TW201807057A - 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 R3independently 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, the resin-sealed type semiconductor device has become the 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, a surface mount type integrated circuit (IC), a large scale integrated circuit (LSI), or the like is a thin and small package. Therefore, the occupied area of the element with respect to the package becomes large, and the thickness of the package becomes very thin.

Furthermore, these packages are different from the conventional pin-inserted package mounting methods. That is, since the pin insertion type package is inserted into the wiring board and soldered from the back side of 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 processed by a solder bath, a reflow soldering apparatus or the like, it is directly exposed to the soldering temperature (reflow temperature). As a result, when the package is moisture-absorbing, the moisture-absorbing moisture is vaporized during reflow, and the generated vapor pressure acts as a peeling stress, and is generated between the insert of the element, the lead frame, and the sealing material. Peeling causes the package crack and electrical characteristics to be poor. Therefore, it has been desired to develop a sealing material excellent in solder heat resistance (reflow resistance).

As the sealing material, in addition to low moisture absorption, it is strongly required to improve the adhesion or adhesion of the lead frame (materials such as Cu, Ag, Au, Pd, etc.) and the wafer interface to various materials. In order to cope with these requirements, various studies have been conducted on an epoxy resin which is a main material. For example, a method using a biphenyl type epoxy resin has been studied (for example, refer to Patent Document 1). In addition, various modifiers of epoxy resins have been studied in view of the above-described background, and examples thereof include a sulfur atom-containing compound (for example, refer to Patent Document 2 and Patent Document 3) and a sulfur atom-containing decane coupling agent (for example, Refer to Patent Document 4). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2000-103940

[Problems to be Solved by the Invention] However, when a sulfonium coupling agent containing a sulfur atom is used (for example, refer to Patent Document 4), the effect of improving the adhesion to a noble metal such as Ag or Au is lacking, and even if the literature is When a compound containing a sulfur atom is added in an amount disclosed (for example, refer to Patent Document 2 and Patent Document 3), the adhesion to a noble metal cannot be sufficiently improved, and the reflow resistance cannot be satisfied.

In view of the above, an object of the present invention is to provide an epoxy resin composition which is excellent in reflow resistance and which does not deteriorate fluidity, and which is excellent in flame retardancy, and has an epoxy resin. An electronic component device that constitutes a component that is sealed. [Means for solving the problem]

The inventors of the present invention have conducted intensive studies in order to solve the above problems, and as a result, have found that the object can be attained by blending an epoxy resin composition having a specific epoxy resin.

<1> An epoxy resin composition comprising: an epoxy resin comprising a compound represented by the following formula (1); and a hardener comprising a phenyl aralkyl resin selected from the group consisting of a phenyl phenol aralkyl resin and a phenol aryl group At least one of the group consisting of an alkyl resin and a triphenylmethane type phenol resin; [Chemical Formula 1] [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 the formula (a), m represents a number of 0 to 20, and p represents 0.5 to 2.0, and R ₃ respectively The hydrogen atom or the monovalent hydrocarbon group having 1 to 6 carbon atoms is independently represented.

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

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

The epoxy resin composition according to 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 from 60% by mass to 95% by mass.

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

<7> The epoxy resin composition according to <6>, wherein the coupling agent comprises a decane 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>. [Effects of the Invention]

According to an aspect of the present invention, it is possible to obtain an epoxy resin composition which is excellent in reflow resistance and which does not deteriorate fluidity, and an electronic component device including an element sealed by the epoxy resin composition. .

In the present specification, the numerical range represented by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. Further, in the present specification, when a plurality of substances corresponding to the respective components are present in the composition, the content of each component in the composition means the plurality of substances present in the composition unless otherwise specified. Total content rate. In the numerical range recited in the specification, the upper limit or the lower limit described in one numerical range may be replaced with the upper or lower limit of the numerical range described in other stages. In addition, in the numerical range described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment. In the present specification, when a plurality of particles corresponding to the respective components are present in the composition, the particle diameter of each component in the composition is a mixture of the plurality of particles present in the composition, unless otherwise specified. Value.

<Epoxy Resin Composition> The epoxy resin composition according to one embodiment of the present invention contains an epoxy resin and contains a compound represented by the following formula (1) (hereinafter also referred to as "specific epoxy resin"). And a hardener comprising at least one selected from the group consisting of a bisphenylene phenol aralkyl resin, a phenol aralkyl resin, and a triphenylmethane phenol resin (hereinafter, also referred to as "specific hardener").

[Chemical 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 the formula (a), m represents a number of 0 to 20, and p represents 0.5 to 2.0, and R _{3 is} independently The ground represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

When the epoxy resin composition has such a configuration, it has good adhesion to a metal such as Cu, Ag, Au, or Pd. Therefore, it is excellent in reflow resistance and is excellent in flame retardancy without lowering fluidity. The reason is not clear, but it can be considered as follows.

By introducing a specific amount of a benzyl group into an epoxy resin which is an epoxide of a novolac type phenol resin, the interaction with the adherend becomes high, and the adhesion is improved. Further, it is considered that the moisture resistance is improved, and the occurrence of peeling of the lead frame or the like with respect to the insert due to moisture absorption of moisture is suppressed, and the adhesion can be maintained even in the case of heat reflow which is exposed to high temperature. The reflow resistance is improved. In particular, by combining a specific curing agent, the adhesion to Ag which can be used as a material of the lead frame is increased, so that the reflow resistance is improved in a comprehensive manner. Further, it is considered that the melt viscosity is lowered, the fluidity is high, and the moldability is excellent.

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

[Chemical 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 the formula (a), m represents a number of 0 to 20, and p represents 0.5 to 2.0, and R _{3 is} independently The ground represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

In the 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 is an average number (number average) of benzyl groups substituted on one benzene ring. p is from 0.5 to 2.0, preferably from 0.7 to 1.5. When p is 0.7 or more, the reflow resistance is further improved, and when p is 1.5 or less, the hardenability is further improved.

Here, p will be described. Up to three benzyl groups may be substituted on the benzene ring at both terminals in the compound represented by the formula (1). Up to two benzyl groups may be substituted on the intermediate benzene ring, so in the case where 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 the present embodiment, p in the formula (1) is from 0.5 to 2.0. Further, in the present embodiment, since p is a numerical average value, the hydrogen atom in the benzene ring in the formula (1) may not be substituted with a benzyl group.

In the 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, more preferably a hydrogen atom.

