CN109071780B

CN109071780B - Epoxy resin composition and electronic component device

Info

Publication number: CN109071780B
Application number: CN201780026111.1A
Authority: CN
Inventors: 石黑正; 马场彻
Original assignee: Showa Denko KK
Current assignee: Lishennoco Co ltd
Priority date: 2016-04-28
Filing date: 2017-04-28
Publication date: 2022-04-08
Anticipated expiration: 2037-04-28
Also published as: JPWO2017188455A1; KR20180136494A; CN109071780A; MY196654A; KR102127589B1; PH12018502283A1; TWI724162B; WO2017188455A1; JP7343978B2; TW201807057A; SG11201809513UA

Abstract

An epoxy resin composition comprising: an epoxy resin containing a compound represented by the following general formula (1); and a curing agent containing at least 1 selected from the group consisting of a biphenylene type phenol aralkyl resin, a phenol aralkyl resin, and a triphenylmethane type phenol resin. R₁Each independently represents a hydrogen atom or a C1-6 monovalent hydrocarbon group, R₂Represents a substituent represented by the formula (a), m represents a number of 0 to 20, p represents 0.5 to 2.0, R₃Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

Description

Epoxy resin composition and electronic component device

Technical Field

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

Background

In recent years, high-density mounting of semiconductor elements has been advanced. Accordingly, the mainstream of the resin-sealed semiconductor device has shifted 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 mount ics (integrated circuits), lsis (large Scale integration), and the like are thin and small packages. Therefore, the area occupied by the element with respect to the package becomes large, and the thickness of the package becomes very thin.

The mounting method of these packages is different from the mounting method of the conventional pin insertion type package. That is, the pin insertion type package is soldered from the rear surface of the wiring board after the pins are inserted into the wiring board, and thus the package is not directly exposed to high temperature. However, since the surface-mount IC is temporarily fixed to the surface of the wiring board and then treated with a solder bath, a reflow apparatus, or the like, it is directly exposed to a soldering temperature (reflow temperature). The result is: when the package absorbs moisture, the moisture absorbed evaporates during reflow, and the generated vapor pressure acts as a peeling stress, so that the interposer such as an element or a lead frame is peeled from the sealing material, which causes package cracks and electrical property defects. Therefore, development of a sealing material having excellent solder heat resistance (reflow resistance) has been desired.

As the sealing material, in addition to low moisture absorption, improvement of adhesion or adhesiveness to a lead frame (Cu, Ag, Au, Pd, etc., as a material), a dissimilar material such as a chip interface, and the like is strongly required. In order to meet these demands, various studies have been made on epoxy resins as main materials, and for example, a method using biphenyl type epoxy resins has been studied (for example, see patent document 1). In addition, various modifiers for epoxy resins have been studied based on the above background, and examples thereof include sulfur atom-containing compounds (see, for example, patent documents 2 and 3) and sulfur atom-containing silane coupling agents (see, for example, patent document 4).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. S64-65116

Patent document 2: japanese patent laid-open publication No. 11-12442

Patent document 3: japanese laid-open patent publication No. 2002-3704

Patent document 4: japanese patent laid-open publication No. 2000-103940

Disclosure of Invention

Problems to be solved by the invention

However, when a silane coupling agent containing a sulfur atom is used (for example, see patent document 4), the effect of improving the adhesion to a noble metal such as Ag or Au is insufficient, and even when a sulfur atom-containing compound is added in an amount disclosed in the literature (for example, see patent documents 2 and 3), the adhesion to the noble metal cannot be sufficiently improved, and the reflow resistance cannot be satisfied in any case.

One aspect of the present invention is an invention made in view of the above situation, and it is intended to provide: an epoxy resin composition having excellent reflow resistance and good flame retardancy without lowering fluidity, and an electronic component device provided with an element sealed with the epoxy resin composition.

Means for solving the problems

The present inventors have made extensive studies to solve the above problems, and as a result, have found that the above object can be achieved by an epoxy resin composition containing a specific epoxy resin.

< 1 > an epoxy resin composition comprising:

an epoxy resin containing a compound represented by the following general formula (1); and

the curing agent contains at least 1 selected from the biphenyl idene type phenol aralkyl resin, phenol aralkyl resin and triphenyl methane type phenolic resin (Japanese: フェノール colophony).

[ solution 1]

〔R₁Each independently represents a hydrogen atom or a C1-6 monovalent hydrocarbon group, R₂Represents a substituent represented by the formula (a), m represents a number of 0 to 20, p represents 0.5 to 2.0, R₃Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Angle (c)

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

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

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

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

< 6 > the epoxy resin composition according to any one of < 1 > to < 5 >, which further comprises a coupling agent.

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

< 8 > an electronic component device comprising:

element, and

a cured product of the epoxy resin composition as described in any one of < 1 > -to < 7 > for sealing the element.

Effects of the invention

According to one aspect of the present invention, an epoxy resin composition having excellent reflow resistance and good flame retardancy without lowering fluidity, and an electronic component device including an element sealed with the epoxy resin composition can be obtained.

