TWI724162B - Epoxy resin composition and electronic component apparatus - Google Patents

Abstract

An epoxy resin composition includes an epoxy resin containing a compound represented by the following formula (1), and a curing agent including 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. Each R₁ independently represents a hydrogen atom or a 1C to 6C monovalent hydrocarbon group, each R₂ independently represents a substituted group represented by the following formula (a), m represents a number from 0 to 20, p represents from 0.5 to 2.0, and each R₃ independently represents a hydrogen atom or a 1C to 6C monovalent hydrocarbon group.

Description

Epoxy resin composition and electronic component device

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

In recent years, high-density mounting of semiconductor elements has been promoted. Along with this, resin-sealed semiconductor devices have become mainstream from the conventional pin-insertion type package to the surface mount type package. In order to increase the mounting density and reduce the mounting height, surface-mounted integrated circuits (IC), large scale integrated circuits (Large Scale Integration, LSI), etc. have become thin and small packages. Therefore, the area occupied by the element with respect to the package becomes larger, and the thickness of the package becomes very thin.

Furthermore, the mounting methods of these packages are different from the existing pin-insertion type packages. That is, the pin insertion type package is soldered from the back of the wiring board after the pins are inserted into the wiring board, so the package is not directly exposed to high temperature. However, surface mount ICs are temporarily fixed on the surface of the wiring board and processed with solder baths, reflow devices, etc., so they are directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture will evaporate during reflow, and the generated vapor pressure acts as a peeling stress, which is generated between the interposer and the sealing material such as components, lead frames, etc. Peeling is a cause of package cracks and poor electrical characteristics. Therefore, it is desired to develop a sealing material having excellent solder heat resistance (reflow resistance).

As a sealing material, in addition to low moisture absorption, there is also a strong demand for improving the adhesion or adhesion of lead frames (materials of Cu, Ag, Au, Pd, etc.) and wafer interfaces to various materials. In order to meet these requirements, various studies have been conducted on epoxy resins used as main materials. For example, a method of using biphenyl type epoxy resins has been studied (for example, refer to Patent Document 1). In addition, various epoxy resin modifiers have been studied based on this background. As an example, there are sulfur atom-containing compounds (for example, refer to Patent Literature 2 and Patent Literature 3) and sulfur atom-containing silane coupling agents (for example, , Refer to Patent Document 4). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 64-65116 [Patent Document 2] Japanese Patent Laid-Open No. 11-12442 [Patent Document 3] Japanese Patent Laid-Open No. 2002-3704 [Patent Document 4] Japanese Patent Bulletin No. 2000-103940

[Problem to be Solved by the Invention] However, when a sulfur atom-containing silane coupling agent (for example, refer to Patent Document 4) is used, the effect of improving the adhesion to precious metals such as Ag and Au is lacking. Adding a sulfur atom-containing compound (for example, refer to Patent Document 2 and Patent Document 3) in the disclosed amount cannot sufficiently improve the adhesion to precious metals, and neither can satisfy the reflow resistance.

One aspect of the present invention is made in view of the above-mentioned circumstances, and its object is to provide an epoxy resin composition having excellent reflow resistance and good flame retardancy without reducing fluidity, and an epoxy resin composition provided with the use of the epoxy resin. The electronic component device of the components sealed by the composition. [Means to solve the problem]

The inventors of the present invention have repeatedly studied hard in order to solve the above-mentioned problems, and as a result, they have found that the above-mentioned object can be achieved by blending an epoxy resin composition with a specific epoxy resin.

[R₁ 分別獨立地表示氫原子或碳數1～6的一價烴基，R₂ 表示式（a）所表示的取代基，m表示0～20的數，p表示0.5～2.0，R₃ 分別獨立地表示氫原子或碳數1～6的一價烴基]。<1> An epoxy resin composition containing: an epoxy resin, including a compound represented by the following general formula (1); and a hardener, including a biphenyl type phenol aralkyl resin, a phenol aromatic At least one of the group consisting of alkyl resin and triphenylmethane type phenol resin; [化1]

[R ₁ each independently represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 6 carbon atoms, R ₂ represents a substituent represented by formula (a), m represents a number from 0 to 20, p represents 0.5 to 2.0, and R _{3 represents} Independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms].

<2> The epoxy resin composition as described in <1>, which further contains a hardening accelerator.

<3> The epoxy resin composition according to <2>, wherein the hardening accelerator includes an adduct of a tertiary phosphine compound and a quinone compound.

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

<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 as described in any one of <1> to <5>, which further contains a coupling agent.

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

<8> An electronic component device, comprising: an element; and a cured product of the epoxy resin composition according to any one of <1> to <7> that seals the element. [Effects of the invention]

According to one aspect of the present invention, it is possible to obtain an epoxy resin composition having excellent reflow resistance and good flame retardancy without reducing fluidity, and an electronic component device including an element sealed by the epoxy resin composition .

In this specification, the numerical range indicated by "～" means a range that includes the numerical values described before and after "～" as the minimum and maximum values, respectively. Furthermore, in this specification, when multiple substances corresponding to each component are present in the composition, unless otherwise specified, the content rate of each component in the composition refers to the content of the multiple substances present in the composition. The total content rate. In the numerical ranges described stepwise in this specification, the upper limit or lower limit described in one numerical range can be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical range described in this specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. In this specification, when there are multiple types of particles corresponding to each component in the composition, unless otherwise specified, the particle diameter of each component in the composition refers to a mixture of the multiple types of particles present in the composition. Value.

<Epoxy resin composition> The epoxy resin composition of one embodiment of the present invention contains an epoxy resin containing a compound represented by the following general formula (1) (hereinafter, also referred to as "specific epoxy resin") ; And a hardener, including at least one selected from the group consisting of biphenyl-type phenol aralkyl resin, phenol aralkyl resin, and triphenylmethane-type phenol resin (hereinafter, also referred to as "specific hardener").

[化2]

R ₁ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ₂ represents a substituent represented by formula (a), m represents a number from 0 to 20, p represents 0.5 to 2.0, and R _{3 represents} each independently Ground represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbons.

By using the epoxy resin composition to have such a configuration, the adhesion to metals such as Cu, Ag, Au, and Pd is good, and therefore, the reflow resistance is excellent and the flame retardancy without reducing fluidity is good. The reason is not clear, but it can be considered as follows.

By introducing a specific amount of benzyl groups into an epoxy resin that is an epoxide of a novolak-type phenol resin, the interaction with the adherend becomes higher and the adhesiveness improves. In addition, it can be considered as the following: the moisture resistance is improved, the peeling of the lead frame and the like from the insert due to moisture absorption is suppressed, and the adhesiveness can be maintained even in reflow exposed to high-temperature heat The reflow resistance is improved. In particular, by combining a specific hardener, the adhesion to Ag, which can be used as a material of the lead frame, becomes higher, and therefore the reflow resistance is comprehensively improved. In addition, it can be considered that as the melt viscosity becomes lower, the fluidity becomes higher and the moldability is excellent.

