group or a hydrogen atom is preferable, desirable.

As R ² in the general formula (VII), a hydrogen atom; An alkyl group such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, and t-butyl group; Alkenyl groups such as a vinyl group, an allyl group and a butenyl group; A monovalent hydrocarbon group having 1 to 5 carbon atoms having a substituent such as a halogenated alkyl group, an amino group-substituted alkyl group or a mercapto group-substituted alkyl group, and among these, a hydrogen atom is preferable. As such a compound, for example, HP-7200 (trade name, DIC Corporation) is available as a commercial product.

Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (VIII). Examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (IX).

In the general formula (VIII), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 12 carbon atoms. (1 + m) is a number of from 1 to 11, and (1 + p) is a number of from 1 to 12, and p is an average value of from 0 to 2, l and m are mean values, 1 to 12 is selected. i represents an integer of 0 to 3, j represents an integer of 0 to 2, and k represents an integer of 0 to 4. Each of the hydrocarbon groups represented by R ¹ to R ³ may independently have a substituent or may not have a substituent.

The naphthalene type epoxy resin represented by the general formula (VIII) includes random copolymers randomly containing 1 structural unit and m structural units, alternating copolymers alternately included, regularly included copolymers and included in block form , And any one of them may be used alone, or two or more of them may be used in combination. As the above-mentioned compound in which R ¹ and R ² are hydrogen atoms and R ³ is a methyl group, for example, NC-7000 (trade name, Nihon Kayaku Co., Ltd.) is available as a commercial product.

In the general formula (IX), each R independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n is an average value and represents a number of 0 to 10. Each of the hydrocarbon groups represented by R may independently have a substituent or may not have a substituent. As the above-mentioned compound in which R is a hydrogen atom, for example, E-1032 (trade name, Mitsubishi Chemical Corporation) is available as a commercial product.

Examples of the biphenylene type epoxy resin include epoxy resins represented by the following general formula (X). Examples of the naphthol aralkyl type epoxy resin include epoxy resins represented by the following general formula (XI).

In the general formula (X), R ¹ to R ⁹ each independently represent a hydrogen atom; An alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group and isobutyl group; An alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group; An aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group and a xylyl group; Or an aralkyl group having 7 to 10 carbon atoms such as a benzyl group and a phenethyl group, and among them, a hydrogen atom or a methyl group is preferable. n is an average value and represents a number of 0 to 10; The alkyl group, alkoxy group, aryl group and aralkyl group represented by R ¹ to R ⁹ each independently may or may not have a substituent.

In the formula (XI), R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 12 carbon atoms, and n is an average value and represents a number of 0 to 10. Each of the hydrocarbon groups represented by R ¹ and R ² may independently have a substituent or may not have a substituent.

As the biphenylene type epoxy resin, for example, NC-3000 (trade name, Nihon Kayaku Co., Ltd.) is available as a commercial product. As the naphthol aralkyl type epoxy resin, for example, ESN-175 (trade name, Shin Nitetsu Sumikin Kagaku Kogyo Co., Ltd.) is available as a commercial product. The biphenylene type epoxy resin may be used singly or in combination of two or more.

As the epoxy resin, an epoxy resin represented by the following general formula (XII) may be used.

R ¹ in formula (XII) each independently represents a hydrocarbon group of 1 to 12 carbon atoms or an alkoxy group of 1 to 12 carbon atoms, and n is an average value and represents a number of 0 to 4. Each R ² independently represents a hydrocarbon group of 1 to 12 carbon atoms or an alkoxy group of 1 to 12 carbon atoms, and m is an average value and represents a number of 0 to 2. The hydrocarbon group and the alkoxy group represented by R ¹ and R ² may each independently have a substituent or may not have a substituent. Among them, an epoxy resin in which n and m are zero is preferable from the viewpoint of flame retardancy and moldability. As such a compound, for example, YX-8800 (trade name, Mitsubishi Kagaku K.K.) is available.

The content of the specific epoxy resin with respect to the total amount of the epoxy resin is preferably 30 mass% or more, more preferably 50 mass% or more, and further preferably 70 mass% or more.