Detailed Description

In the present specification, the numerical range indicated by "to" represents a range including numerical values described before and after "to" as a minimum value and a maximum value, respectively.

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

In the numerical ranges recited in the present specification, the upper limit or the lower limit recited in one numerical range may be replaced with the upper limit or the lower limit recited in another numerical range recited in a stepwise manner. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.

In the present specification, when a plurality of types of particles belonging to each component are present in a composition, the particle diameter of each component in the composition refers to a value related to a mixture of the plurality of types of particles present in the composition unless otherwise specified.

< epoxy resin composition >

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

[ solution 2]

R₁Each independently represents a hydrogen atom or a C1-6 monovalent hydrocarbon group, R₂Represents a substituent represented by the formula (a), m represents a number of 0 to 20, p represents 0.5 to 2.0, R₃Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

By adopting such a configuration, the epoxy resin composition has good adhesion to metals such as Cu, Ag, Au, and Pd, and thus has excellent reflow resistance and good flame retardancy without lowering fluidity. The reason is not clear, and the following is considered.

By incorporating a specific amount of benzyl group into an epoxy resin that is an epoxide of a phenol novolac (japanese: ノボラック) type phenol resin, the interaction with an adherend is increased, and the adhesiveness is improved. In addition, it is considered that: the moisture resistance is improved, the occurrence of peeling from an insert such as a lead frame due to moisture absorption is suppressed, and the reflow resistance is improved by maintaining the adhesiveness even in reflow soldering exposed to high-temperature heat. In particular, by combining a specific curing agent, the adhesion with Ag, which can be used as a material of a lead frame, is increased, and therefore, the reflow resistance is synergistically improved.

In addition, it is considered that: by lowering the melt viscosity, the fluidity is increased 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 general formula (1).

[ solution 3]

R₁Each independently represents a hydrogen atom or a C1-6 monovalent hydrocarbon group, R₂Represents a substituent represented by the formula (a), m represents 0 to 20, p represents 0.5 to 2.0, R₃Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

In the general formula (1), R₂A substituent represented by the formula (a) (hereinafter also referred to as "benzyl group"). p represents a number of 0.5 to 2.0, which means the average number (mathematical average) of benzyl groups substituted on 1 benzene ring. p is 0.5 to 2.0, preferably 0.7 to 1.5. When p is 0.7 or more, reflow resistance is further improved, and when p is 1.5 or less, curability is further improved.

Here, p will be explained. At most 3 benzyl groups may be substituted on the benzene rings at both ends of the compound represented by the general formula (1). A maximum of 2 benzyl groups can be substituted on the middle phenyl ring, so in the case of m being 1, the maximum total number of benzyl groups is 8, and in this case the maximum value of p is 2.7(8/3 ≈ 2.7). However, in this embodiment, p in the general formula (1) is 0.5 to 2.0. In the present embodiment, p is a mathematical average value, and therefore, may be a compound in which a hydrogen atom in the benzene ring in the general formula (1) is not substituted with a benzyl group.

In the formula (a), R₃Each 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), R₁Each 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 or a methyl group. In addition, R₁May 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 of 0 to 20, preferably 1.0 to 5.0.

The melt viscosity of the specific epoxy resin at 150 ℃ is preferably 0.01 pas to 0.30 pas, more preferably 0.01 pas to 0.20 pas. From the viewpoint of handling properties, the lower the melt viscosity is, the more preferable the melt viscosity is.

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

(1) Setting the temperature range to 150 ℃, (2) melting 0.15g to 0.25g of the sample on a plate, lowering the cone, and putting it until the ignition of the temperature control lamp was repeated 5 times. (3) Stirring was performed for about 20 seconds up and down in a cone, and then the mixture was left until the temperature control lamp was turned on and off 5 times. (4) After the cone had rotated, the value was read after about 15 seconds. (5) The operations (3) to (4) were repeated until they became the same, and the value was recorded. (6) The operations (2) to (5) were repeated 3 or more times in the same batch, and the average value was set as the viscosity.

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

The epoxy equivalent is measured by the following method.

Epoxy resin was metered into a 100-mL flask so that the solid content became 3g to 4g, and 20mL of acetic acid, 10mL of a tetraethylammonium bromide acetic acid solution (a mixed solution of 100g of tetraethylammonium bromide and 400mL of acetic acid), and 4 to 5 drops of crystal violet were added. The solution was titrated with a 0.1mol/L perchloric acid acetic acid solution. The blank was titrated similarly. The epoxy equivalent is calculated according to the following formula.