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

[化3]

R ₁ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ₂ represents a substituent represented by formula (a), m represents a number from 0 to 20, p represents 0.5 to 2.0, and R _{3 represents} each independently Ground represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbons.

In the general formula (1), R ₂ represents a substituent represented by the formula (a) (hereinafter, also referred to as a "benzyl group"). p represents a number from 0.5 to 2.0, which refers to the average number (number average) of benzyl groups substituted on one benzene ring. p is 0.5 to 2.0, preferably 0.7 to 1.5. If p is 0.7 or more, the reflow resistance is further improved, and if p is 1.5 or less, the hardenability is further improved.

Here, p is explained. Up to three benzyl groups can be substituted on the benzene rings at both ends in the compound represented by the general formula (1). A maximum of two benzyl groups can be substituted on the middle benzene ring. Therefore, when m is 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 this embodiment, p in general formula (1) is 0.5 to 2.0. In addition, in this embodiment, p is a number average value, so it may be the one in which the hydrogen atom in the benzene ring in general formula (1) is not substituted with a benzyl group.

In formula (a), R ₃ each 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, and more preferably a hydrogen atom.

In the general formula (1), R ₁ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbons, preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom or a methyl group . In addition, R ₁ may be located at any of the ortho, meta, and para positions of the benzene ring, and 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 from 0 to 20, preferably a number from 1.0 to 5.0.

The melt viscosity of the specific epoxy resin at 150°C 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 better.

The melt viscosity can be measured by the following method using a rotary viscoelasticity measuring device (for example, Shimadzu Corporation, product name: CFD-100D). (1) Set the temperature range to 150℃, (2) Melt the sample of 0.15 g～0.25 g on the plate, and lower the cone, and place it until the temperature control lamp is repeated 5 times Until the blinking. (3) Stir the cone up and down for about 20 seconds, and then leave it to stand until the temperature control lamp blinks 5 times. (4) After the cone rotates, read the value after about 15 seconds. (5) Repeat the operations from (3) to (4) until the value becomes the same, and record the value. (6) Repeat the operations of (2) to (5) 3 times or more in the same batch, and set the average value as the viscosity.

The epoxy equivalent of the specific epoxy resin is preferably 240 g/eq～270 g/eq, more preferably 255 g/eq～270 g/eq, and still more preferably 257 g/eq～270 g/eq, especially preferred It is 259 g/eq～270 g/eq.

The epoxy equivalent can be measured by the following method. Measure the epoxy resin into a 100 mL flask so that the solid content becomes 3 g～4 g, add 20 mL of acetic acid and 10 mL of tetraethylammonium bromide acetic acid solution (100 g of tetraethylammonium bromide And 400 mL of acetic acid mixture) and 4 to 5 drops of crystal violet (crystal violet). The solution was titrated with a 0.1 mol/L perchloric acid acetic acid solution. Titrate the blank sample in the same way. The epoxy equivalent is calculated by the following formula.

Epoxy equivalent = 1,000 × the mass of the epoxy resin actually measured [g] × the solid content concentration of the epoxy resin [mass%]/((titer amount [mL]-blank sample titer [mL]) × 0.1 mol/L×The factor of perchloric acid acetic acid solution f)

From the viewpoint of formability and reflow resistance, the softening point of the specific epoxy resin is preferably 50°C to 80°C, more preferably 55°C to 70°C, and still more preferably 56°C to 65°C. The softening point of a specific epoxy resin can be determined by the ring and ball method. The so-called ring and ball method refers to setting the resin in a support ring in a water bath, placing a 3.5 g±0.05 g ball in the center of the ring, and increasing the bath temperature at a rate of 5°C±0.5°C per minute, and then measuring the resin The temperature when the ball sags due to the weight of the ball. Specifically, it is measured in accordance with Japanese Industrial Standards (JIS) K7234:1986.

The specific epoxy resin can be obtained by combining a compound containing a benzyl group corresponding to the formula (a) (hereinafter, also referred to as a "raw material containing a benzyl group") and a phenol corresponding to the general formula (1) Novolak resin (hereinafter, also referred to as "raw material phenol novolak resin") is reacted in the presence of an acid catalyst to obtain a specific phenol novolak resin, and the specific phenol novolak resin is epoxidized.

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, it is preferable to formulate the raw material phenol phenol with the addition of 0.5 to 2.0, more preferably 0.7 to 1.5, relative to 1 benzene ring of the raw material phenol novolak resin. Varnish resins and raw materials containing benzyl compounds. Here, the benzene ring of the raw material phenol novolak resin has one hydroxyl group, so relative to 1 mol of the hydroxyl group in the raw material phenol novolak resin, the blending ratio of the benzyl group-containing compound of the raw material is preferably 0.5 mol to 2.0 mol, More preferably, it is 0.7 mol to 1.5 mol.

The raw material phenol novolak resin contains _{a structure in which a phenol compound having R 1} (a hydrogen atom or a monovalent hydrocarbon group with 1 to 6 carbon atoms) is linked with a methylene group. Examples of phenol compounds include phenol, cresol, ethyl phenol, isopropyl phenol, n-propyl phenol, isobutyl phenol, tertiary butyl phenol, n-pentyl phenol, n-hexyl phenol, and the like. Among these, the phenol compound is preferably ortho-cresol or cresol containing ortho-cresol as a main component. In the case of using cresol containing ortho-cresol as a main component, the content of ortho-cresol relative to the entire cresol is preferably 50% by mass or more, and more preferably 70% by mass or more. In the case of using cresol containing o-cresol as a main component, cresol containing o-cresol as a main component may include m-cresol and p-cresol.

The raw material phenol novolak resin _{may have a structure in which a phenol compound having R 1} is connected to a methylene group, and may have a structure in which another phenol compound is connected to a part of a methylene group. Examples of other phenol compounds include: allylphenol, phenylphenol, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcinol, catechol, 1 -Naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, etc. A part of the compound represented by the general formula (1) may contain a structural unit derived from another phenol compound. The compound represented by the general formula (1) preferably contains 10% by mass or less of the source relative to all the structural units. The structural unit from another phenol compound is more preferably contained at 5 mass% or less, and further preferably not contained substantially.

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

As an acid catalyst, what is necessary is just to select suitably from a well-known inorganic acid and organic acid. Specifically, examples include: mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, and diethyl sulfuric acid; zinc chloride, aluminum chloride, Lewis acids such as ferric chloride and boron trifluoride; solid acids such as ion exchange resin, activated clay, silica-alumina, zeolite, etc.

The reaction for synthesizing a specific phenol novolak resin is usually carried out at 10°C to 250°C for 1 hour to 20 hours. Furthermore, when the reaction is performed, a solvent may also be used. Examples of solvents include alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, and ethyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents; ether solvents such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzene, etc.