In the formula (1), R ₁ 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, more preferably a hydrogen atom or a methyl group. . Further, R ₁ may be located in any of the ortho, meta and para positions of the benzene ring, preferably in the ortho position of the benzene ring.

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

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

The melt viscosity can be measured by the following method using a rotary viscoelasticity measuring apparatus (for example, Shimadzu Corporation, product name: CFD-100D). (1) The temperature range is set to 150 ° C, (2) 0.15 g to 0.25 g of the sample is melted on the plate, and the cone is lowered, and placed until the temperature control lamp is repeated 5 times. The flashing is up. (3) The cone was stirred up and down for about 20 seconds, and then placed until the temperature control lamp was flashed five times. (4) After the cone is rotated, read the value after about 15 seconds. (5) Repeat the operations of (3) to (4) until the values become the same, and record the value. (6) Repeat the operations of (2) to (5) three times or more in the same batch, and set the average value to the viscosity.

The epoxy equivalent of the specific epoxy resin is preferably from 240 g/eq to 270 g/eq, more preferably from 255 g/eq to 270 g/eq, still more preferably from 257 g/eq to 270 g/eq. It is 259 g/eq to 270 g/eq.

The epoxy equivalent can be determined by the following method. Epoxy resin was taken into a 100 mL flask with a solid content of 3 g to 4 g, and 20 mL of acetic acid and 10 mL of tetraethylammonium bromide solution (100 g of tetraethylammonium bromide) were added. 4 ml to 5 drops of crystal violet with a mixture of 400 mL of acetic acid). The solution was titrated with a 0.1 mol/L perchloric acid acetic acid solution. The blank sample was titrated in the same manner. The epoxy equivalent is calculated by the following formula.

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

The softening point of the specific epoxy resin is preferably from 50 ° C to 80 ° C, more preferably from 55 ° C to 70 ° C, even more preferably from 56 ° C to 65 ° C from the viewpoint of moldability and reflow resistance. The softening point of a particular epoxy resin can be determined by the ring and ball method. The so-called ring and ball method means that the resin is placed in a support ring in a water bath, and a ball of 3.5 g ± 0.05 g is placed in the center of the ring, and the temperature of the bath is raised at a rate of 5 ° C ± 0.5 ° C per minute. The temperature at which the ball hangs due to the weight of the ball. Specifically, it was measured in accordance with Japanese Industrial Standards (JIS) K7234:1986.

The specific epoxy resin can be obtained by a compound containing a benzyl group corresponding to the formula (a) (hereinafter also referred to as "a compound containing a benzyl group") and a phenol corresponding to the formula (1). A 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 to the raw material benzyl group-containing compound is adjusted according to the desired value of p in the general formula (1). Therefore, it is preferred to formulate the raw material phenol novolac with respect to the benzene ring of the raw material phenol novolak resin, preferably 0.5 to 2.0, more preferably 0.7 to 1.5, of the benzyl group-containing compound. A varnish resin and a benzyl group-containing compound. Here, since the benzene ring of the raw material phenol novolak resin has one hydroxyl group, the compounding ratio of the raw material benzyl group-containing compound is preferably from 0.5 mol to 2.0 mol, relative to the hydroxyl group of 1 mol of the raw material phenol novolak resin. More preferably 0.7 to 1.5 moles.

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

The raw material phenol novolak resin may have a structure in which a part of the phenol compound is bonded to the other phenol compound by a methylene group, in addition to a structure in which a methylene group has a phenol compound having R ₁ . Examples of the other phenol compound include allylphenol, phenylphenol, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcin, catechol, and 1 - naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, and the like. A part of the compound represented by the formula (1) may contain a structural unit derived from another phenol compound, and the compound represented by the formula (1) preferably contains a source of 10% by mass or less based on all the structural units. The structural unit of the other phenol compound is more preferably contained in an amount of 5% by mass or less, and further preferably substantially not contained.

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

The acid catalyst may be appropriately selected from known inorganic acids and organic acids. Specific examples thereof 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, dimethylsulfuric acid, and diethylsulfuric acid; zinc chloride and aluminum chloride; Lewis acid such as ferric chloride or boron trifluoride; solid acid such as ion exchange resin, activated clay, ceria-alumina, or zeolite.

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. Further, 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; acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. Ketone solvent; ether solvent such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran or dioxane; aromatic compounds such as benzene, toluene, chlorobenzene or dichlorobenzene.

The reaction may be a method in which a raw material of a raw material phenol novolak resin and a raw material of a benzyl group-containing compound are directly introduced into a batch, and a reaction is carried out directly at a predetermined temperature; and a raw material phenol novolak resin and a catalyst are introduced. A method in which the reaction is carried out while maintaining a predetermined temperature and dropping a benzyl group-containing compound. At this time, the dropping time is usually from 1 hour to 10 hours, preferably not more than 5 hours. When a solvent is used after the reaction, the catalyst is removed as necessary, and the solvent is distilled off to obtain a specific phenol novolak resin.

The method of epoxidizing a specific phenol novolak resin, for example, a method of reacting a specific phenol novolak resin with epichlorohydrin; and reacting a specific phenol novolak resin with a halogenated allyl group to obtain an allyl group A method of reacting an ether compound with a peroxide.

For example, after dissolving a specific phenol novolak resin in excess epichlorohydrin, it is in the presence of an alkali metal hydroxide such as sodium hydroxide or 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 amount of the alkali metal hydroxide used at this time is preferably from 0.8 mol to 1.5 mol, more preferably from 0.9 mol to 1.2 mol, based on the hydroxyl group of 1 mol of the specific phenol novolak resin. Further, epichlorohydrin is excessively used with respect to the hydroxyl group 1 mole of the specific phenol novolak resin, and is usually 1.5 to 30 moles per mole of the hydroxyl group of the specific phenol novolak resin. It ranges from 2 moles to 15 moles. After the completion of the reaction, the excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off, whereby the target specificity can be obtained. Epoxy resin.