Epoxy equivalent of 1,000 × mass of epoxy resin [ g ] multiplied by solid content concentration of epoxy resin [ mass% ]/((titration amount [ mL ] -blank titration amount [ mL ]) × 0.1mol/L × factor f of perchloroacetic acid solution)

The softening point of the specific epoxy resin is preferably 50 to 80 ℃, more preferably 55 to 70 ℃, and further preferably 56 to 65 ℃ from the viewpoint of moldability and reflow resistance. The softening point of a particular epoxy resin is determined using the ring and ball method. The ring and ball method is: the resin was placed on a support ring in a water bath, a ball of 3.5. + -. 0.05g was placed at the center of the ring, the bath temperature was increased at a rate of 5. + -. 0.5 ℃ per minute, and then the temperature at which the resin sags due to the weight of the ball was measured. In detail, the following is measured according to JIS K7234: 1986.

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

The compounding ratio of the raw material phenol novolak resin to the raw material benzyl group-containing compound is adjusted in accordance with the desired value of p in the general formula (1). Therefore, it is preferable that: the raw material phenol novolac resin and the raw material benzyl-containing compound are blended so that 0.5 to 2.0, more preferably 0.7 to 1.5 benzyl-containing compounds are added to 1 benzene ring of the raw material phenol novolac resin. Here, since the benzene ring of the raw material phenol novolac resin has 1 hydroxyl group, the blending ratio of the raw material benzyl group-containing compound is preferably 0.5 to 2.0 moles, and more preferably 0.7 to 1.5 moles, with respect to 1 mole of the hydroxyl group in the raw material phenol novolac resin.

The phenol novolac resin as a raw material has: having R bound by methylene₁(a monovalent hydrocarbon group having 1 to 6 hydrogen atoms or carbon atoms) and a phenol compound. As the phenol compound, there may be mentioned: phenol, cresol, ethylphenol, isopropylphenol, n-propylphenol, isobutylphenol, tert-butylphenol, n-pentylphenol, n-hexylphenol, etc. Among these, o-cresol or cresol containing o-cresol as a main component is preferable as the phenol compound. When cresol containing o-cresol as a main component is used, the content of o-cresol is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the whole cresol. In the case of using cresol containing o-cresol as a main component, the cresol containing o-cresol as a main component may include m-cresol and p-cresol.

With respect to the starting phenol novolac resin, except that it has R linked by methylene₁The phenol compound (b) may have a structure in which a part of the phenol compound (b) is linked to another phenol compound by a methylene group. Examples of the other phenol compounds include: allyl phenol, phenylphenol, 2, 6-xylenol, 2, 6-diethylphenol, hydroquinone, and the like,Resorcinol, catechol, 1-naphthol, 2-naphthol, 1, 5-naphthalenediol, 1, 6-naphthalenediol, 1, 7-naphthalenediol, 2, 6-naphthalenediol, 2, 7-naphthalenediol, etc. The compound represented by the general formula (1) may contain a structural unit derived from another phenol compound in a part thereof, and the compound represented by the general formula (1) preferably contains a structural unit derived from another phenol compound in an amount of 10% by mass or less, more preferably contains 5% by mass or less, and further preferably does not substantially contain the structural unit.

The raw material of the benzyl-containing compound is a compound having a radical R₃(a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) in a benzyl group. Examples of the benzyl group-containing compound as the raw material include: benzyl alcohol, benzyl chloride, benzyl bromide, benzyl iodide, and the like. The raw material benzyl-containing compound such as benzyl alcohol, benzyl chloride, benzyl bromide, benzyl iodide and the like may have C1-6 monovalent hydrocarbon group as R₃. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl and the like.

The acid catalyst may be appropriately selected from known inorganic acids and organic acids. Specifically, there may be mentioned: inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid, and diethylsulfuric acid; lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride; ion exchange resins, activated clay, silica-alumina, zeolite, and other solid acids.

The reaction for synthesizing the specific phenol novolac resin is usually carried out at 10 to 250 ℃ for 1 to 20 hours. In addition, 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, ethyl cellosolve, etc.; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene.

The reaction may be carried out, for example, by the following method: a method in which the phenol novolac resin as a raw material and all the raw materials containing a benzyl compound as a raw material are charged together and reacted at a predetermined temperature; and a method of charging the raw material phenol novolac resin and the catalyst, maintaining the temperature at a predetermined level, and reacting the raw material benzyl group-containing compound dropwise. In this case, the dropping time is usually 1 hour to 10 hours, preferably 5 hours or less. When a solvent is used after the reaction, the catalyst is removed if necessary, and then the solvent is distilled off to obtain a specific phenol novolac resin.

Examples of the method for epoxidizing a specific phenol novolak resin include: a method of reacting a specific phenol novolac resin with epichlorohydrin; and a method in which a specific phenol novolac resin is reacted with an allyl halide to produce an allyl ether compound, and then the allyl ether compound is reacted with a peroxide.