Regarding this reaction, the following methods can be cited: a method of batching all the raw materials of the raw material phenol novolak resin and the raw material benzyl-containing compound, and directly reacting at a predetermined temperature; and adding the raw material phenol novolak resin and a catalyst, A method of carrying out the reaction while keeping the temperature at a predetermined temperature and adding dropwise the benzyl-containing compound as the raw material. At this time, the dropping time is usually 1 hour to 10 hours, preferably 5 hours or less. When a solvent is used after the reaction, after removing the catalyst as needed, the solvent is distilled off to obtain a specific phenol novolak resin.

Examples of methods for epoxidizing specific phenol novolak resin include: a method of reacting a specific phenol novolak resin with epichlorohydrin; and a method of reacting a specific phenol novolak resin with a halogenated allyl group to form an allyl group A method of reacting ether compounds with peroxides.

For example, after dissolving a specific phenol novolak resin in excess epichlorohydrin, in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, at 20°C to 150°C, preferably 30°C A method of reacting in the range of ~80°C for 1 hour to 10 hours. The usage amount of the alkali metal hydroxide at this time is preferably 0.8 mol to 1.5 mol, and more preferably 0.9 mol to 1.2 mol relative to 1 mol of the hydroxyl group of the specific phenol novolak resin. In addition, epichlorohydrin is used in excess relative to 1 mol of the hydroxyl group of the specific phenol novolak resin, and is usually 1.5 mol to 30 mol relative to 1 mol of the hydroxyl group of the specific phenol novolak resin, preferably It is in the range of 2 mol to 15 mol. After the reaction, the excess epichlorohydrin is distilled off, and the residue is dissolved in toluene, methyl isobutyl ketone and other solvents, filtered and washed with water to remove inorganic salts, and then the solvent is distilled off to obtain the target specific Epoxy resin.

In addition to the specific epoxy resin, the epoxy resin composition may further use a conventionally known epoxy resin in combination. Examples of epoxy resins that can be used in combination include phenolic compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F, and α-naphthol, β -At least one of naphthol compounds such as naphthol and dihydroxynaphthalene is condensed or co-condensed with a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicaldehyde under an acidic catalyst to obtain a novolac resin, Novolak type epoxy resin obtained by epoxidizing this novolak resin [for example, phenol novolak type epoxy resin (except specific epoxy resin), o-cresol novolak type epoxy resin (except specific epoxy resin) And triphenylmethane type epoxy resin]; bisphenol A, bisphenol F, bisphenol S, alkyl substituted or unsubstituted diglycidyl ether epoxy resin; stilbene type Epoxy resin; hydroquinone type epoxy resin; glycidyl ester type epoxy resin obtained by the reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; Glycidylamine-type epoxy resin obtained by the reaction of polyamines such as phenylmethane and isocyanuric acid with epichlorohydrin; dicyclopentadiene as an epoxide of the co-condensed resin of dicyclopentadiene and phenolic compounds Diene type epoxy resin; naphthalene type epoxy resin with naphthalene ring; phenol aralkyl type epoxy resin as epoxide of phenol aralkyl resin; biphenyl type ring containing a biphenyl skeleton Oxygen resin; naphthol aralkyl type epoxy resin as the epoxide of naphthol aralkyl resin; trimethylolpropane type epoxy resin; terpene modified epoxy resin; Linear aliphatic epoxy resins obtained by oxidation of olefin bonds; cycloaliphatic epoxy resins; epoxy resins containing sulfur atoms, etc. As the epoxy resin which can be used together, one of these may be used alone, or two or more of them may be used in combination.

Among them, as epoxy resins that can be used in combination, bisphenol F type epoxy resins, sulfur atom-containing epoxy resins, and phenol aralkyl type epoxy resins are preferred from the viewpoints of fluidity and reflow resistance. From the viewpoint of curability, novolac type epoxy resin (except for specific epoxy resins) is preferred, and from the viewpoint of low moisture absorption, dicyclopentadiene type epoxy resin is preferred. From the viewpoints of heat resistance and low warpage properties, naphthalene type epoxy resins and triphenylmethane type epoxy resins are preferred, and from the viewpoint of flame retardancy, stretched biphenyl type epoxy resins are preferred And naphthol aralkyl type epoxy resin. From the viewpoint of improving high-temperature storage characteristics, it is preferable to use an epoxy resin with good flame retardancy in combination to form a halogen-free, antimony-free epoxy resin composition.

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

[化4]

In the general formula (III), R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 10 carbons, an aryl group having 6 to 10 carbons, or 7 ～10 aralkyl group. n is an average value and represents a number from 0 to 3. The alkyl group, alkoxy group, aryl group, and aralkyl group represented by R ¹ to R ^{8 may or may not have a substituent each independently.}

[化5]

In the general formula (IV), R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbons, or an alkoxy group having 1 to 10 carbons. n is an average value and represents a number from 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.

[化6]

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

As the bisphenol F epoxy resin represented by the general formula (III), for example, it can be obtained as a commercially available product. R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, and R ² , R ⁴ , R ⁵ and YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which R ^{7 is a hydrogen atom and n=0 as the main component.}

Among the sulfur atom-containing epoxy resins represented by the general formula (IV), those 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 are preferred The epoxy resin is more preferably an epoxy resin in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are tertiary butyl groups, and R ⁴ and R ⁵ are methyl groups. As such a compound, YSLV-120TE (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) can be obtained as a commercially available product, for example.

As the epoxy resin represented by the general formula (V), for example, NC-2000L (Nippon Kayaku Co., Ltd., trade name) ^{in which R 1} to R ^{5 are hydrogen atoms can be obtained as a commercially available product.} Any one of these epoxy resins may be used alone, or two or more of them may be used in combination.

As a novolak type epoxy resin, the epoxy resin represented by the following general formula (VI) is mentioned, for example.

[化7]

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

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

Among the novolak type epoxy resins represented by the general formula (VI), ortho-cresol novolak type epoxy resins are preferred. As such a compound, EOCN-1020 (Nippon Kayaku Co., Ltd., trade name) can be obtained as a commercially available product, for example.

As a dicyclopentadiene type epoxy resin, the epoxy resin represented by the following general formula (VII) is mentioned, for example.

[化8]

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

^{Examples of R 1} in the general formula (VII) include hydrogen atom; alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, and tertiary butyl; vinyl, allyl, butenyl Alkenyl groups; substituted monovalent hydrocarbon groups such as halogenated alkyl groups, amino-substituted alkyl groups, and mercapto-substituted alkyl groups with 1 to 5 carbon atoms. Among them, alkyl groups such as methyl and ethyl groups or hydrogen atoms are preferred. , More preferably a methyl group or a hydrogen atom.