In addition to the specific epoxy resin, the epoxy resin composition may be used in combination with a conventionally known epoxy resin. Examples of the epoxy resin which can be used together include a phenol compound selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F, and α-naphthol, β. - at least one of a naphthol compound such as naphthol or dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde or salicylaldehyde are condensed or co-condensed under an acidic catalyst to obtain a novolak resin. A novolac type epoxy resin obtained by epoxidizing the novolak resin [for example, a phenol novolak type epoxy resin (excluding a specific epoxy resin), an o-cresol novolac type epoxy resin (excluding a 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 reaction of polybasic acid such as phthalic acid or dimer acid with epichlorohydrin; Glycidol obtained by the reaction of polyamines such as phenylmethane and iso-cyanuric acid with epichlorohydrin An amine type epoxy resin; a dicyclopentadiene type epoxy resin as an epoxide of a cocondensation resin of dicyclopentadiene and a phenol compound; a naphthalene type epoxy resin having a naphthalene ring; and a phenol aralkyl resin Epoxide phenol aralkyl type epoxy resin; extended biphenyl type epoxy resin containing a stretched phenyl skeleton; naphthol aralkyl type epoxy as an epoxide of a naphthol aralkyl resin Resin; trimethylolpropane type epoxy resin; terpene modified epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond by peracid such as peracetic acid; alicyclic epoxy resin; sulfur Atomic epoxy resin, etc. The epoxy resin which can be used in combination may be used alone or in combination of two or more.

Among them, as the epoxy resin which can be used in combination, from the viewpoints of fluidity and reflow resistance, a bisphenol F type epoxy resin, a sulfur atom-containing epoxy resin, and a phenol aralkyl type epoxy resin are preferable. From the viewpoint of hardenability, a novolac type epoxy resin (excluding a specific epoxy resin) is preferred, and from the viewpoint of low hygroscopicity, a dicyclopentadiene type epoxy resin is preferred. From the viewpoint of heat resistance and low warpage, a naphthalene type epoxy resin and a triphenylmethane type epoxy resin are preferable, and from the viewpoint of flame retardancy, a biphenyl type epoxy resin is preferred. And naphthol aralkyl type epoxy resin. From the viewpoint of improving the high-temperature placement characteristics, it is preferred to use an epoxy resin having good flame retardancy in combination to form an epoxy resin composition such as halogen-free or ruthenium-free.

Examples of the bisphenol F-type epoxy resin include an epoxy resin represented by the following formula (III), and examples of the sulfur atom-containing epoxy resin include an epoxy represented by the following formula (IV). The resin, as the phenol aralkyl type epoxy resin, for example, an epoxy resin represented by the following formula (V).

[Chemical 4]

In the 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 or a carbon number of 7 ～10 aralkyl. n is an average value and represents a number from 0 to 3. The alkyl group, the alkoxy group, the aryl group and the aralkyl group represented by R ¹ to R ⁸ may each independently have a substituent or may not.

[Chemical 5]

In the 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 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.

[Chemical 6]

In the 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 from 0 to 3. The alkyl group and the alkoxy group represented by R ¹ to R ⁵ each independently may have a substituent or may not.

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

In the sulfur atom-containing epoxy resin represented by the formula (IV), it is preferred that R ² , R ³ , R ⁶ and R ⁷ are a hydrogen atom and R ¹ , R ⁴ , R ⁵ and R ⁸ are an alkyl group. The epoxy resin is more preferably an epoxy resin in which R ² , R ³ , R ⁶ and R ⁷ are a hydrogen atom, R ¹ and R ⁸ are a third butyl group, and R ⁴ and R ⁵ are a methyl group. As such a compound, for example, YSLV-120TE (Nippon Steel & Sumitomo Chemical Co., Ltd., trade name) can be obtained as a commercial product.

As the epoxy resin represented by the formula (V), for example, NC-2000L (Nippon Chemical Co., Ltd., trade name) in which R ¹ to R ⁵ are a hydrogen atom can be obtained as a commercially available product. These epoxy resins may be used alone or in combination of two or more.

The novolac type epoxy resin is, for example, an epoxy resin represented by the following formula (VI).

[Chemistry 7]

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

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

Among the novolac type epoxy resins represented by the formula (VI), an o-cresol novolac type epoxy resin is preferred. As such a compound, EOCN-1020 (Nippon Chemical Co., Ltd., trade name) can be obtained, for example, in the form of a commercial product.

The dicyclopentadiene type epoxy resin is, for example, an epoxy resin represented by the following formula (VII).

[化8]

In the 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 of 0 to 10, and m represents an integer of 0 to 6. The hydrocarbon groups represented by R ¹ and R ² may each independently have a substituent or may not have.

As R ¹ in the formula (VII), a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a t-butyl group; a vinyl group, an allyl group, and a butenyl group are mentioned. An alkenyl group; a monovalent hydrocarbon group having 1 to 5 carbon atoms having a substituent such as a halogenated alkyl group, an amino-substituted alkyl group or a mercapto-substituted alkyl group; and an alkyl group or a hydrogen atom such as a methyl group or an ethyl group; More preferably, it is a methyl group or a hydrogen atom.

As R ² in the formula (VII), a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a t-butyl group; a vinyl group, an allyl group, and a butenyl group are mentioned. The alkenyl group; a monovalent hydrocarbon group having 1 to 5 carbon atoms having a substituent such as a halogenated alkyl group, an amino-substituted alkyl group or a mercapto-substituted alkyl group; and a hydrogen atom is preferred. As such a compound, for example, HP-7200 (Dicense Co., Ltd., trade name) can be obtained as a commercially available product.

The naphthalene type epoxy resin is, for example, an epoxy resin represented by the following formula (VIII). The triphenylmethane type epoxy resin is, for example, an epoxy resin represented by the following formula (IX).

[Chemistry 9]

In the formula (VIII), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. p is an average value, and represents a number of 0 to 2, and l and m are average values, and each independently represents a number of 0 to 11, and (l+m) is a number of 1 to 11 and (l+p) becomes 1 to Choose the number of 12 ways. 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 each independently have a substituent or may not.

The naphthalene type epoxy resin represented by the formula (VIII) includes a random copolymer containing one structural unit and m constituent units randomly, and alternately including one constituent unit and m constituent units. The copolymer includes a copolymer having one constituent unit and m constituent units in a regular manner, and a block copolymer including one constituent unit and m constituent units in a block form, and any of these may be used alone. Two or more types may 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 Chemical Co., Ltd., trade name) can be obtained as a commercially available product.

[化10]

In the formula (IX), R 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 of 0 to 10. The hydrocarbon groups represented by R may each independently have a substituent or may not have. As the compound in which R is a hydrogen atom, for example, E-1032 (Mitsubishi Chemical Co., Ltd., trade name) can be obtained as a commercially available product.