Examples thereof include the following methods: a specific phenol novolac resin is dissolved in an excessive amount of epichlorohydrin, and then reacted in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at a temperature in the range of 20 to 150 ℃, preferably 30 to 80 ℃ for 1 to 10 hours. The amount of the alkali metal hydroxide used in this case is preferably 0.8 to 1.5 moles, and more preferably 0.9 to 1.2 moles, based on 1 mole of the hydroxyl group of the specific phenol novolac resin. The epichlorohydrin is used in an excess amount to 1 mole of the hydroxyl group of the specific phenol novolac resin, and is usually in the range of 1.5 to 30 moles, preferably 2 to 15 moles, based on 1 mole of the hydroxyl group of the specific phenol novolac resin. After the reaction is completed, the excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, and the inorganic salt is removed by filtration and washing with water, and then the solvent is distilled off, whereby the objective specific epoxy resin can be obtained.

The epoxy resin composition may further contain a conventionally known epoxy resin in addition to the specific epoxy resin. Examples of epoxy resins that can be used in combination include: a phenol novolac type epoxy resin obtained by condensing or co-condensing at least 1 selected from phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, and bisphenol F, and naphthol compounds such as α -naphthol, β -naphthol, and dihydroxynaphthalene with a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst (for example, a phenol novolac type epoxy resin (excluding a specific epoxy resin), an o-cresol novolac type epoxy resin (excluding a specific epoxy resin), and a triphenylmethane type epoxy resin); epoxy resins as diglycidyl ethers of bisphenol a, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted diphenols and the like; stilbene type epoxy resins; p-phenylene bisphenol type epoxy resin; glycidyl ester type epoxy resins obtained by the reaction of epichlorohydrin with polybasic acids such as phthalic acid and dimer acid; glycidyl amine type epoxy resins obtained by the reaction of epichlorohydrin with polyamines such as diaminodiphenylmethane and isocyanuric acid; an epoxide of a co-condensation resin of dicyclopentadiene and a phenol compound, i.e., a dicyclopentadiene type epoxy resin; naphthalene type epoxy resins having a naphthalene ring; an epoxide of a phenol aralkyl resin, i.e., a phenol aralkyl type epoxy resin; a biphenylene type epoxy resin containing a biphenylene skeleton; an epoxide of a naphthol aralkyl resin, i.e., a naphthol aralkyl type epoxy resin; trimethylolpropane type epoxy resins; terpene-modified epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; a cycloaliphatic epoxy resin; sulfur atom-containing epoxy resins, and the like. The epoxy resins that can be used in combination may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among them, as the epoxy resin that can be used in combination, 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 fluidity and reflow resistance, a phenol type epoxy resin (excluding a specific epoxy resin) is preferable from the viewpoint of curability, a dicyclopentadiene type epoxy resin is preferable from the viewpoint of low moisture absorption, a naphthalene type epoxy resin and a triphenylmethane type epoxy resin are preferable from the viewpoint of heat resistance and low warpage, and a biphenylene type epoxy resin and a naphthol aralkyl type epoxy resin are preferable from the viewpoint of flame retardancy. From the viewpoint of improving the high-temperature storage characteristics, it is preferable to use an epoxy resin having good flame retardancy in combination to prepare a halogen-free and antimony-free epoxy resin composition.

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

[ solution 4]

In the general formula (III), R¹～R⁸Each independently represents 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 an aralkyl group having 7 to 10 carbon atoms. n is an average value and represents a value of 0 to 3. R¹～R⁸The alkyl group, the alkoxy group, the aryl group and the aralkyl group may have a substituent or may not have a substituent, respectively.

[ solution 5]

In the general formula (IV), R¹～R⁸Each independently represents 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 value of 0 to 3. R¹～R⁸The alkyl group and the alkoxy group may have a substituent or may have no substituent, respectively.

[ solution 6]

In the general formula (V), R¹～R⁵Each independently represents 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 value of 0 to 3. R¹～R⁵The alkyl group and the alkoxy group may have a substituent independently of each other, or may have no substituent.

The bisphenol F-type epoxy resin represented by the general formula (III) can be obtained, for example, as R in the form of a commercially available product¹、R³、R⁶And R⁸Is methyl, R²、R⁴、R⁵And R⁷YSLV-80 XY (trade name, product name, new york chemical) which is a hydrogen atom and contains n ═ 0 as a main component.

In the sulfur atom-containing epoxy resin represented by the general formula (IV), R is preferable²、R³、R⁶And R⁷Is a hydrogen atom and R¹、R⁴、R⁵And R⁸Epoxy resins which are alkyl, more preferably R²、R³、R⁶And R⁷Is a hydrogen atom, R¹And R⁸Is tert-butyl and R⁴And R⁵Epoxy resin which is methyl. As such a compound, YSLV-120 TE (trade name, Nippon Tekken chemical Co., Ltd.) can be obtained, for example, as a commercially available product.

As the epoxy resin represented by the general formula (V), R can be obtained, for example, as a commercially available product¹～R⁵NC-2000L (trade name, Nippon Kagaku Co., Ltd.) as a hydrogen atom. These epoxy resins may be used alone in any 1 kind, or may be used in combination in 2 or more kinds.

Examples of the novolac-type epoxy resin include: an epoxy resin represented by the following general formula (VI).