^{Examples of R 2} in the general formula (VII) include hydrogen atom; alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, and tertiary butyl; vinyl, allyl, butenyl Alkenyl groups; monovalent hydrocarbon groups having 1 to 5 carbon atoms such as halogenated alkyl groups, amino-substituted alkyl groups, and mercapto-substituted alkyl groups, etc., among which a hydrogen atom is preferred. As such a compound, HP-7200 (DIC Co., Ltd., trade name) can be obtained as a commercially available product, for example.

As a naphthalene type epoxy resin, the epoxy resin represented by the following general formula (VIII) is mentioned, for example. As a triphenylmethane type epoxy resin, the epoxy resin represented by the following general formula (IX) is mentioned, for example.

[化9]

In the general formula (VIII), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbons. p is the average value, representing the number from 0 to 2, l and m are the average values, each independently representing the number from 0 to 11, with (l+m) being a number from 1 to 11 and (l+p) being 1 to Select the number of ways of 12. 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. The hydrocarbon groups represented by R ¹ to R ³ may or may not have a substituent each independently.

Examples of the naphthalene type epoxy resin represented by the general formula (VIII) include a random copolymer containing 1 structural unit and m structural units randomly, and an alternation of 1 structural unit and m structural units alternately. Copolymers, copolymers regularly containing 1 structural unit and m structural units, and block copolymers containing 1 structural unit and m structural units in a block form, any of these can be used alone, Two or more types can also be used in combination. As ^{the compound in which R 1} and R ² are a hydrogen atom and R ³ is a methyl group, for example, NC-7000 (Nippon Kayaku Co., Ltd., trade name) is available as a commercially available product.

[化10]

In the general formula (IX), R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbons, and n is an average value and represents a number from 0 to 10. The hydrocarbon group represented by R may have a substituent each independently, and may not have it. As the compound in which R is a hydrogen atom, for example, E-1032 (Mitsubishi Chemical Corporation, trade name) can be obtained as a commercially available product.

As a biphenylene type epoxy resin, the epoxy resin represented by the following general formula (X) is mentioned, for example. As a naphthol aralkyl type epoxy resin, the epoxy resin represented by the following general formula (XI) is mentioned, for example.

[化11]

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, ethyl, propyl, butyl, isopropyl, and isobutyl; methoxy Alkoxy groups with 1 to 10 carbons such as phenyl, ethoxy, propoxy, butoxy; aryl groups with 6 to 10 carbons such as phenyl, tolyl, and xylyl; or benzyl, phenethyl Among other aralkyl groups having 7 to 10 carbon atoms, a hydrogen atom or a methyl group is preferred. n is an average value and represents a number from 0 to 10. The alkyl group, alkoxy group, aryl group, and aralkyl group represented by R ¹ to R ^{9 may each independently have a substituent, or may not have.}

[化12]

In the general formula (XI), R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbons, and n is an average value and represents a number from 0 to 10. The hydrocarbon group represented by R ¹ and R ² may each independently have a substituent, or may not have.

As a biphenyl type epoxy resin, NC-3000 (Nippon Kayaku Co., Ltd., trade name) can be obtained as a commercially available product, for example. In addition, as the naphthol aralkyl type epoxy resin, for example, ESN-175 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) can be obtained as a commercially available product. Any one of the biphenyl-type epoxy resins may be used alone, or two or more of them may be used in combination.

In addition, as the epoxy resin, an epoxy resin represented by the following general formula (XII) may also be used.

[化13]

^{R 1} in the general formula (XII) each independently represents a hydrocarbon group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons, and n is an average value and represents a number of 0 to 4. In addition, R ² each independently represents a hydrocarbon group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons, and m is an average value and represents a number of 0 to 2. The hydrocarbon group and alkoxy group represented by R ¹ and R ² each independently may have a substituent, or may not have. Among them, from the viewpoint of flame retardancy and moldability, epoxy resins in which n and m are zero are preferred. As such a compound, for example, YX-8800 (Mitsubishi Chemical Corporation, trade name) can be obtained.

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

(Hardening agent) The epoxy resin composition contains a hardening agent. The hardener includes at least one selected from the group consisting of biphenyl-type phenol aralkyl resin, phenol aralkyl resin, and triphenylmethane-type phenol resin.

Preferably, it is a biphenyl-type phenol aralkyl resin represented by the following general formula (XVII).

[化14]

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

Examples of the biphenyl-type phenol aralkyl resin represented by the general formula (XVII) include ^{compounds in which all of R 1} to R ⁹ are hydrogen atoms. Among them, from the viewpoint of melt viscosity, it is preferable to contain 50 mass % Or more of n is a mixture of condensates of 1 or more condensates. As such a compound, MEH-7851 (Minghe Chemical Co., Ltd., trade name) can be obtained as a commercially available product, for example. In the case of using these biphenyl-type phenol aralkyl resins, in order to exert its performance, its content relative to the total amount of hardener is preferably 30% by mass or more, and more preferably 50% by mass or more.

From the viewpoints of reflow resistance, flame retardancy, and formability, a phenol aralkyl resin represented by the following general formula (XIII) is preferred.

[化15]

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

Among the compounds represented by the general formula (XIII), a phenol aralkyl resin in which R is a hydrogen atom and the average value of n is 0 to 8 is more preferable. As a specific example, a p-xylylene-type phenol aralkyl resin, a m-xylylene-type phenol aralkyl resin, etc. are mentioned. As such a compound, XLC (Mitsui Chemicals Co., Ltd., trade name) can be obtained as a commercially available product, for example. In the case of using these phenol aralkyl resins, in order to exhibit its performance, its content relative to the total amount of the hardener is preferably 30% by mass or more, and more preferably 50% by mass or more.

From the viewpoint of reducing warpage, a triphenylmethane type phenol resin is preferred. As a triphenylmethane type phenol resin, the phenol resin represented by the following general formula (XVI) is mentioned, for example.

[化16]

In the general formula (XVI), R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an average value and represents a number from 0 to 10. The hydrocarbon group represented by R may have a substituent each independently, and may not have it. As the compound in which R is a hydrogen atom, for example, MEH-7500 (Minghe Chemical Co., Ltd., trade name) can be obtained as a commercially available product. In the case of using these triphenylmethane type phenol resins, in order to exhibit its performance, the content of the curing agent is preferably 30% by mass or more, and more preferably 50% by mass or more with respect to the total amount of the hardener.

Any one of the specific hardeners may be used alone, or two or more of them may be used in combination. Furthermore, in addition to the specific hardener, the hardener may also be used in combination with other hardeners. The content of the specific curing agent in all curing agents is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more.

Other hardeners include: novolak type phenol resin, naphthol aralkyl resin, dicyclopentadiene type phenol resin, terpene modified phenol resin, paraxylylene modified phenol resin, metaxylylene Modified phenol resin, melamine modified phenol resin, cyclopentadiene modified phenol resin, phenol resin obtained by copolymerizing two or more of these, and the like.