The epoxy resin represented by the following general formula (X) is exemplified as the extended biphenyl type epoxy resin. The naphthol aralkyl type epoxy resin is, for example, an epoxy resin represented by the following formula (XI).

[11]

In the formula (X), R ¹ to R ⁹ each independently represent a hydrogen atom; 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; Alkoxy group having 1 to 10 carbon atoms such as a group, an ethoxy group, a propoxy group or a butoxy group; an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; or a benzyl group or a phenethyl group; The aralkyl group having 7 to 10 carbon atoms 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, the alkoxy group, the aryl group and the aralkyl group represented by R ¹ to R ⁹ each independently may have a substituent or may not.

[化12]

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

As the phenylene type epoxy resin, for example, NC-3000 (Nippon Chemical Co., Ltd., trade name) can be obtained as a commercially available product. In addition, as a naphthol aralkyl type epoxy resin, for example, ESN-175 (Nippon Steel & Metal Co., Ltd., trade name) can be obtained as a commercial product. The phenylene type epoxy resin may be used singly or in combination of two or more.

Further, as the epoxy resin, an epoxy resin represented by the following formula (XII) can also be used.

[Chemistry 13]

R ¹ in the formula (XII) each independently represents a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and n is an average value and represents a number of 0 to 4. Further, R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 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 each independently may have a substituent or may not have. Among them, from the viewpoint of flame retardancy and moldability, an epoxy resin having n and m is preferably used. As such a compound, for example, YX-8800 (Mitsubishi Chemical Co., Ltd., trade name) can be obtained.

The content of the specific epoxy resin relative 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.

(hardener) The epoxy resin composition contains a hardener. The hardener contains at least one selected from the group consisting of a bisphenylene phenol aralkyl resin, a phenol aralkyl resin, and a triphenylmethane phenol resin.

The extended biphenyl type phenol aralkyl resin represented by the following formula (XVII) is preferred.

[Chemistry 14]

Here, R ¹ to R ⁹ each independently represent a hydrogen atom; 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; a methoxy group and an ethoxy group; Alkoxy group having 1 to 10 carbon atoms such as a group, a propoxy group or a butoxy group; an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; or a carbon number of 7 or 10 such as a benzyl group or a phenethyl group; 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, the alkoxy group, the aryl group or the aralkyl group represented by R ¹ to R ⁹ may each independently have a substituent or may not.

The exophenylene type phenol aralkyl resin represented by the formula (XVII) is, for example, a compound in which all of R ¹ to R ⁹ are a hydrogen atom, and it is preferable to contain 50 mass from the viewpoint of melt viscosity. A mixture of condensate of % or more of n or more is a mixture of condensates. As such a compound, for example, MEH-7851 (Mingwa Chemical Co., Ltd., trade name) can be obtained as a commercially available product. In the case of using the extended biphenyl phenol aralkyl resin, the content thereof is preferably 30% by mass or more, and more preferably 50% by mass or more based on the total amount of the curing agent.

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

[化15]

In the general formula (XIII), R 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 of 0 to 10. The hydrocarbon groups represented by R may each independently have a substituent or may not have.

Among the compounds represented by the 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. Specific examples thereof include a p-xylylene phenol aralkyl resin and an exo-dimethylphenyl phenol aralkyl resin. As such a compound, for example, XLC (Mitsui Chemical Co., Ltd., trade name) can be obtained as a commercially available product. In the case of using the phenol aralkyl resin, the content of the phenol aralkyl resin is preferably 30% by mass or more, and more preferably 50% by mass or more based on the total amount of the curing agent.

From the viewpoint of reducing warpage, a triphenylmethane type phenol resin is preferred. The phenol resin represented by the following general formula (XVI) is exemplified as the triphenylmethane type phenol resin.

[Chemistry 16]

In the 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 of 0 to 10. The hydrocarbon groups represented by R may each independently have a substituent or may not have. As the compound in which R is a hydrogen atom, for example, MEH-7500 (Mingwa Chemical Co., Ltd., trade name) can be obtained as a commercially available product. In the case of using the triphenylmethane type phenol resin, the content thereof is preferably 30% by mass or more, and more preferably 50% by mass or more based on the total amount of the curing agent.

The specific hardener may be used singly or in combination of two or more. Further, in addition to the specific curing agent, the curing agent may be used in combination with other curing agents. The content of the specific curing agent in all of the 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.

Examples of the other curing agent include a novolak type phenol resin, a naphthol aralkyl resin, a dicyclopentadiene type phenol resin, a terpene modified phenol resin, a p-xylylene modified phenol resin, and an exomethyl phenyl group. A modified phenol resin, a melamine-modified phenol resin, a cyclopentadiene-modified phenol resin, and a phenol resin obtained by copolymerizing two or more of these.

Examples of the novolac type phenol resin include a phenol novolak resin, a cresol novolak resin, and a naphthol novolak resin. Among them, a phenol novolak resin is preferable.

The naphthol aralkyl resin may, for example, be a phenol resin represented by the following formula (XIV).

[化17]

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

Examples of the naphthol aralkyl resin represented by the formula (XIV) include a compound in which all of R ¹ and R ² are a hydrogen atom, and as such a compound, for example, SN-170 can be obtained as a commercially available product (New Day) Tiezhujin Chemical Co., Ltd., trade name).

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

[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 of 0 to 10, and m represents an integer of 0 to 6. The hydrocarbon groups 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 a hydrogen atom, for example, DPP (Nippon Petrochemical Co., Ltd., trade name) can be obtained as a commercially available product.

The other hardener may be used alone or in combination of two or more. Among the other curing agents to be used together, a novolac type phenol resin is preferred from the viewpoint of hardenability.

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

The method for measuring the hydroxyl equivalent in the hardener is as follows. The hydroxy group of the hardener is chlorinated in a pyridine solution by pyridine-acetonitrile method, and the excess reagent is decomposed by water, and the produced acetic acid is titrated with a solution containing potassium hydroxide and ethanol. Thus, the hydroxyl equivalent is determined.