(Hardener)

The epoxy resin composition contains a curing agent. The curing agent includes at least one selected from the group consisting of a biphenylene type phenol aralkyl resin, a phenol aralkyl resin and a triphenylmethane type phenol resin.

A biphenylene type phenol aralkyl resin represented by the following general formula (XVII) is preferable.

Here, R ¹ to R ⁹ each independently represent a hydrogen atom; An alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group and isobutyl group; An alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group; An aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group and a xylyl group; Or an aralkyl group having 7 to 10 carbon atoms such as a benzyl group and a phenethyl group, and among them, a hydrogen atom or a methyl group is preferable. n is an average value and represents a number of 0 to 10; The alkyl group, alkoxy group, aryl group or aralkyl group represented by R ¹ to R ⁹ may each independently have a substituent or may not have a substituent.

Examples of the biphenylene phenol aralkyl resin represented by the general formula (XVII) include, for example, compounds in which all of R ¹ to R ⁹ are hydrogen atoms. Among them, from the viewpoint of the melt viscosity, A mixture of a condensate containing not less than 50% by mass is preferable. As such a compound, for example, MEH-7851 (trade name, product of Meiwa Kasei Kabushiki Kaisha) is available as a commercial product. When these biphenylene phenol aralkyl resins are used, the content of the biphenylene type phenol aralkyl resin is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the total amount of the curing agent in order to exhibit its performance.

From the viewpoint of flowability, flame retardancy and moldability, phenol aralkyl resins represented by the following general formula (XIII) are preferable.

In the general formula (XIII), each R independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n is an average value and represents a number of 0 to 10. Each of the hydrocarbon groups represented by R may independently have a substituent or may not have a substituent.

Among the compounds represented by the general formula (XIII), a phenol aralkyl resin in which R is a hydrogen atom and an average value of n is 0 to 8 is more preferable. Specific examples include p-xylylene-type phenol aralkyl resins and m-xylylene-type phenol aralkyl resins. As such a compound, for example, XLC (Mitsui-Kagaku Kogyo Co., Ltd.) is available as a commercial product. When these phenol aralkyl resins are used, the content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent for achieving the performance.

From the viewpoint of reducing the warpage, triphenylmethane type phenol resin is preferable. Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XVI).

In the formula (XVI), each R independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n is an average value and represents a number of 0 to 10. Each of the hydrocarbons represented by R may independently have a substituent or may not have a substituent. As the above-mentioned compound wherein R is a hydrogen atom, for example, MEH-7500 (trade name, product of Meiwa Kasei Kabushiki Kaisha) is available as a commercial product. When these triphenylmethane type phenol resins are used, the content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent for achieving the performance.

Any one kind of the specific curing agent may be used alone, or two or more kinds may be used in combination.

The curing agent may be used in combination with other curing agents other than the specific curing agent. The content of the specific curing agent in the total curing agent is preferably 30 mass% or more, more preferably 50 mass% or more, and further preferably 70 mass% or more.

Examples of other curing agents include novolak type phenol resins, naphthol aralkyl resins, dicyclopentadiene type phenol resins, terpene modified phenol resins, paraxylylene modified phenol resins, meta xylene modified phenol resins, melamine modified phenol resins, cyclo A phenanthrene-modified phenol resin, and a phenol resin obtained by copolymerizing two or more of them.

Examples of the novolak-type phenol resin include phenol novolak resins, cresol novolak resins, naphthol novolac resins and the like, among which phenol novolac resins are preferable.

Examples of the naphthol aralkyl resin include phenol resins represented by the following general formula (XIV).

In the formula (XIV), R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon having 1 to 10 carbon atoms, and n is an average value and represents a number of 0 to 10. Each of the hydrocarbon groups represented by R ¹ and R ² may independently have a substituent or may not have a substituent.

Examples of the naphthol aralkyl resin represented by the general formula (XIV) include a compound in which R ¹ and R ² are both hydrogen atoms. Examples of such compounds include SN-170 (Shin-Nettetsu Sumikin Kagaku Co., Ltd.) is available as a commercial product.

Examples of the dicyclopentadiene type phenol resin include a phenol resin represented by the following general formula (XV).