Examples of novolak-type phenol resins include phenol novolac resins, cresol novolac resins, naphthol novolac resins, and the like. Among them, phenol novolac resins are preferred.

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

[化17]

In the general formula (XIV), R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbons, and n is an average value and represents a number from 0 to 10. The hydrocarbon group represented by R ¹ and R ² may each independently have a substituent, or may not have.

As the naphthol aralkyl resin represented by the general formula (XIV), for example ^{, a compound in which all of R 1} and R ² are hydrogen atoms can be cited. As such a compound, for example, SN-170 (New Japan Iron & Steel Chemical Co., Ltd., trade name).

As a dicyclopentadiene type phenol resin, the phenol resin represented by the following general formula (XV) is mentioned, for example.

[化18]

In the general formula (XV), R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an average value and represents a number from 0 to 10, and m represents an integer from 0 to 6. The hydrocarbon group represented by R ¹ and R ² may each independently have a substituent, or may not have. As ^{the compound in which R 1} and R ² are hydrogen atoms, for example, DPP (New Japan Petrochemical Co., Ltd., trade name) can be obtained as a commercially available product.

One of these other hardeners may be used alone, or two or more of them may be used in combination. Among other curing agents used in combination, a novolak-type phenol resin is preferable from the viewpoint of curability.

The hydroxyl equivalent of the hardener is preferably 100 g/eq to 199 g/eq, more preferably 130 g/eq to 199 g/eq, and still more preferably 175 g/eq to 199 g/eq.

The measuring method of the hydroxyl equivalent in the hardening agent is as follows. The pyridine-acetyl chloride method is used to chlorinate the hydroxyl group of the hardening agent 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. , So as to obtain the hydroxyl equivalent.

The equivalent ratio of epoxy resin to hardener, that is, the ratio of the number of hydroxyl groups in the hardener to the number of epoxy groups in the epoxy resin (the number of hydroxyl groups in the hardener/the number of epoxy groups in the epoxy resin) is not particularly limited In order to reduce the respective unreacted components, it is preferably set in the range of 0.5-2, and more preferably set in the range of 0.6-1.3. In order to obtain an epoxy resin composition excellent in formability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

(Curing accelerator) From the viewpoint of accelerating the reaction between the epoxy resin and the curing agent, a curing accelerator may be used in the epoxy resin composition as necessary. The hardening accelerator can be used for general users in the epoxy resin composition without particular limitation. Examples of hardening accelerators include: 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-di Butylamino-1,8-diaza-bicyclo[5.4.0]undecene-7 and other cycloamidine compounds; add maleic anhydride, 1,4-benzoquinone, 2,5-methylbenzoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1, Quinone compounds such as 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenol resins and other compounds with p bonds Compounds with intramolecular polarization; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of tertiary amine compounds; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and other imidazole compounds; derivatives of imidazole compounds; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, triphenylphosphine (4-methylphenyl)phosphine, diphenylphosphine, phenylphosphine and other phosphine compounds; adding maleic anhydride, the quinone compound, diazophenylmethane, phenol resin, etc. to these phosphine compounds has p Phosphorus compound with intramolecular polarization formed by the bond compound; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, Tetraphenyl boron salts such as N-methylmorpholine tetraphenyl borate; derivatives of tetraphenyl borate, etc. One of these hardening accelerators may be used alone, or two or more of them may be used in combination.

Among them, from the viewpoint of flame retardancy, curability, fluidity, and mold release properties, the curing accelerator is preferably an adduct of a tertiary phosphine compound and a quinone compound.

The tertiary phosphine compound is not particularly limited, and examples include tricyclohexyl phosphine, tributyl phosphine, dibutyl phenyl phosphine, butyl diphenyl phosphine, ethyl diphenyl phosphine, triphenyl phosphine, Tris(4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(isopropylbenzene) Yl)phosphine, tris(tertiary butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6 -Trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl) ) Tertiary phosphine compounds having alkyl or aryl groups such as phosphine.

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

As the hardening accelerator, from the viewpoint of reflow resistance, an adduct of triphenylphosphine and p-benzoquinone is preferred, and from the viewpoint of mold release properties, tris(4-methylbenzene) is preferred. Group) phosphine and p-benzoquinone adduct.

The content rate of the hardening accelerator is not particularly limited as long as the hardening accelerator effect can be achieved. When the epoxy resin composition contains a hardening accelerator, the content of the hardening accelerator is preferably 0.005% to 2% by mass in the epoxy resin composition, and more preferably 0.01% to 0.5% by mass. When it is 0.005 mass% or more, the curability tends to improve, and when it is 2 mass% or less, the pot life tends to increase.

(Inorganic filler)

The epoxy resin composition may further contain an inorganic filler. If it contains an inorganic filler, it tends to reduce moisture absorption, reduce linear expansion coefficient, increase thermal conductivity, and increase strength. Examples of inorganic fillers include: fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, Powders such as beryllium oxide, zirconia, forsterite, steatite, spinel, mullite, and titanium oxide, beads formed by spheroidizing these, glass fibers, and the like. Furthermore, as an inorganic filler having a flame-retardant effect, aluminum hydroxide, magnesium hydroxide, composite metal hydroxide, zinc borate, zinc molybdate, and the like can be cited. Here, as zinc borate, FB-290, FB-500 (US Borax Corporation), FRZ-500C (Mizusawa Chemical Industry Co., Ltd.), etc. can be obtained as commercially available products, respectively, as zinc molybdate KEMGARD 911B, KEMGARD 911C, KEMGARD 1100 (Sherwin-Williams) are available as commercially available products. )Wait.

These inorganic fillers may be used alone or in combination of two or more. Among them, from the viewpoints of filling properties and reduction of the linear expansion coefficient, fused silica is preferred, and from the viewpoint of high thermal conductivity, alumina is preferred. From the viewpoint of filling properties and mold wear properties, the shape of the inorganic filler is preferably spherical.

The average particle size of the inorganic filler is preferably 1 μm to 50 μm, more preferably 10 μm to 30 μm. If the average particle size is 1 μm or more, the increase in the viscosity of the epoxy resin composition tends to be suppressed. If the average particle size is 50 μm or less, preferably 30 μm or less, it has filling properties in narrow gaps. Tendency to improve. The average particle size of the inorganic filler is measured in the form of volume average particle size using a laser scattering diffraction method particle size distribution measuring device.

From the standpoint of flame retardancy and fluidity, the specific surface area of the inorganic filler is preferably 1 m ² /g to 5 m ² /g, more preferably 2 m ² /g to 4 m ² /g.

When the epoxy resin composition contains inorganic fillers, in terms of fluidity, flame retardancy, formability, reduced moisture absorption, reduced linear expansion coefficient, improved strength and reflow resistance, inorganic fillers The content of the epoxy resin composition is preferably 50% by mass or more. From the standpoint of flame retardancy, it is more preferably 60% to 95% by mass, and more preferably 70% to 90% by mass. . If the content of the inorganic filler is 50% by mass or more, fluidity tends to improve, and if it is 95% by mass or less, flame retardancy and reflow resistance tend to improve.