The equivalent ratio of the epoxy resin to the 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 suppress the amount of each unreacted component, it is preferably set in the range of 0.5 to 2, and more preferably in the range of 0.6 to 1.3. In order to obtain an epoxy resin composition excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

(Curing accelerator) From the viewpoint of promoting the reaction between the epoxy resin and the curing agent, a curing accelerator may be used as needed in the epoxy resin composition. The hardening accelerator can be used for a general user in an epoxy resin composition without any particular limitation. Examples of the hardening accelerator include 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-di a cycloamidine compound of butylamino-1,8-diaza-bicyclo[5.4.0]undecene-7; addition of maleic anhydride, 1,4-benzoquinone to a cyclic oxime compound, 2,5-toluene, 1,4-naphthoquinone, 2,3-dimethylphenylhydrazine, 2,6-dimethylphenylhydrazine, 2,3-dimethoxy-5-methyl-1, a quinone compound such as 4-phenylhydrazine, 2,3-dimethoxy-1,4-benzoquinone or phenyl-1,4-benzoquinone, a compound having a p bond such as diazophenylmethane or a phenol resin. a compound having an intramolecular polarization; a tertiary amine compound such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; a derivative of a tertiary amine compound; Imidazole compound such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; derivative of imidazole compound; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, three a phosphine compound such as (4-methylphenyl)phosphine, diphenylphosphine or phenylphosphine; addition of maleic anhydride, the anthraquinone compound, diazophenyl group to the phosphine compound a phosphorus compound having an intramolecular polarization formed by a compound having a p bond such as a phenol resin; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole a tetraphenylborate such as tetraphenylborate or N-methylmorpholinetetraphenylborate; a derivative of tetraphenylborate or the like. The hardening accelerator may be used alone or in combination of two or more.

Among them, from the viewpoint of flame retardancy, hardenability, fluidity, and mold release property, an addition product of a tertiary phosphine compound and a ruthenium compound is preferable as the hardening accelerator.

The tertiary phosphine compound is not particularly limited, and examples thereof include tricyclohexylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, and triphenylphosphine. Tris(4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(isopropylbenzene) Phosphine, tris(t-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) a tertiary phosphine compound having an alkyl group or an aryl group such as a phosphine.

Examples of the ruthenium compound include o-benzoquinone, p-benzoquinone, biphenyl fluorene, 1,4-naphthoquinone, anthracene, and the like. Among them, as the hydrazine compound, p-benzoquinone is preferred from the viewpoint of moisture resistance and storage stability.

The hardening accelerator is preferably an adduct of triphenylphosphine and p-benzoquinone from the viewpoint of reflow resistance, and is preferably tris(4-methylbenzene) from the viewpoint of mold releasability. Addition of phosphine to p-benzoquinone.

The content rate of the hardening accelerator is not particularly limited as long as it is an amount capable of achieving a hardening promoting effect. When the epoxy resin composition contains a curing accelerator, the content of the curing accelerator is preferably from 0.005% by mass to 2% by mass, more preferably from 0.01% by mass to 0.5% by mass, based on the epoxy resin composition. When it is 0.005% by mass or more, the curing property tends to be improved, and when it is 2% by mass or less, the pot life tends to be improved.

(Inorganic Filler) The epoxy resin composition may further contain an inorganic filler. When an inorganic filler is contained, there is a tendency to reduce hygroscopicity, reduce the coefficient of linear expansion, improve thermal conductivity, and increase strength. Examples of the inorganic filler include molten cerium oxide, crystalline cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, potassium titanate, strontium carbide, tantalum nitride, aluminum nitride, and boron nitride. Powders such as cerium oxide, zirconium oxide, zircon, forsterite, talat, spinel, mullite, and titanium oxide, such spheroidized beads, glass Fiber, etc. Further, examples of the inorganic filler having a flame retarding effect include aluminum hydroxide, magnesium hydroxide, a composite metal hydroxide, zinc borate, and zinc molybdate. Here, as zinc borate, FB-290, FB-500 (US Borax Company, FRZ-500C (Yaezawa Chemical Industry Co., Ltd.), etc., as zinc molybdate can be obtained as a commercial product, respectively. KEMGARD 911B, KEMGARD 911C, KEMGARD 1100 (Sherwin-Williams), respectively, in the form of commercial products )Wait.

These inorganic fillers may be used alone or in combination of two or more. Among them, from the viewpoint of the filling property and the reduction of the coefficient of linear expansion, molten cerium oxide is preferred, and from the viewpoint of high thermal conductivity, alumina is preferred. The shape of the inorganic filler is preferably spherical in view of the filling property and the mold wearability.

The average particle diameter of the inorganic filler is preferably from 1 μm to 50 μm, more preferably from 10 μm to 30 μm. When the average particle diameter is 1 μm or more, the increase in the viscosity of the epoxy resin composition tends to be suppressed, and when the average particle diameter is 50 μm or less, preferably 30 μm or less, the filling property in the narrow gap is obtained. The tendency to improve. The average particle diameter of the inorganic filler is measured by a laser scattering diffraction particle size distribution measuring apparatus in the form of a volume average particle diameter.

The inorganic filler preferably has a specific surface area of from 1 m ² /g to 5 m ² /g, more preferably from 2 m ² /g to 4 m ² /g, from the viewpoint of flame retardancy and fluidity.

In the case where the epoxy resin composition contains an inorganic filler, the inorganic filler is used in terms of fluidity, flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient, improvement in strength, and reflow resistance. The content of the epoxy resin composition is preferably 50% by mass or more, and more preferably 60% by mass to 95% by mass, and still more preferably 70% by mass to 90% by mass, from the viewpoint of flame retardancy. . When the content of the inorganic filler is 50% by mass or more, the fluidity tends to be improved, and when it is 95% by mass or less, the flame retardancy and the reflow resistance tend to be improved.

(Coupling Agent) The epoxy resin composition may further contain a coupling agent. When an inorganic filler is used for the epoxy resin composition, the coupling agent tends to improve the adhesion between the resin component and the inorganic filler. As the coupling agent, it can be used for a general user in an epoxy resin composition without any particular limitation. Examples of the coupling agent include a decane compound having a primary amino group, a secondary amino group or a tertiary amino group, various decane compounds such as epoxy decane, decyl decane, alkyl decane, ureido decane, and vinyl decane, and titanium. A compound, an aluminum chelate compound, a compound containing aluminum and zirconium, and the like.