In formula (XV), R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms, n is an average value, 0 to 10, and m represents 0 to 6 Represents an integer. Each of the hydrocarbon groups represented by R ¹ and R ² may independently have a substituent or may not have a substituent. As the above compound in which R ¹ and R ² are hydrogen atoms, for example, DPP (Shin-Nippon Sekiyu Kagaku Kogyo Co., Ltd.) is available as a commercial product.

These other curing agents may be used singly or in combination of two or more kinds. Of the other curing agents used in combination, novolak type phenol resins are preferable from the viewpoint of curability.

The hydroxyl group equivalent of the curing agent is preferably 100 g / eq to 199 g / eq, more preferably 130 g / eq to 199 g / eq, and even more preferably 175 g / eq to 199 g / eq.

The method of measuring the hydroxyl group equivalent in the curing agent is as follows.

Pyridine-acetyl chloride method, the hydroxyl group of the curing agent is acetylated with chloride in a pyridine solution, the excess reagent is decomposed with water, and the resulting acetic acid is titrated with a solution containing potassium hydroxide and ethanol to obtain the hydroxyl group equivalent .

The ratio of the equivalent ratio of the epoxy resin to the curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is not particularly limited, Is preferably set in the range of 0.5 to 2, and more preferably in the range of 0.6 to 1.3. And more preferably in the range of 0.8 to 1.2 in order to obtain an epoxy resin composition excellent in moldability and downflow resistance.

(Hardening accelerator)

In the epoxy resin composition, a curing accelerator may be used as needed in order to accelerate the reaction between the epoxy resin and the curing agent.

As the curing accelerator, those generally used in the epoxy resin composition can be used without particular limitation. Examples of the curing accelerator include 1,8-diaza-bicyclo [5.4.0] undecene-7,1,5-diaza-bicyclo [4.3.0] - diazabicyclo [5.4.0] undecene-7; Cyclooctane, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3 Quinone compounds such as dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane, A compound having an intramolecular polarization formed by adding a compound having? Bonds of? Tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; Derivatives of tertiary amine compounds; Imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole; Derivatives of imidazole compounds; Phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine; A phosphorus compound having an intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, quinone compound, diazophenylmethane, or phenol resin to the phosphine compound; Tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate; And derivatives of tetraphenylboron salts. These curing accelerators may be used alone or in combination of two or more.

Among them, adducts of a tertiary phosphine compound and a quinone compound are preferable as a curing accelerator from the viewpoints of flame retardancy, curability, flowability and releasability.

The third phosphine compound is not particularly limited and includes tricyclohexylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4- Methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6- A tertiary phosphine compound having an alkyl group or an aryl group such as tris (4-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine and tris (4-ethoxyphenyl) phosphine.

Examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. Among them, p-benzoquinone is preferable as the quinone compound from the viewpoints of moisture resistance and storage stability.

As the curing accelerator, adducts of triphenylphosphine and p-benzoquinone are preferable from the viewpoint of flowability, and adducts of tris (4-methylphenyl) phosphine and p-benzoquinone are preferable from the viewpoint of releasability.

The content of the curing accelerator is not particularly limited so long as the effect of accelerating the curing is achieved. When the epoxy resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.005 mass% to 2 mass%, more preferably 0.01 mass% to 0.5 mass%, in the epoxy resin composition. When the amount is 0.005 mass% or more, the curability tends to be improved, and when it is 2 mass% or less, the time for use tends to be improved.

(Inorganic filler)

The epoxy resin composition may further contain an inorganic filler. The inclusion of an inorganic filler tends to reduce the hygroscopicity, reduce the coefficient of linear expansion, improve the thermal conductivity, and improve the strength. Examples of the inorganic filler include inorganic fillers such as fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllium, zirconia, zircon, , Mullite, titania and the like, spherical beads and glass fibers. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide, zinc borate and zinc molybdate. Examples of the zinc borate include FB-290, FB-500 (available from USBorax), FRZ-500C (available from Mizusawa Kagaku Kogyo K.K.), and commercially available products such as KEMGARD 911B, 911C, 1100 (manufactured by Sherwin-Williams) are commercially available.