[ solution 7]

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

The novolak type epoxy resin represented by the general formula (VI) is 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 a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, or the like, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or the like, and 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 general formula (VI), o-cresol novolac type epoxy resins are preferable. Such a compound is commercially available, for example, as EOCN-1020 (product name, japan chemical corporation).

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

[ solution 8]

In the general formula (VII), R¹And R²Each independently represents 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. R¹And R²The hydrocarbon group may or may not have a substituent independently of each other.

As R in the general formula (VII)¹Examples thereof include: a hydrogen atom; alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, and tert-butyl; alkenyl groups such as vinyl, allyl, butenyl and the like; and monovalent hydrocarbon groups having 1 to 5 carbon atoms and having a substituent such as a haloalkyl group, an amino-substituted alkyl group, or a mercapto-substituted alkyl group. Among them, an alkyl group such as a methyl group or an ethyl group or a hydrogen atom is preferable, and a methyl group or a hydrogen atom is more preferable.

As R in the general formula (VII)²Examples thereof include: a hydrogen atom; alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, and tert-butyl; alkenyl groups such as vinyl, allyl, butenyl and the like; halogenated alkyl, amino radicalsAnd monovalent hydrocarbon groups having 1 to 5 carbon atoms and having a substituent such as an alkyl group, a mercapto group-substituted alkyl group, and the like. Among them, a hydrogen atom is preferable. As such a compound, HP-7200 (trade name, available from DIC) can be obtained, for example, as a commercially available product.

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

[ solution 9]

In the general formula (VIII), R¹～R³Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. p is an average value and represents a numerical value of 0 to 2, and l and m are average values, each independently represents a numerical value of 0 to 11, and is selected so that (l + m) is a numerical value of 1 to 11 and (l + p) is a numerical value of 1 to 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. R¹～R³The hydrocarbon group may or may not have a substituent independently of each other.

Examples of the naphthalene type epoxy resin represented by the general formula (VIII) include: a random copolymer randomly containing l constituent units and m constituent units, an alternating copolymer alternately containing l constituent units and m constituent units, a copolymer regularly containing l constituent units and m constituent units, and a block copolymer containing l constituent units and m constituent units in a block form may be used alone or in combination of 2 or more. As R¹And R²Is a hydrogen atom and R³The above-mentioned compound having a methyl group is commercially available, for example, as NC-7000 (trade name, Nippon chemical Co., Ltd.).

[ solution 10]

In the general formula (IX), R independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an average value of 0 to 10. Each of the hydrocarbon groups represented by R may or may not have a substituent independently. The compound wherein R is a hydrogen atom can be obtained, for example, as E-1032 (trade name, Mitsubishi chemical corporation) which is commercially available.

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

[ solution 11]

In the general formula (X), R¹～R⁹Each independently represents: a hydrogen atom; alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, and the like; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, xylyl and the like; or an aralkyl group having 7 to 10 carbon atoms such as a benzyl group or a phenethyl group, and among them, a hydrogen atom or a methyl group is preferable. n is an average value and represents a value of 0 to 10. R¹～R⁹The alkyl group, the alkoxy group, the aryl group and the aralkyl group may each independently represent a substituent or may have no substituent.

[ solution 12]

In the general formula (XI), R¹And R²Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and n represents a number of 0 to 10 as an average value. R¹And R²The hydrocarbon group may or may not have a substituent independently of each other.

The biphenyl-based epoxy resin is available, for example, as NC-3000 (trade name, Nippon chemical Co., Ltd.). Further, as the naphthol aralkyl type epoxy resin, ESN-175 (trade name, Nissian chemical Co., Ltd.) is available as a commercially available product, for example. Any 1 kind of the biphenylene type epoxy resin may be used alone, or 2 or more kinds may be used in combination.

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

[ solution 13]

R in the formula (XII)¹Each independently represents a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and n represents a number of 0 to 4 as an average value. In addition, R²Each independently represents a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and m represents an average value and is a number of 0 to 2. R¹And R²The hydrocarbon group and the alkoxy group may or may not have a substituent, respectively. Among them, from the viewpoint of flame retardancy and moldability, epoxy resins having zero n and m are preferable. As such a compound, YX-8800 (Mitsubishi chemical Co., Ltd., trade name) can be obtained, for example.

The content 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.

(curing agent)

The epoxy resin composition contains a curing agent. The curing agent contains at least 1 selected from the group consisting of a biphenylene type phenol aralkyl resin, a phenol aralkyl resin and a triphenylmethane type phenol resin.

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

[ solution 14]

Herein, R is¹～R⁹Each independently represents: a hydrogen atom; alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, and the like; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, xylyl and the like; or an aralkyl group having 7 to 10 carbon atoms such as a benzyl group or a phenethyl group, and among them, a hydrogen atom or a methyl group is preferable. n is an average value and represents a value of 0 to 10. R¹～R⁹The alkyl group, alkoxy group, aryl group or aralkyl group may or may not have a substituent, independently of each other.