If a coupling agent is exemplified, vinyl trichloromethane, vinyl triethoxy decane, vinyl tris (β-methoxyethoxy) decane, γ-methyl propylene methoxy propyl trimethoxide Baseline, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldimethoxy Decane, vinyltriethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-amine Propyltriethoxydecane, γ-aminopropylmethyldiethoxydecane, γ-anilinopropyltrimethoxydecane, γ-anilinopropyltriethoxydecane, γ-(N, N-dimethyl)aminopropyltrimethoxydecane, γ-(N,N-diethyl)aminopropyltrimethoxydecane, γ-(N,N-dibutyl)aminopropyl Trimethoxydecane, γ-(N-methyl)anilinopropyltrimethoxydecane, γ-(N-ethyl)anilinopropyltrimethoxydecane, γ-(N,N-dimethyl) Aminopropyltriethoxydecane, γ-(N,N-diethyl)aminopropyltriethoxydecane, γ- (N,N-dibutyl)aminopropyltriethoxydecane, γ-(N-methyl)anilinopropyltriethoxydecane, γ-(N-ethyl)anilinopropyltri Ethoxy decane, γ-(N,N-dimethyl)aminopropylmethyldimethoxydecane, γ-(N,N-diethyl)aminopropylmethyldimethoxydecane , γ-(N,N-dibutyl)aminopropylmethyldimethoxydecane, γ-(N-methyl)anilinopropylmethyldimethoxydecane, γ-(N-B Anilinopropylmethyldimethoxydecane, N-(trimethoxydecylpropyl)ethylenediamine, N-(dimethoxymethyldecylisopropyl)ethylenediamine, methyl Trimethoxydecane, dimethyldimethoxydecane, methyltriethoxydecane, γ-chloropropyltrimethoxydecane, hexamethyldioxane, vinyltrimethoxydecane, γ-mercaptopropyl a decane coupling agent such as methyl dimethoxy decane; isopropyl triisostearyl decyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N-amino group) Ethyl-aminoethyl) titanate, tetraoctyl bis(di-tridecyl phosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl ) double (two-thirteen) Phosphite) titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)exidine ethyl titanate, isopropyltrioctylphosphonium titanate Ester, isostearyl methacrylate, isopropyl tri-dodecyl benzene sulfonate titanate, isopropyl isostearyl bis acrylate diacrylate, iso A titanate coupling agent such as propyl tris(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate or tetraisopropylbis(dioctylphosphite) titanate. As the coupling agent, one of these may be used alone or two or more kinds may be used in combination.

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

Examples of the decane coupling agent having a secondary amine group include γ-anilinopropyltrimethoxydecane, γ-anilinopropyltriethoxydecane, and γ-anilinopropylmethyldimethoxydecane. , γ-anilinopropylmethyldiethoxydecane, γ-anilinopropylethyldiethoxydecane, γ-anilinopropylethyldimethoxydecane, γ-anilinomethyltrimethyl Oxaloxane, γ-anilinomethyltriethoxydecane, γ-anilinomethylmethyldimethoxydecane, γ-anilinomethylmethyldiethoxydecane, γ-anilinomethyl Ethyldiethoxydecane, γ-anilinomethylethyldimethoxydecane, N-(p-methoxyphenyl)-γ-aminopropyltrimethoxydecane, N-(p-methoxy Phenyl)-γ-aminopropyltriethoxydecane, N-(p-methoxyphenyl)-γ-aminopropylmethyldimethoxydecane, N-(p-methoxybenzene) -γ-aminopropylmethyldiethoxydecane, N-(p-methoxyphenyl)-γ-aminopropylethyldiethoxydecane, N-(p-methoxybenzene) -γ-aminopropylethyldimethoxydecane, γ-(N-methyl)aminopropyltrimethoxydecane, γ- (N-ethyl)aminopropyltrimethoxydecane, γ-(N-butyl)aminopropyltrimethoxydecane, γ-(N-benzyl)aminopropyltrimethoxydecane, γ -(N-methyl)aminopropyltriethoxydecane, γ-(N-ethyl)aminopropyltriethoxydecane, γ-(N-butyl)aminopropyltriethoxy Baseline, γ-(N-benzyl)aminopropyltriethoxydecane, γ-(N-methyl)aminopropylmethyldimethoxydecane, γ-(N-ethyl)amine Propylmethyldimethoxydecane, γ-(N-butyl)aminopropylmethyldimethoxydecane, γ-(N-benzyl)aminopropylmethyldimethoxydecane , N-β-(Aminoethyl)-γ-aminopropyltrimethoxydecane, γ-(β-aminoethyl)aminopropyltrimethoxydecane, N-β-(N-ethylene Alkylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane, and the like.

When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably from 0.037% by mass to 5% by mass, more preferably from 0.05% by mass to 4.75% by mass, based on the epoxy resin composition, and further It is preferably from 0.1% by mass to 2.5% by mass. When it is 0.037 mass% or more, the adhesion to the frame is improved, and when it is 5% by mass or less, the hardenability is improved.

(Flame Retardant) The epoxy resin composition may further contain a conventionally known flame retardant from the viewpoint of improving flame retardancy, and in particular, it may contain halogen-free as needed in view of environmental and reliability. And flawless flame retardant. Examples of the flame retardant include inorganic compounds such as red phosphorus, phosphoric acid esters, and zinc oxide. The resin such as red phosphorus or phosphine oxide coated with a thermosetting resin such as a phenol resin is coated with a phosphorus compound, and melamine, a melamine derivative, and a melamine are modified. a phenol resin, a compound having a triazine ring, a nitrogen-containing compound such as a cyanuric acid derivative or an isocyanuric acid derivative, a phosphorus-containing or nitrogen-containing compound such as a cyclophosphazene, aluminum hydroxide, magnesium hydroxide, or a composite metal hydroxide A compound containing a metal element such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate or dicyclopentadienyl iron. One type of the flame retardant may be used alone or two or more types may be used in combination.

(Polymer-Containing Polymer) The epoxy resin composition may also contain a ruthenium-containing polymer from the viewpoint of reducing warpage. The ruthenium-containing polymer preferably has the following bond (c) and bond (d) and the terminal is a group selected from the group consisting of R ¹ , a hydroxyl group and an alkoxy group and has an epoxy equivalent of 500 g. /eq ~ 4000 g / eq of the compound. As the ruthenium-containing polymer, for example, a branched polyoxane called an fluorenone resin can be mentioned.

[Chemistry 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 the bond (c) and the bond (d) include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group. An alkyl group such as octyl or 2-ethylhexyl; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group; a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group; An aryl group; an aralkyl group such as a benzyl group or a phenethyl group; and the like, and a methyl group or a phenyl group is preferred.

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 the epoxy group is preferably bonded to the terminal of the organic group.