(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 a coupling agent, it can be used for general users in an epoxy resin composition without particular limitation. Examples of coupling agents include: silane compounds having primary, secondary, or tertiary amine groups, epoxy silanes, mercapto silanes, alkyl silanes, ureido silanes, vinyl silanes and other silane compounds, titanium Compounds, aluminum chelate compounds, compounds containing aluminum and zirconium, etc.

Examples of coupling agents include: vinyl trichlorosilane, vinyl triethoxy silane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyl trimethoxy Yl silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl methyl dimethoxy Silane, vinyl triacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-amino Propyl triethoxysilane, γ-aminopropylmethyl diethoxysilane, γ-anilinopropyl trimethoxysilane, γ-anilinopropyl triethoxysilane, γ-(N, N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyl Trimethoxysilane, γ-(N-methyl)anilinopropyl trimethoxysilane, γ-(N-ethyl)anilinopropyl trimethoxysilane, γ-(N,N-dimethyl) Aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxy Silane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyltriethoxysilane, γ-(N,N-dimethyl)amine Propylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyl Dimethoxysilane, γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-( Trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltri Silane coupling agents such as ethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.; isopropyl triisopropyl Stearyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis( Di-tridecyl phosphite) titanate, tetrakis (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl phosphite) titanate, Bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, isopropyl trioctyl titanate, isopropyl dimethacrylic acid Isostearyl titanate, isopropyl tris-dodecylbenzenesulfonyl titanate, isopropyl isostearyl diacrylate titanate, isopropyl tris(dioctyl phosphate) ) Titanate coupling agents such as titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate, etc. As the coupling agent, one of these may be used alone, or two or more of them may be used in combination.

Among them, from the viewpoints of fluidity, reduction of wire deformation, and flame retardancy, the coupling agent is preferably a silane coupling agent having a secondary amine group. The silane coupling agent having a secondary amine group is not particularly limited as long as it is a silane compound having a secondary amine group in the molecule.

As a silane coupling agent having a secondary amino group, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, and γ-anilinopropylmethyldimethoxysilane can be mentioned. , Γ-anilinopropylmethyl diethoxysilane, γ-anilinopropyl ethyl diethoxysilane, γ-anilinopropyl ethyldimethoxysilane, γ-anilinomethyl trimethyl Oxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyl diethoxysilane, γ-anilinomethyl Ethyl diethoxysilane, γ-anilinomethylethyldimethoxysilane, N-(p-methoxyphenyl)-γ-aminopropyl trimethoxysilane, N-(p-methoxy Phenyl)-γ-aminopropyltriethoxysilane, N-(p-methoxyphenyl)-γ-aminopropylmethyldimethoxysilane, N-(p-methoxybenzene) Group)-γ-aminopropylmethyl diethoxysilane, N-(p-methoxyphenyl)-γ-aminopropylethyl diethoxysilane, N-(p-methoxybenzene Yl)-γ-aminopropylethyldimethoxysilane, γ-(N-methyl)aminopropyltrimethoxysilane, γ-(N-ethyl)aminopropyltrimethoxysilane , Γ-(N-butyl)aminopropyl trimethoxysilane, γ-(N-benzyl)aminopropyl trimethoxysilane, γ-(N-methyl)aminopropyl triethoxy Silane, γ-(N-ethyl)aminopropyltriethoxysilane, γ-(N-butyl)aminopropyltriethoxysilane, γ-(N-benzyl)aminopropyl Triethoxysilane, γ-(N-methyl)aminopropylmethyldimethoxysilane, γ-(N-ethyl)aminopropylmethyldimethoxysilane, γ-( N-butyl)aminopropylmethyldimethoxysilane, γ-(N-benzyl)aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ- Aminopropyltrimethoxysilane, γ-(β-aminoethyl)aminopropyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyl Trimethoxysilane, etc.

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

(Flame retardant) From the viewpoint of improving the flame retardancy, the epoxy resin composition may further contain a conventionally known flame retardant, and in particular, from the viewpoint of environmental protection and reliability, it may also contain halogen-free And antimony-free flame retardant. Examples of flame retardants include inorganic compounds such as red phosphorus, phosphoric acid esters, and zinc oxide; resin-coated phosphorus compounds such as red phosphorus and phosphine oxide coated with thermosetting resins such as phenol resin; melamine, melamine derivatives, and melamine modification Phenolic resins, compounds with triazine rings, cyanuric acid derivatives, isocyanuric acid derivatives and other nitrogen-containing compounds, cyclophosphazene and other phosphorus- and nitrogen-containing compounds, aluminum hydroxide, magnesium hydroxide, and composite metal hydroxides , Zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron and other compounds containing metal elements. One of these flame retardants may be used alone, or two or more of them may be used in combination.

(Silicon-containing polymer) From the viewpoint of reducing warpage, the epoxy resin composition may also contain a silicon-containing polymer. As the silicon-containing polymer, it is preferable to have the following bond (c) and bond (d), and the terminal is a ^{group selected from the group consisting of R 1} , hydroxyl, and alkoxy, and has an epoxy equivalent of 500 g /eq～4000 g/eq compound. Examples of the silicon-containing polymer include branched polysiloxanes called silicone resins.

[化19]

Here, R ¹ each independently represents a monovalent hydrocarbon group having 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 undergoes a ring-opening reaction, and X may also become a divalent group.

^{Examples of R 1 in} bond (c) and bond (d) include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, Alkyl groups such as octyl and 2-ethylhexyl; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl; phenyl, tolyl, xylyl, naphthyl, biphenyl Aryl groups such as benzyl groups and phenethyl groups; aralkyl groups such as benzyl groups and phenethyl groups. Among them, methyl or phenyl groups are preferred.

In addition, 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 the epoxy group is preferably bonded to the end of the organic group.

Specifically, as X, 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3- Glycidyloxypropyl, 4-glycidyloxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, etc., of which , Preferably 3-glycidoxypropyl.

In addition, from the viewpoint of the storage stability of the polymer, it is preferable that the terminal of the silicon-containing polymer is such that R ^{1 is} independently a hydroxyl group or an alkoxy group. As for the alkoxy group as a terminal, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. are mentioned.

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 fluidity of the epoxy resin composition tends to improve, and when it is 4000 g/eq or less, the cured product is prevented from bleeding to the The surface has a tendency to reduce the occurrence of poor molding.

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

(Other components) From the viewpoint of improving the humidity resistance and high temperature storage characteristics of semiconductor elements such as ICs, the epoxy resin composition may optionally contain compounds selected from the following composition formula (XXXIII) and the following composition At least one of the group consisting of compounds represented by formula (XXXIV).