As the biphenylene type phenol aralkyl resin represented by the general formula (XVII), for example, R is mentioned¹～R⁹Among all the compounds which are hydrogen atoms, a mixture containing a condensate of a condensate in which n is 1 or more in an amount of 50 mass% or more is preferable from the viewpoint of melt viscosity. As such a compound, MEH-7851 (product name, Minghua chemical Co., Ltd.) is available, for example, as a commercially available product. In the case of using these biphenylene type phenol aralkyl resins, the content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, relative to the total amount of the curing agent in order to exert the performance thereof.

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

[ solution 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 represents a number of 0 to 10 on average. Each of the hydrocarbon groups represented by R may or may not have a substituent independently.

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. Specific examples thereof include: p-xylylene type phenol aralkyl resins, m-xylylene type phenol aralkyl resins, and the like. As such a compound, XLC (trade name, mitsui chemical) is available, for example, as a commercial product. In the case of using these phenol aralkyl resins, the content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, relative to the total amount of the curing agent in order to exert the performance thereof.

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

[ solution 16]

In the general formula (XVI), R independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an average value and a numerical value of 0 to 10. Each of the hydrocarbons represented by R may or may not have a substituent independently. As the above-mentioned compound wherein R is a hydrogen atom, MEH-7500 (product name, manufactured by Minghua chemical Co., Ltd.) can be obtained, for example, as a commercially available product. When these triphenylmethane type phenol resins are used, the content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agents, in order to exert the performance thereof.

Any 1 kind of the specific curing agent may be used alone, or 2 or more kinds may be used in combination.

The curing agent other than the specific curing agent may be used in combination. The content of the specific curing agent in the total 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 other curing agents include: phenol resins such as phenol novolac resins, naphthol aralkyl resins, dicyclopentadiene phenol resins, terpene-modified phenol resins, p-xylylene-modified phenol resins, m-xylylene-modified phenol resins, melamine-modified phenol resins, cyclopentadiene-modified phenol resins, and phenol resins obtained by copolymerizing 2 or more of these.

As the phenol novolac resin, cresol novolac resin, naphthol novolac resin, and the like can be cited, and among them, phenol novolac resin is preferable.

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

[ solution 17]

In the general formula (XIV), R¹And R²Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 0 to 10 as an average value. R¹And R²The hydrocarbon group may or may not have a substituent independently of each other.

Examples of the naphthol aralkyl resin represented by the general formula (XIV) include R¹And R²Such a compound is, for example, SN-170 (trade name, Nissian chemical Co., Ltd.) which is commercially available.

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

[ solution 18]

In the general formula (XV), R¹And R²Each independently represents 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. R¹And R²The hydrocarbon group may or may not have a substituent independently of each other. As R¹And R²The above-mentioned compound as a hydrogen atom is, for example, DPP (New Nissan petrochemical Co., Ltd., trade name) available as a commercially available product.

As for the other curing agents, 1 kind of them may be used alone, or 2 or more kinds may be used in combination. Among the other curing agents used in combination, a phenol novolac resin is preferable from the viewpoint of curability.

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

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

The hydroxyl group equivalent of the curing agent was determined by acetyl-chlorinating the hydroxyl group of the curing agent in a pyridine solution by the pyridine-acetyl chloride method, then decomposing the excess reagent with water, and titrating the generated acetic acid with a solution containing potassium hydroxide and ethanol.

The equivalent ratio of the epoxy resin and the curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (the number of hydroxyl groups in the curing agent/the number of epoxy groups in the epoxy resin) is not particularly limited, and is preferably set in the range of 0.5 to 2, more preferably 0.6 to 1.3, in order to suppress the amount of each unreacted epoxy resin to a small amount. In order to obtain an epoxy resin composition having excellent moldability and reflow resistance, it is preferable to set the range of 0.8 to 1.2.

(curing accelerators)

A curing accelerator may be used as needed in the epoxy resin composition from the viewpoint of accelerating the reaction between the epoxy resin and the curing agent.

The curing accelerator may be used without particular limitation as the curing accelerator generally used in epoxy resin compositions. Examples of the curing accelerator include: cyclic amidine compounds such as 1, 8-diaza-bicyclo [5.4.0] undecene-7, 1, 5-diaza-bicyclo [4.3.0] nonene, 5, 6-dibutylamino-1, 8-diaza-bicyclo [5.4.0] undecene-7 and the like; compounds having intramolecular polarization, which are obtained by adding a quinone compound such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluenequinone (japanese: トルキノン), 1, 4-naphthoquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, 2, 3-dimethoxy-1, 4-benzoquinone, or phenyl-1, 4-benzoquinone, or a compound having a pi bond such as diazophenylmethane or phenol resin to a cyclic amidine compound; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like; derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole; derivatives of imidazole compounds; phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine; phosphorus compounds having intramolecular polarization, which are obtained by adding a compound having a pi bond such as maleic anhydride, the quinone compound, diazophenylmethane, or a phenol resin to these phosphine compounds; tetraphenylborons such as tetraphenylphosphonium tetraphenylboron ate, triphenylphosphine tetraphenylboron ate, 2-ethyl-4-methylimidazolium tetraphenylboron ate and N-methylmorpholine tetraphenylboron ate; derivatives of tetraphenylboron salts, and the like. The curing accelerator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

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

The tertiary phosphine compound is not particularly limited, and includes: tertiary phosphine compounds having an alkyl group or an aryl group such as tricyclohexylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (tert-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, and tris (4-ethoxyphenyl) phosphine.