Specifically, examples of X include 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3- Glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, etc., wherein It is preferably 3-glycidoxypropyl.

Further, from the viewpoint of storage stability of the polymer, it is preferred that the terminal of the ruthenium-containing polymer is independently R ¹ or alkoxy. Examples of the alkoxy group as the terminal include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

In the case where the ruthenium-containing polymer has an epoxy group, the epoxy equivalent is preferably in the range of from 500 g/eq to 4000 g/eq, more preferably from 1000 g/eq to 2500 g/eq. When the epoxy equivalent of the ruthenium-containing polymer is 500 g/eq or more, the fluidity of the epoxy resin composition tends to be improved, and when it is 4000 g/eq or less, the cured product is prevented from oozing out to The surface is formed with a tendency to reduce the formation failure.

When the epoxy resin composition contains a ruthenium-containing polymer, the content of the ruthenium-containing polymer is preferably 0.2% by mass to 1.5% by mass, more preferably 0.3% by mass to the epoxy resin composition. 1.3% by mass. When the amount is 0.2% by mass or more, the effect of reducing the amount of warpage 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 may optionally contain a compound selected from the following composition formula (XXXIII) and the following composition, from the viewpoint of improving the moisture resistance and high-temperature placement characteristics of a semiconductor element such as an IC. At least one of the group consisting of the compounds represented by formula (XXXIV).

[Chemistry 20] (0<x≦0.5, m is a positive number)

[Chem. 21] (0.9≦x≦1.1, 0.6≦y≦0.8, 0.2≦z≦0.4)

Further, the compound of the formula (XXXIII) can be obtained as a commercial product in the form of a commercial product name DHT-4A of Kyowa Chemical Industry Co., Ltd. Further, the compound of the formula (XXXIV) can be obtained as a commercial product of the East Asia Synthetic Co., Ltd. under the trade name of IXE500. In addition, other anion exchangers may be added as needed. The anion exchanger is not particularly limited, and a conventionally known one may be used, and examples thereof include hydroxides containing elements such as magnesium, aluminum, titanium, zirconium, and hafnium. As the anion exchanger, one type of these may be used alone or two or more types may be used in combination.

Further, in the epoxy resin composition, a high-fat fatty acid, a higher fatty acid metal salt, an ester wax, a polyolefin wax, a polyethylene, an oxidized polyethylene, or the like, a coloring agent such as carbon black, an eucalyptus oil, and an anthraquinone may be contained as needed. A stress relieving agent such as a gum powder or the like is used as another additive.

<Method for Preparing Epoxy Resin Composition> The epoxy resin composition can be prepared by any method as long as it can uniformly disperse and mix various raw materials. As a general preparation method, a predetermined mixing amount of a raw material is sufficiently mixed by a mixer or the like, and then mixed, melted and kneaded by a mixing roll, an extruder, a kneader, a planetary mixer, or the like, and cooled. A method of defoaming and pulverizing as needed. Further, the epoxy resin composition may be ingotd in a size and quality in accordance with the molding conditions as needed.

<Electronic Part 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. The method of sealing the element using the epoxy resin composition of the present embodiment as a sealing material is usually a low-pressure transfer molding method, and examples thereof include an injection molding method and a compression molding method. As a method of imparting the epoxy resin composition, a dispensing method, a casting method, a printing method, or the like can be used.

The electronic component device of the present embodiment including the element sealed by the epoxy resin composition of the present embodiment includes a lead frame, a tape carrier, a wiring board, a glass, a silicon wafer, and the like, and a mounting member. An active component such as a semiconductor wafer, a transistor, a diode, or a thyristor, or a passive component such as a capacitor, a resistor, or a coil, and the like, and an electronic component obtained by sealing a desired portion with the epoxy resin composition of the present embodiment is mounted on a substrate or the like. Device, etc.

Here, the mounting substrate is not particularly limited, and examples thereof include an interposer substrate such as an organic substrate, an organic film, a ceramic substrate, and a glass substrate, a glass substrate for liquid crystal, and a substrate for a multi-chip module (MCM). A substrate for IC or the like is mixed.

Examples of the electronic component device including such a device include a semiconductor device, and specifically, an element such as a semiconductor wafer is fixed to a lead frame (island or tab), and components such as bonding pads are used. After the terminal portion and the lead portion are connected by wire bonding or bumping, a double in-line package (DIP) or plastic which is sealed by transfer molding or the like using the epoxy resin composition of the present embodiment is used. Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package (SOP), Small Outline J-lead Package (SOJ) a resin-sealed IC such as a Thin Small Outline Package (TSOP) or a Thin Quad Flat Package (TQFP); the epoxy resin composition of the present embodiment is used for wire bonding to a tape carrier Tape carrier package (TCP) sealed by a semiconductor wafer; using the epoxy resin composition of the present embodiment Chip On Board (COB) and Chip On Glass (Chip On Glass) obtained by sealing a semiconductor wafer obtained by bonding a wiring such as wire bonding, flip chip bonding, or solder to a wiring board or a glass. A semiconductor device in which a bare wafer is mounted, such as COG), and a semiconductor wafer in which an epoxy resin composition of the present embodiment is bonded to a wiring board or a glass by wire bonding, flip chip bonding, solder, or the like. a hybrid IC such as an active component such as a transistor, a diode, or a thyristor, or a passive component such as a capacitor, a resistor, or a coil; and a terminal for forming a multi-chip module (MCM) motherboard connection The semiconductor wafer is mounted on the interposer substrate, and the semiconductor wafer is connected to the wiring formed on the interposer substrate by bumping or wire bonding, and then the semiconductor wafer mounting side is sealed by the epoxy resin composition of the present embodiment. Ball Grid Array (BAG), Chip Size Package (CSP), Multi Chip Package (Multi Chip Package) , MCP) and so on. Further, the semiconductor devices may be stacked (laminated) packages in which two or more elements are mounted on a mounting substrate in an overlapping manner, or two or more devices may be sealed at one time by using an epoxy resin composition. Batch module package. [Examples]

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

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

[Table 1]