These inorganic fillers may be used singly or in combination of two or more kinds. Among them, fused silica is preferable from the viewpoint of reducing the packing property and the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The shape of the inorganic filler is preferably spherical in view of filling property and mold abrasion resistance.

The average particle diameter of the inorganic filler is preferably 1 탆 to 50 탆, more preferably 10 탆 to 30 탆. When the average particle diameter is 1 mu m or more, the viscosity of the epoxy resin composition tends to be suppressed. When the average particle diameter is 50 mu m or less, preferably 30 mu m or less, the filling property with respect to a narrow gap tends to be improved. The average particle diameter of the inorganic filler is measured as a volume average particle diameter by a laser scattering diffraction particle size distribution measuring apparatus.

The specific surface area of the inorganic filler is preferably 1 m2 / g to 5 m2 / g, and more preferably 2 m2 / g to 4 m2 / g, from the viewpoints of flame retardancy and fluidity.

When the epoxy resin composition contains an inorganic filler, the content of the inorganic filler is preferably 50% by mass or less in the epoxy resin composition from the viewpoints of fluidity, flame retardance, moldability, reduction of hygroscopicity, reduction of linear expansion coefficient, By mass, more preferably 60% by mass to 95% by mass from the viewpoint of flame retardancy, and still more preferably 70% by mass to 90% by mass. When the content of the inorganic filler is 50 mass% or more, the flowability tends to be improved. When the content of the inorganic filler is 95 mass% or less, the flame retardancy and flowability tend to be improved.

(Coupling agent)

The epoxy resin composition may further contain a coupling agent. When an inorganic filler is used in the epoxy resin composition, the coupling agent tends to improve the adhesion between the resin component and the inorganic filler. As the coupling agent, those generally used in the epoxy resin composition can be used without particular limitation. Examples of the coupling agent include silane compounds having primary, secondary or tertiary amino groups, various silane compounds such as epoxy silane, mercaptosilane, alkylsilane, ureido silane and vinyl silane, titanium compounds, aluminum chelate compounds, aluminum and zirconium compounds Compounds and the like.

Examples of the coupling agent include vinyl trichlorosilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane,? -Methacryloxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl ) Ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane,? -Mercaptopropyltrimethoxysilane,? -Aminopropyltri Aminopropyltrimethoxysilane, gamma -aminopropyltrimethoxysilane, gamma -aminopropyltrimethoxysilane, gamma -aminopropyltrimethoxysilane, gamma -aminopropyltrimethoxysilane, gamma -aminopropyltrimethoxysilane, , γ- (N, N-dimethyl) aminopropyltrimethoxysilane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- , γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N-ethyl) anilinopropyltrimethoxysilane, γ- (N (N, N-dibutyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- -Methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- Ethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropylmethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (Trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ- Silane coupling agents such as chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane and? -Mercaptopropylmethyldimethoxysilane; Isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate , Bis (dodecyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, Isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, isopropyltriethoxysilane titanate, Octylphosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis (dioctylphosphite) titanate. . These coupling agents may be used alone or in combination of two or more.

Among them, as the coupling agent, a silane coupling agent having a secondary amino group is preferable from the viewpoint of fluidity, reduction of wire strain and flame retardancy. The silane coupling agent having a secondary amino group is not particularly limited as long as it is a silane compound having a secondary amino group in the molecule.

Examples of the silane coupling agent having a secondary amino group include γ-anilinopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ- anilinomethylethyldiethoxysilane,? - anilinomethylethyldimethoxysilane, N- (p-methoxyphenyl) -? - aminopropyltrimethoxysilane, N - (p-methoxyphenyl) - gamma -aminopropyltriethoxysilane, N- (p-methoxyphenyl) - gamma -aminopropylmethyldimethoxysilane, N- (p- methoxyphenyl) N- (p-methoxyphenyl) -? - aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -? - amide (N-methyl) aminopropyltrimethoxysilane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- (N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyltriethoxysilane, γ- (N-ethyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxysilane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropylmethyldimethoxysilane, γ- -Butyl) aminopropylmethyldimethoxysilane,? - (N-benzyl) aminopropylmethyldimethoxysilane, N- (aminoethyl) -? - aminopropyltrimethoxysilane,? - Aminopropyltrimethoxysilane, and N -? - (N-vinylbenzylaminoethyl) -? - aminopropyltrimethoxysilane.