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

As the curing accelerator, an adduct of triphenylphosphine and p-benzoquinone is preferable from the viewpoint of reflow resistance, and an adduct of tris (4-methylphenyl) phosphine and p-benzoquinone is preferable from the viewpoint of mold releasability.

The content of the curing accelerator is not particularly limited as long as the curing accelerator can achieve the curing acceleration effect. When the epoxy resin composition contains a curing accelerator, the content of the curing accelerator in the epoxy resin composition is preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass. When the amount is 0.005% by mass or more, curability tends to be improved, and when the amount is 2% by mass or less, pot life tends to be improved.

(inorganic Filler)

The epoxy resin composition may further contain an inorganic filler. When the inorganic filler is contained, the hygroscopicity tends to be low, the linear expansion coefficient tends to be low, the thermal conductivity tends to be high, and the strength tends to be high. Examples of the inorganic filler include: powders such as fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconia, zircon, forsterite, steatite, spinel, mullite, and titanium dioxide; beads and glass fibers obtained by spheroidizing them. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide, zinc borate, and zinc molybdate. As zinc borate, FB-290, FB-500 (u.s. borax), FRZ-500C (shizikia chemical) and the like are commercially available, and as zinc molybdate, KEMGARD911B, 911C, 1100 (Sherwin-Williams) and the like are commercially available.

These inorganic fillers may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among them, fused silica is preferable from the viewpoint of filling property and reduction of linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The shape of the inorganic filler is preferably spherical from the viewpoint of filling properties and mold wear resistance.

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

The specific surface area of the inorganic filler is preferably 1m from the viewpoint of flame retardancy and fluidity²/g～5m²G, more preferably 2m²/g～4m²/g。

When the epoxy resin composition contains an inorganic filler, the content of the inorganic filler in the epoxy resin composition is preferably 50% by mass or more, more preferably 60% by mass to 95% by mass, and even more preferably 70% by mass to 90% by mass, from the viewpoint of fluidity, flame retardancy, moldability, reduction in moisture absorption, reduction in linear expansion coefficient, improvement in strength, and reflow resistance. When the content of the inorganic filler is 50% by mass or more, the fluidity tends to be improved, and when the content 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 in an epoxy resin composition, the coupling agent tends to improve the adhesiveness between the resin component and the inorganic filler. As the coupling agent, a coupling agent generally used in epoxy resin compositions can be used without particular limitation. Examples of coupling agents include: various silane compounds such as a silane compound having a primary, secondary or tertiary amino group, epoxysilane, mercaptosilane, alkylsilane, ureylsilane, and vinylsilane, titanium compounds, aluminum chelates, and aluminum and zirconium-containing compounds.

Examples of the coupling agent include: vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-anilinopropyltrimethoxysilane, gamma- (N, N-dimethyl) aminopropyltrimethoxysilane, gamma- (N, N-diethyl) aminopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidyloxy-1-2-glycidyloxy-2-hydroxy-methyl-2-hydroxy-or a-hydroxy-or-hydroxy-or-hydroxy-or-hydroxy-or a-hydroxy-or-hydroxy-or a-hydroxy-or-hydroxy-, Gamma- (N, N-dibutyl) aminopropyltrimethoxysilane, gamma- (N-methyl) anilinopropyltrimethoxysilane, gamma- (N-ethyl) anilinopropyltrimethoxysilane, gamma- (N, N-dimethyl) aminopropyltriethoxysilane, gamma- (N, N-diethyl) aminopropyltriethoxysilane, gamma- (N, N-dibutyl) aminopropyltriethoxysilane, gamma- (N-methyl) anilinopropyltriethoxysilane, gamma- (N-ethyl) anilinopropyltriethoxysilane, gamma- (N, N-dimethyl) aminopropylmethyldimethoxysilane, gamma- (N, N-diethyl) aminopropylmethyldimethoxysilane, gamma- (N, N-dibutyl) aminopropylmethyldimethoxysilane, gamma- (N-methyl) anilinopropylmethyldimethoxysilane, Silane coupling agents such as gamma- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, gamma-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, and gamma-mercaptopropylmethyldimethoxysilane; isopropyltriisostearoyltitanate, isopropyltris (dioctylpyrophosphate (Japanese: パイロホスフェート)) titanate, isopropyltris (N-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetrakis (2, 2-diallyloxymethyl-1-butyl) bis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylenetitanate, titanate coupling agents such as isopropyl trioctyl titanate, isopropyl dimethacryloyl isostearyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearyl diacryloyl titanate, isopropyl tris (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis (dioctyl phosphite) titanate. As the coupling agent, 1 kind of them may be used alone, or 2 or more kinds may be used in combination.