（0＜x≦0.5，m為正數）[化20]

(0＜x≦0.5, m is a positive number)

（0.9≦x≦1.1，0.6≦y≦0.8，0.2≦z≦0.4）[化21]

(0.9≦x≦1.1, 0.6≦y≦0.8, 0.2≦z≦0.4)

Furthermore, the compound of formula (XXXIII) can be obtained as a commercially available product as the trade name DHT-4A of Concord Chemical Industry Co., Ltd. In addition, the compound of formula (XXXIV) can be obtained as a commercially available product as the trade name IXE500 of Toagosei Co., Ltd. In addition, other anion exchangers can also be added as needed. The anion exchanger is not particularly limited, and conventionally known ones can be used, and examples thereof include hydroxides containing elements such as magnesium, aluminum, titanium, zirconium, and antimony. As the anion exchanger, one of these can be used alone or two or more of them can be used in combination.

Furthermore, the epoxy resin composition may optionally contain higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, oxidized polyethylene and other mold release agents, carbon black and other colorants, silicone oil, and silicone Stress relievers such as rubber powder are used as other additives.

<Method for preparing epoxy resin composition> The epoxy resin composition can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general preparation method, the raw materials of a predetermined blending amount are thoroughly mixed with a mixer or the like, then mixed or melt-kneaded with a mixing roll, extruder, crusher, planetary mixer, etc., and then cooled. Defoaming and crushing methods are carried out as needed. In addition, the epoxy resin composition may be ingot in a size and quality that meets the molding conditions as needed.

<Electronic component device> An electronic component device according to an embodiment of the present invention includes an element and a cured product of the epoxy resin composition that seals the element. As a method of sealing an element using the epoxy resin composition of this embodiment as a sealing material, a low-pressure transfer molding method is usually used, and an injection molding method, a compression molding method, etc. can also be mentioned. As a method of applying the epoxy resin composition, a dispensing method, a casting method, a printing method, etc. can be used.

Examples of the electronic component device of the present embodiment having components sealed with the epoxy resin composition of the present embodiment include: supporting members such as lead frames, wired tape carriers, wiring boards, glass, silicon wafers, etc., and mounting Electronic components such as semiconductor chips, transistors, diodes, thyristors, and other active components, capacitors, resistors, coils, and other passive components are mounted on a substrate, and the required parts are sealed with the epoxy resin composition of this embodiment. Devices, etc.

Here, the mounting substrate is not particularly limited, and examples include: organic substrates, organic membranes, ceramic substrates, glass substrates and other interposer substrates, glass substrates for liquid crystals, substrates for multi-chip modules (Multi Chip Module, MCM), Substrates for hybrid ICs, etc.

Examples of electronic component devices equipped with such elements include semiconductor devices. Specifically, they include: fixing elements such as semiconductor wafers to lead frames (islands, tabs), and attaching elements such as bonding pads. After the terminal part and the lead part are connected by wire bonding or bumping, the epoxy resin composition of this embodiment is used to seal the dual inline package (DIP) by injection molding, etc., plastic Leaded Chip Carrier (Plastic Leaded Chip Carrier, PLCC), Quad Flat Package (QFP), Small Outline Package (SOP), Small Outline J-lead Package (SOJ) ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP) and other resin-sealed ICs; the epoxy resin composition of this embodiment is used to bond the wires to the tape carrier A Tape Carrier Package (TCP) made by sealing the semiconductor chip of the present invention; the epoxy resin composition of this embodiment is used to connect wire bonding, flip chip bonding, solder, etc. to the wiring board, glass, etc. Semiconductor devices with bare chips, such as chip on board (COB), chip on glass (COG), etc., obtained by sealing a semiconductor chip made of wiring, etc.; use the epoxy resin of this embodiment The object will be connected to the semiconductor chip, transistor, diode, thyristor and other active components, capacitors, resistors, coils, etc., which are formed by wire bonding, flip chip bonding, solder, etc. Hybrid IC with sealed components; mount a semiconductor chip on an interposer substrate with terminals for connecting to a multi-chip module (Multi Chip Module, MCM) motherboard, and connect the semiconductor chip to the substrate by bumps or wire bonding. After the wiring formed on the interposer substrate is connected, the semiconductor chip mounting side is sealed with the epoxy resin composition of this embodiment to obtain a Ball Grid Array (BAG) and Chip Size Package (CSP) ), Multi Chip Package (MCP), etc. In addition, these semiconductor devices may also be a stacked (multilayer) type package in which two or more components are stacked on a mounting substrate, or may be a package that seals two or more components at a time with an epoxy resin composition. Bulk modular packaging. [Example]

Next, the present invention will be described with synthesis examples and examples, but the scope of the present invention is not limited to these examples.

[Synthesis Example 1 to Synthesis Example 4] The specific epoxy resin can be synthesized as described below. First, a raw material phenol novolak resin and a raw material benzyl group-containing compound are reacted using p-toluenesulfonic acid as an acid catalyst to obtain a specific phenol novolak resin. At this time, in the same manner as the method for measuring the hydroxyl equivalent in the curing agent, the hydroxyl equivalent is measured, and the value of p in the general formula (1) is obtained from this value. Then, epichlorohydrin is used to epoxidize the obtained specific phenol novolak resin. The epoxy equivalent, softening point, and melt viscosity at 150°C of the obtained resin are shown in Table 1 below. Furthermore, in the obtained specific epoxy resin, R ₂ in the general formula (1) is a benzyl group (R ₃ is a hydrogen atom).

[Table 1]

[Example 1 to Example 4, Comparative Example 1 to Comparative Example 8] The following components were blended in the parts by mass shown in Table 2 and Table 3, respectively, and rolled under the conditions of a kneading temperature of 80°C and a kneading time of 10 minutes. By kneading, Examples 1 to 4 and Comparative Example 1 to Comparative Example 8 were produced.

(Epoxy resin) × Epoxy resin 1: epoxy equivalent 240 g/eq, softening point 55°C, compound represented by general formula (1), epoxy resin with p=0.6 × epoxy resin 2: epoxy equivalent 263 g/eq, softening point 58°C, compound represented by general formula (1), epoxy resin with p=0.9 × epoxy resin 3: epoxy equivalent 264 g/eq, softening point 60°C, general formula (1 ) Represented by the compound, p=1.0 epoxy resin × epoxy resin 4: epoxy equivalent 265 g/eq, softening point 61°C, compound represented by general formula (1), p=1.1 epoxy resin × Epoxy resin 5: Epoxy equivalent 251 g/eq, softening point 60℃, 2-methoxynaphthalene and o-cresol novolac type epoxy resin copolymer (DIC Co., Ltd., trade name HP -5000) ×Epoxy resin 6: epoxy equivalent 190 g/eq, melting point 59°C, o-cresol novolac type epoxy resin (DIC Co., Ltd., trade name N-500P-1)