When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably 0.037 mass% to 5 mass%, more preferably 0.05 mass% to 4.75 mass%, more preferably 0.1 mass% More preferably 2.5% by mass. When it is 0.037 mass% or more, adhesion with the frame is improved, and when it is 5 mass% or less, curability is improved.

(Flame retardant)

From the viewpoint of improving the flame retardancy, the epoxy resin composition may contain flame retardants of conventionally known flame retardants, particularly non-halogen and non-antimony, from the viewpoints of environmental compatibility and reliability. Examples of the flame retardant include inorganic compounds such as phosphoric acid ester and zinc oxide, compounds coated with a thermosetting resin such as phenol resin, compounds coated with a resin such as phosphine oxide, melamine, melamine derivatives, melamine modified phenol resins, Containing compound such as cyclophosphazene, a nitrogen-containing compound, aluminum hydroxide, magnesium hydroxide, complex metal hydroxide, zinc oxide, zinc stearate, zinc borate, iron oxide, And compounds containing metal elements such as molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, and the like. These flame retardants may be used alone or in combination of two or more.

(Silicon-containing polymer)

The epoxy resin composition may contain a silicon-containing polymer in view of reducing warpage. The silicon-containing polymer is preferably a compound having the following bonds (c) and (d) and having a terminal group selected from the group consisting of R ¹ , a hydroxyl group and an alkoxy group, and an epoxy equivalent of 500 g / eq to 4000 g / eq . As the silicon-containing polymer, there may be mentioned, for example, a branched polysiloxane called silicone resin.

Here, each R ¹ independently represents a monovalent hydrocarbon group of 1 to 12 carbon atoms. X represents a monovalent organic group containing an epoxy group. The hydrocarbon group represented by R ¹ may have a substituent. The epoxy group contained in X may undergo ring-opening reaction, and X may be a bivalent group.

Examples of R ¹ in the bonds (c) and (d) include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, An alkyl group such as an ethylhexyl group; Alkenyl groups such as a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group; Aryl groups such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group; And aralkyl groups such as a benzyl group and a phenethyl group, and among these, a methyl group or a phenyl group is preferable.

Further, X in the bond (d) is a monovalent organic group containing an epoxy group. The bonding position of the epoxy group in the organic group is not particularly limited, and it is preferable that the epoxy group is bonded to the terminal of the organic group.

Specific examples of X include a 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3- glycidoxypropyl group, Group, a 2- (3,4-epoxycyclohexyl) ethyl group and a 3- (3,4-epoxycyclohexyl) propyl group. Among them, a 3-glycidoxypropyl group is preferable.

Further, from the viewpoint of storage stability of the ends of the silicon-containing polymer is a polymer, R ¹ is preferably, each independently, a hydroxyl group or an alkoxy group. Examples of the terminal alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

When the silicon-containing polymer has an epoxy group, the epoxy equivalent is preferably in the range of 500 g / eq to 4000 g / eq, more preferably 1000 g / eq to 2500 g / eq. When the epoxy equivalent of the silicon-containing polymer is 500 g / eq or more, the flowability of the epoxy resin composition tends to be improved. When the silicon equivalent is 4000 g / eq or less, the occurrence of defective molding tends to be suppressed, .

When the epoxy resin composition contains a silicon-containing polymer, the content of the silicon-containing polymer is preferably 0.2% by mass to 1.5% by mass, more preferably 0.3% by mass to 1.3% by mass in the epoxy resin composition. When the amount is 0.2% by mass or more, the effect of reducing the deflection of the package tends to be improved, and when it is 1.5% by mass or less, the curability tends to be improved.

(Other components)

The epoxy resin composition is selected from the group consisting of a compound represented by the following composition formula (XXXIII) and a compound represented by the following composition formula (XXXIV), if necessary, from the viewpoint of improving moisture resistance and high temperature storage characteristics of a semiconductor device such as IC And may contain at least one species.