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

(epoxy resin) × epoxy resin 1: epoxy equivalent 240 g/eq, softening point 55 ° C, compound represented by the formula (1), epoxy resin of p = 0.6 × epoxy resin 2: epoxy equivalent 263 g/eq, softening point: 58 ° C, compound represented by the formula (1), epoxy resin of p = 0.9 × epoxy resin 3: epoxy equivalent: 264 g/eq, softening point: 60 ° C, general formula (1) ) the compound represented, epoxy resin of p = 1.0 × epoxy resin 4: epoxy equivalent 265 g / eq, softening point 61 ° C, compound represented by the formula (1), epoxy resin of p = 1.1 × Epoxy resin 5: Epoxy equivalent 251 g/eq, softening point 60 ° C, copolymer of 2-methoxynaphthalene and o-cresol novolak-type epoxy resin (Di Ai Sheng (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 (Di Ai Sheng (DIC) Co., Ltd., trade name N-500P-1)

(hardener) × hardener 1: phenol aralkyl resin having a hydroxyl group equivalent of 175 g/eq and a softening point of 70 ° C (Mingwa Chemical Co., Ltd., trade name MEH-7800SS) × hardener 2: hydroxyl equivalent 106 g/eq , a 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) × epoxy decane: γ-glycidoxypropyl trimethoxy decane

(Inorganic filler) × Spherical molten cerium oxide: average particle diameter 14.5 μm, specific surface area 2.8 m ² /g

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

[Table 2]

[table 3]

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

(1) Spiral flow (indicator of fluidity) The epoxy resin composition was applied to a mold temperature of 180 ° C, a molding pressure of 6.9 MPa, and a hardening time of 90 seconds using a mold for spiral flow measurement according to EMMI-1-66. Formed under the conditions and the flow distance (cm) is obtained.

(2) Hardness at the time of heat The epoxy resin composition was formed into a circular plate having a diameter of 50 mm × a thickness of 3 mm under the molding conditions of the above (1), and was measured immediately after molding using a Shore D type hardness tester. .

(3) Flame retardancy The epoxy resin composition was molded under the molding conditions of the above (1) using a mold of a test piece having a thickness of 1/32 吋 (0.8 mm), and further, at 180 ° C. After hours of hardening, the flame retardancy was evaluated in accordance with the UL-94 test method.

(4) Reflow-resistant (4.1) Cu lead frame for 80-pin flat package (QFP) of 20 mm × 14 mm × 2 mm with 8 mm × 10 mm × 0.4 mm tantalum wafer (Lead frame material: copper alloy, treated product of silver plating on the upper surface of the wafer pad portion and the leading end of the lead), and formed by using the epoxy resin composition under the conditions of the above (3), and then hardening, at 85 ° C The mixture was humidified under conditions of 85% RH, and subjected to reflow treatment at 240 ° C for 10 seconds for a predetermined period of time to visually observe the presence or absence of cracks, and to produce a package with respect to the number of test packages (5). The number is evaluated.

(4.2) PPF lead frame The evaluation was carried out in the same manner as in (4.1) except that PPF (core material: copper alloy, treated with three layers of Ni/Pd/Au) was used for the lead frame.

(5) Moisture resistance The test size of a 6 mm × 6 mm × 0.4 mm test crucible wafer of 20 mm × 6 mm × 0.4 mm with a wire width of 10 μm and a thickness of 1 μm was applied to a 5 μm thick tantalum oxide film. ×40 mm × 2.7 mm 80-pin flat package (four-sided flat package (QFP)), which is formed by forming an epoxy resin composition under the conditions of (3) and hardening it, and pre-treating it. Wet, and the number of defective packages caused by the corrosion of the aluminum wiring was investigated for a predetermined period of time, and the number of defective packages was evaluated with respect to the number of test packages (10).

Further, the pretreatment was performed by humidifying the flat package at 85 ° C, 85% RH, and 72 hours, and then performing a vapor phase reflow treatment at 215 ° C for 90 seconds. Subsequent humidification was carried out under the conditions of 0.2 MPa and 121 °C.

(6) High-temperature placement characteristics Using a silver paste, a 5 mm × 9 mm × 0.4 mm test crucible wafer having a line width of 10 μm and a thickness of 1 μm was applied to a 5 μm thick yttrium oxide film. A 16-pin type dual in-line type for connecting a bonding pad of a wafer to an inner lead at 200 ° C by a thermosonic wire bonding device on a partially silver plated 42 alloy lead frame A package (Dual Inline Package, DIP) is produced by molding and post-hardening under the conditions of the above (3), and is stored in a high-temperature tank at 200 ° C, and taken out and turned on after a predetermined period of time. In the test, the high-temperature placement characteristics were evaluated with respect to the number of poorly-sealed packages of the number of test packages (10).

[Table 4]

[table 5]

In Comparative Example 5 and Comparative Example 7 which did not contain the compound represented by the formula (1), the heat resistance was low, and thus the moldability was inferior. In Comparative Example 6 and Comparative Example 8, the reflow resistance was poor, and the flame retardancy did not reach V-0. No specific curing agent was used. In Comparative Examples 1 to 4, compared with Examples 1 to 4, the spiral flow was small and the formability was poor. Further, the reflow resistance (especially 72 h and 96 h) in the Cu lead frame of Comparative Examples 1 to 4 which did not use a specific curing agent as compared with Examples 1 to 4 using a specific curing agent Also slightly worse.

On the other hand, in Examples 1 to 4 containing the compound represented by the formula (1), the fluidity and the reflow resistance were good, and all of them reached UL-94 V-0, and the flame retardancy was good and the moldability was also improved. good.

The disclosure of Japanese Patent Application No. 2016-091768, filed on Apr. 28,,,,,,,,, All documents, patent applications, and technical specifications described in the specification are incorporated herein by reference to the same extent as in the In the manual.

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Claims (8)

An epoxy resin composition comprising: an epoxy resin comprising a compound represented by the following formula (1); and a hardener comprising a phenylarylene resin selected from the group consisting of a phenyl phenol aralkyl resin and a phenol aralkyl resin And at least one of the group consisting of triphenylmethane type phenol resins; [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 the formula (a), m represents a number of 0 to 20, and p represents 0.5 to 2.0, and R ₃ respectively The hydrogen atom or the monovalent hydrocarbon group having 1 to 6 carbon atoms is independently represented. The epoxy resin composition according to claim 1, which further contains a curing accelerator. The epoxy resin composition according to claim 2, wherein the hardening accelerator comprises an adduct of a tertiary phosphine compound and a hydrazine 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 Item 4, wherein the content of the inorganic filler is from 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 decane coupling agent having a secondary amine group. An electronic component device comprising: an element; and a cured product of the epoxy resin composition according to any one of claims 1 to 7 of the present invention.