(Hardener) ×hardener 1: phenol aralkyl resin with hydroxyl equivalent of 175 g/eq and softening point of 70℃ (Minghe Chemical Co., Ltd., trade name MEH-7800SS) ×hardener 2: hydroxy equivalent of 106 g/eq , Novolak-type phenol resin with a softening point of 82°C (Hitachi Chemical Co., Ltd., trade name HP-850N)

(Hardening accelerator) ×hardening accelerator 1: adduct of triphenylphosphine and 1,4-benzoquinone

(Coupling agent) ×Epoxysilane: γ-glycidoxypropyltrimethoxysilane

(Inorganic filler) ×Spherical fused silica: average particle size 14.5 μm, specific surface area 2.8 m ² /g

(Other additives) × carnauba wax (Clariant) × carbon black (Mitsubishi Chemical Corporation, trade name MA-600)

[Table 2]

[table 3]

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

(1) Spiral flow (indicator of fluidity) Using a mold for spiral flow measurement based on EMMI-1-66, use a transfer molding machine to put the epoxy resin composition at a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Under the conditions of forming, and calculate the flow distance (cm).

(2) Hardness during heat: The epoxy resin composition is molded into a circular plate with a diameter of 50 mm × a thickness of 3 mm under the molding conditions described in (1), and it is measured with a Shore D hardness tester immediately after molding. .

(3) Flame Retardancy Using a mold for forming a test piece with a thickness of 1/32 inch (0.8 mm), the epoxy resin composition was molded under the molding conditions of (1), and further, it was performed at 180°C for 5 Harden after hours, and evaluate the flame retardancy according to the UL-94 test method.

(4) Reflow resistance (4.1) Cu lead frame is designed for 80-pin flat package (quad flat package (QFP) with an external size of 20 mm×14 mm×2 mm equipped with a silicon chip of 8 mm×10 mm×0.4 mm) ) (Lead frame material: copper alloy, processed with silver plating on the upper surface of the chip pad and the tip of the lead), using an epoxy resin composition to be molded and post-hardened under the conditions of (3) above, at 85°C , Humidify under the condition of 85% RH, perform reflow treatment at 240°C for 10 seconds after the specified time, visually observe whether there are cracks, and produce packaging with respect to the number of cracks in the test package (5) Number of evaluations.

(4.2) PPF lead frame Except that PPF (core material: copper alloy, three-layer plating (Ni/Pd/Au) processed product) is used for the lead frame, the evaluation was carried out in the same manner as in (4.1).

(5) Humidity resistance: The external dimensions of a 6 mm × 6 mm × 0.4 mm test silicon wafer with aluminum wiring with a line width of 10 μm and a thickness of 1 μm mounted on a 5 μm-thick silicon oxide film is 20 mm The 80-pin flat package (Quad Flat Package (QFP)) of ×14 mm×2.7 mm is manufactured by molding and post-curing the epoxy resin composition under the conditions described in (3) above. After pre-processing, it is added Wet, investigating the broken wire caused by corrosion of aluminum wiring after a predetermined period of time, and evaluate the number of defective packages relative to the number of tested packages (10).

In addition, the pre-treatment is to humidify the flat package at 85°C, 85%RH for 72 hours, and then perform a vapor phase reflow (vapor phase reflow) treatment at 215°C for 90 seconds. The subsequent humidification was performed under the conditions of 0.2 MPa and 121°C.

(6) High temperature storage characteristics Use silver paste to apply a 5 μm thick silicon oxide film on a 5 μm thick silicon oxide film with a 5 mm×9 mm×0.4 mm test silicon wafer with a line width of 10 μm and a thickness of 1 μm. Partially silver-plated 42 alloy lead frame, with thermosonic wire bonder, is aimed at the 16-pin dual in-line type that connects the bonding pads of the chip and the inner leads with Au wires at 200°C The package (Dual Inline Package, DIP) is made by molding and post-curing the epoxy resin composition under the conditions of (3) above. It is stored in a high temperature bath at 200°C, and the one that has passed a predetermined time is taken out and connected. In the test, the high-temperature storage characteristics were evaluated by the number of poorly-conducted packages relative to the number of tested packages (10).

[Table 4]

[table 5]

The comparative example 5 and the comparative example 7 which do not contain the compound represented by general formula (1) have low heat-time hardness, and therefore, they are inferior in formability. Comparative Example 6 and Comparative Example 8 had poor reflow resistance, and the flame retardancy did not reach V-0. Compared with Examples 1 to 4, Comparative Examples 1 to 4 did not use a specific hardening agent, and the spiral flow was small, and the moldability was inferior. In addition, the reflow resistance (especially 72h and 96h) in the Cu lead frames of Comparative Examples 1 to 4 that do not use a specific hardener compared with Examples 1 to 4 that use a specific hardener It is also slightly worse.

In contrast, Examples 1 to 4 containing the compound represented by the general formula (1) have good fluidity and reflow resistance, and all achieve UL-94 V-0, and have good flame retardancy and moldability. good.

The disclosure of Japanese Patent Application No. 2016-091768 for which it applied on April 28, 2016 is incorporated into this specification as a whole by reference. All documents, patent applications, and technical specifications described in this specification are incorporated by reference to the same extent as the respective documents, patent applications, and technical specifications are incorporated by reference. In the manual.

no

no

Claims (9)

An epoxy resin composition comprising: an epoxy resin, including a compound represented by the following general formula (1); and a hardener, including a biphenyl type phenol aralkyl resin and a phenol aralkyl resin And at least one of the group consisting of triphenylmethane type phenol resin; the content rate of the compound represented by the general formula (1) relative to the total amount of epoxy resin is 50% by mass or more;

[R ₁ each independently represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 6 carbon atoms, R ₂ represents a substituent represented by formula (a), m represents a number from 0 to 20, p represents 0.7 to 2.0, and R _{3 represents} each Independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms]. The epoxy resin composition described in item 1 of the scope of the patent application further contains a hardening accelerator. The epoxy resin composition as described in item 2 of the scope of patent application, wherein The hardening accelerator includes an adduct of a tertiary phosphine compound and a quinone compound. The epoxy resin composition according to any one of items 1 to 3 of the scope of patent application, which further contains an inorganic filler. In the epoxy resin composition described in item 4 of the scope of the patent application, the content of the inorganic filler is 60% by mass to 95% by mass. The epoxy resin composition according to any one of items 1 to 3 of the scope of patent application, which further contains a coupling agent. The epoxy resin composition according to item 6 of the scope of patent application, wherein the coupling agent includes a silane coupling agent having a secondary amine group. The epoxy resin composition according to any one of items 1 to 3 in the scope of the patent application, wherein the epoxy equivalent of the epoxy resin is 255g/eq~270g/eq. An electronic component device, comprising: an element; and a cured product of the epoxy resin composition according to any one of items 1 to 8 of the scope of patent application for sealing the element.