(0 < X &lt; = 0.5, m is a positive number)

(0.9? X? 1.1, 0.6? Y? 0.8, 0.2? Z? 0.4)

The compound of the formula (XXXIII) is commercially available as DHT-4A, trade name of Kyoe Kagaku Kogyo K.K. The compound of the formula (XXXIV) is available as a commercial product under the trade name IXE500 from Toagosei Co., Ltd. If necessary, other anion exchangers may be added. The anion exchanger is not particularly limited and conventionally known ones can be used, and hydrous oxides of elements such as magnesium, aluminum, titanium, zirconium, antimony and the like can be mentioned. These anion exchangers may be used alone or in combination of two or more.

The epoxy resin composition may further contain other additives such as a higher fatty acid, a higher fatty acid metal salt, an ester wax, a polyolefin wax, a releasing agent such as polyethylene or polyethylene oxide, a coloring agent such as carbon black, a stress reliever such as a silicone oil or a silicone rubber powder .

&Lt; Process for producing epoxy resin composition >

The epoxy resin composition may be produced by any method as long as it can uniformly disperse and mix various raw materials. As a general production method, a method of thoroughly mixing a predetermined amount of a raw material with a mixer or the like and then mixing or melt-kneading the mixture with a mixing roll, an extruder, a pulverizer, a planetary mixer, etc., cooling, And the like. In addition, the epoxy resin composition may be tableted to dimensions and masses that meet the molding conditions, if necessary.

<Electronic parts device>

An electronic component device according to an embodiment of the present invention includes a device and a cured product of the above-described epoxy resin composition for sealing the device. A low-pressure transfer molding method is generally used as a method of sealing an element by using the epoxy resin composition of the present embodiment as a sealing material, but an injection molding method, a compression molding method, and the like can also be used. As a method of applying the epoxy resin composition, a dispensing method, a mold method, a printing method, or the like may be used.

As the electronic component device of the present embodiment including the device sealed with the epoxy resin composition of the present embodiment, a semiconductor chip such as a lead frame, a tape carrier of wiring completion, a supporting member such as glass, a silicon wafer, An electronic component device in which elements such as active elements such as transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils are mounted, and necessary portions are sealed with the epoxy resin composition of the present embodiment.

Here, the mounting substrate is not particularly limited and may be an interposer substrate such as an organic substrate, an organic film, a ceramic substrate, or a glass substrate, a glass substrate for a liquid crystal, a substrate for an MCM (Multi Chip Module), a substrate for a hybrid IC, have.

The electronic component device having such a device may be, for example, a semiconductor device. Specifically, a device such as a semiconductor chip is fixed on a lead frame (island, tab) PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Plate), which is formed by connecting the lead portions with wire bonding or bumps and then sealing them by transfer molding or the like using the epoxy resin composition of the present embodiment. a resin encapsulation type IC such as a small outline tape (SOP), a small outline tape (SOJ), a thin outline tape (TSOP), and a thin quad flat tape (TQFP) A semiconductor chip bonded with a semiconductor chip by wire bonding, flip chip bonding, solder, or the like on a TCP (Tape Carrier Packet) sealed with an epoxy resin composition of the present embodiment, a wiring board, Embodiment Flip chip bonding, solder, or the like to a semiconductor device mounted on a bare chip such as a COB (Chip On Board) or a COG (Chip On Glass) obtained by sealing with an epoxy resin composition, a wiring board, A hybrid IC in which an active element such as a semiconductor chip, a transistor, a diode, and a thyristor, a passive element such as a capacitor, a resistor, and a coil is sealed with the epoxy resin composition of this embodiment, a terminal for connecting an MCM (Multi Chip Module) A semiconductor chip is mounted on an interposer substrate on which a semiconductor chip is mounted and a wiring formed on the interposer substrate is connected by bump or wire bonding to seal the semiconductor chip mounting side with the epoxy resin composition of the present embodiment, (Ball Grid Array), CSP (Chip Size Packaging), and MCP (Multi Chip Packaging). These semiconductor devices may be stacked (laminated) packages mounted on a mounting substrate in a stacked manner with two or more elements, or may be a batch molded package in which two or more elements are sealed at one time with an epoxy resin composition.

Example

The present invention will be described below by way of Synthesis Examples and Examples, but the scope of the present invention is not limited to these Examples.

[Synthesis Examples 1 to 4]

The specific epoxy resin can be synthesized as follows.

The starting phenol novolak resin is reacted with the starting benzyl group-containing compound using p-toluenesulfonic acid as an acid catalyst to obtain a specific phenol novolak resin first. At this time, the equivalent of hydroxyl group is measured in the same manner as in the above-mentioned method of measuring the hydroxyl group equivalent in the curing agent, and the value of p in the general formula (1) is obtained from this value.

The specific phenol novolak resin obtained above is then epoxidized with epichlorohydrin. The epoxy equivalent, softening point, and melt viscosity at 150 캜 of the obtained resin are shown in Table 1 below. In the specific epoxy resin thus obtained, R ₂ in the general formula (1) was a benzyl group (R ₃ was a hydrogen atom).

[Examples 1 to 4, Comparative Examples 1 to 8]

The following components were compounded in the mass parts shown in Tables 2 and 3, respectively, and kneaded at a kneading temperature of 80 占 폚 and a kneading time of 10 minutes to perform Examples 1 to 4 and Comparative Examples 1 to 8.

(Epoxy resin)

Epoxy resin 1: Epoxy resin having an epoxy equivalent of 240 g / eq, a softening point of 55 占 폚, and a compound represented by the general formula (1)

Epoxy resin 2: an epoxy equivalent of 263 g / eq; a softening point of 58 占 폚; a compound represented by the general formula (1)

Epoxy resin 3: epoxy equivalent 264 g / eq, softening point 60 캜, compound represented by general formula (1), epoxy resin having p = 1.0

Epoxy resin 4: epoxy equivalent 265 g / eq, softening point 61 캜, compound represented by formula (1), p = 1.1 epoxy resin

Epoxy resin 5: a copolymer (DIC Corporation, product name: HP-5000) of 2-methoxynaphthalene and orthocresol novolak type epoxy resin with an epoxy equivalent of 251 g / eq,

Epoxy resin 6: epoxy equivalent 190 g / eq, melting point 59 캜, orthocresol novolak type epoxy resin (DIC Corporation, trade name N-500P-1)

(Hardener)

Curing agent 1: phenol aralkyl resin having a hydroxyl equivalent of 175 g / eq and a softening point of 70 DEG C (MEH-7800SS, trade name, manufactured by Meiwa Kasei K.K.)

Curing agent 2: Novolak type phenol resin (HP-850N, trade name, manufactured by Hitachi Kasei K.K.) having a hydroxyl group equivalent of 106 g / eq and a softening point of 82 캜,

(Hardening accelerator)

Curing accelerator 1: adduct of triphenylphosphine and 1,4-benzoquinone

(Coupling agent)

Epoxysilane:? -Glycidoxypropyltrimethoxysilane

(Inorganic filler)

Spherical fused silica: average particle diameter 14.5 占 퐉, specific surface area 2.8 m2 / g

(Other additives)

· Carnauba wax (Clariant)

Carbon black (MA-600, product of Mitsubishi Kagaku KK)

The properties of the prepared epoxy resin compositions of Examples 1 to 4 and Comparative Examples 1 to 8 were determined by the following respective tests. The results are shown in Tables 4 and 5.

(1) Spiral flow (indicator of liquidity)

The epoxy resin composition was molded by a transfer molding machine under the conditions of a mold temperature of 180 캜, a molding pressure of 6.9 MPa and a curing time of 90 seconds using a mold for spiral flow measurement according to EMMI-1-66, I got it.

(2) Open hardness

The epoxy resin composition was molded into an original plate having a diameter of 50 mm and a thickness of 3 mm under the molding conditions described in the above (1), and immediately after molding, measurement was carried out using a Shore D type hardness meter.

(3) Flammability

The epoxy resin composition was molded under the above molding conditions (1) using a mold for molding a test piece having a thickness of 1/32 inch (0.8 mm), further cured at 180 캜 for 5 hours, and then subjected to UL-94 test The flame retardancy was evaluated according to the law.

(4) Flowing Castle

(4.1) Cu lead frame

An 80-pin flat package (QFP) having an external dimension of 20 mm x 14 mm x 2 mm with a silicon chip of 8 mm x 10 mm x 0.4 mm (Lead frame material: copper alloy, top surface of die pad, Molded at a temperature of 85 캜 under a condition of 85% RH and subjected to a predetermined time after reflowing at a temperature of 240 캜 for 10 seconds. The epoxy resin composition was molded under the above conditions (3) The presence or absence of cracks was visually observed and evaluated by the number of crack occurrence packages with respect to the number of test packages (5).

(4.2) PPF lead frame

Evaluation was carried out in the same manner as in (4.1) except that PPF (core material: copper alloy, plated 3 layer (Ni / Pd / Au)) was used for the lead frame.

(5) Moisture resistance

A test silicon chip of 6 mm x 6 mm x 0.4 mm having an aluminum wire with a line width of 10 mu m and a thickness of 1 mu m formed on a 5 mu m thick silicon oxide film was mounted on an 80 pin A flat package (QFP) was produced by molding and curing under the above-mentioned conditions (3) using an epoxy resin composition. After the preprocessing was carried out and humidified for a predetermined time, , And the number of defective packages with respect to the number of test packages (10) was evaluated.

In the pretreatment, the flat package was humidified under the conditions of 85 ° C and 85% RH for 72 hours, followed by a vapor phase reflow treatment at 215 ° C for 90 seconds. The subsequent humidification was carried out under the conditions of 0.2 MPa and 121 캜.

(6) High temperature disposition characteristics

A test silicon chip of 5 mm x 9 mm x 0.4 mm having a line width of 10 mu m and a thickness of 1 mu m formed on a 5 mu m thick silicon oxide film was coated with a silver paste on a 42- And a 16-pin DIP (Dual Inline Packing) in which bonding pads of the chips and an inner lead were connected to each other by Au wires at 200 占 폚 by a thermonic type wire bonder was prepared in the same manner as in the above (3) And stored in a high-temperature bath at 200 ° C. After a predetermined time had elapsed, a conduction test was conducted to evaluate the high-temperature and temperature-standing characteristics with the number of conduction defect packages to the number of test packages (10) .

In Comparative Examples 5 and 7 which did not contain the compound represented by the general formula (1), the moldability was poor because of low hardness at the time of heat treatment. In Comparative Examples 6 and 8, the flow resistance was poor and the flame retardancy did not achieve V-0.

In Comparative Examples 1 to 4 in which a specific curing agent was not used, the spiral flow was smaller and the moldability was lower than that in Examples 1 to 4. In Comparative Examples 1 to 4, in which a specific curing agent was not used, the underflow property (particularly, 72h and 96h) in the Cu lead frame was slightly different as compared with Examples 1 to 4 in which a specific curing agent was used.

On the other hand, Examples 1 to 4 containing the compound represented by the general formula (1) showed good flowability and bottoming property, all achieved UL-94 V-0, good flame retardancy and good moldability Do.

The disclosure of Japanese Patent Application 2016-091768, filed on April 28, 2016, is incorporated herein by reference in its entirety.

All publications, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, and technical specification were specifically and individually indicated to be incorporated by reference.

Claims (8)

An epoxy resin comprising a compound represented by the following general formula (1)
A curing agent comprising at least one member selected from the group consisting of a biphenylene type phenol aralkyl resin, a phenol aralkyl resin and a triphenylmethane type phenol resin
And an epoxy resin.

R ₁ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms, R ₂ represents a substituent represented by the formula (a), m represents a number of 0 to 20, and p represents an integer of 0.5 to 2.0 And each R ₃ independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms. The epoxy resin composition according to claim 1, further comprising a curing accelerator. 3. The epoxy resin composition according to claim 2, wherein the curing accelerator comprises an adduct of a third phosphine compound and a quinone compound. The epoxy resin composition according to any one of claims 1 to 3, further comprising an inorganic filler. The epoxy resin composition according to claim 4, wherein the content of the inorganic filler is 60% by mass to 95% by mass. The epoxy resin composition according to any one of claims 1 to 5, further comprising a coupling agent. The epoxy resin composition according to claim 6, wherein the coupling agent comprises a silane coupling agent having a secondary amino group. A device,
A cured product of the epoxy resin composition according to any one of claims 1 to 7, which seals the device
And an electronic component device.