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

As the silane coupling agent having a secondary amino group, there can be mentioned: gamma-anilinopropyltrimethoxysilane, gamma-anilinopropyltriethoxysilane, gamma-anilinopropylmethyldimethoxysilane, gamma-anilinopropylmethyldiethoxysilane, gamma-anilinopropylethylethyldiethoxysilane, gamma-anilinomethyltrimethoxysilane, gamma-anilinomethyltriethoxysilane, gamma-anilinomethylmethyldimethoxysilane, gamma-anilinomethylmethyldiethoxysilane, gamma-anilinomethyldiethoxysilane, gamma-anilinomethyldimethoxysilane, N- (p-methoxyphenyl) -gamma-aminopropyltrimethoxysilane, N- (p-methoxyphenyl) -gamma-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -gamma-aminopropylmethyldimethoxysilane, gamma-anilinomethyldimethoxysilane, gamma-anilinopropyltrimethoxysilane, gamma-methoxysilane, gamma-anilinopropyltrimethoxysilane, gamma-anilinomethyldimethoxysilane, gamma-anilinopropyltrimethoxysilane, gamma-anilinomethylmethoxysilane, gamma-anilinomethyldimethoxysilane, gamma-p-anilinopropyltrimethoxysilane, gamma-anilinomethylmethoxysilane, gamma-p-anilinomethylmethoxysilane, gamma-p-anilinopropyltrimethoxysilane, gamma-p-anilinomethylmethoxysilane, gamma-p-anilinopropylty-p-methyl-p-methyl-p-methyl-p-methyl-p-methyl-N-p-N-p-methyl-N-p-methyl-N-p-methyl-p-methyl-N-, N- (p-methoxyphenyl) -gamma-aminopropylmethyldiethoxysilane, N- (p-methoxyphenyl) -gamma-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -gamma-aminopropylethyldimethoxysilane, gamma- (N-methyl) aminopropyltrimethoxysilane, gamma- (N-ethyl) aminopropyltrimethoxysilane, gamma- (N-butyl) aminopropyltrimethoxysilane, gamma- (N-benzyl) aminopropyltrimethoxysilane, gamma- (N-methyl) aminopropyltriethoxysilane, gamma- (N-ethyl) aminopropyltriethoxysilane, gamma- (N-butyl) aminopropyltriethoxysilane, gamma- (N-benzyl) aminopropyltriethoxysilane, gamma- (N-methyl) aminopropylmethyldimethoxysilane, gamma- (N-ethyl) aminopropylmethyldimethoxysilane, gamma- (N-propyl) trimethoxysilane, gamma- (N-butyl) aminopropyl-trimethoxysilane, gamma- (N-propyl) aminopropyl-trimethoxysilane, gamma- (N-methyl) amino-propylmethyldimethoxysilane, gamma- (N-ethyl) aminopropyl-trimethoxysilane, gamma- (N-ethyl) amino-propyltrimethoxysilane, gamma- (N-propyl) trimethoxysilane, gamma-ethyl) amino-propyltrimethoxysilane, gamma-N-butyl) trimethoxysilane, gamma-butyl-amino-propyl-trimethoxysilane, gamma-butyl-amino-propyl-trimethoxysilane, gamma-ethyl-propyl-ethyl-amino-propyl-methyl-triethoxysilane, gamma-propyl-ethyl-propyl-ethyl-trimethoxysilane, gamma-propyl-ethyl-trimethoxysilane, or-propyl-ethyl-propyl-ethyl-propyl-ethyl-propyl-ethyl-propyl-ethyl-or-propyl-ethyl-propyl-or-ethyl-propyl-ethyl-or-ethyl-propyl-ethyl-propyl-ethyl-propyl-ethyl-propyl-or-ethyl-propyl-ethyl-propyl-ethyl-or-ethyl-propyl-ethyl-or-ethyl-propyl-ethyl-or-ethyl-propyl-, Gamma- (N-butyl) aminopropylmethyldimethoxysilane, gamma- (N-benzyl) aminopropylmethyldimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma- (beta-aminoethyl) aminopropyltrimethoxysilane, N-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropyltrimethoxysilane, and the like.

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

(flame retardant)

The epoxy resin composition may further contain a conventionally known flame retardant from the viewpoint of improving flame retardancy, and may further contain a halogen-free and antimony-free flame retardant as required from the viewpoint of environmental compatibility and reliability. As the flame retardant, there may be mentioned: inorganic compounds such as red phosphorus, phosphoric acid esters, and zinc oxide; a resin-coated phosphorus compound such as red phosphorus and phosphine oxide coated with a thermosetting resin such as a phenol resin, a nitrogen-containing compound such as melamine, a melamine derivative, a melamine-modified phenol resin, a compound having a triazine ring, a cyanuric acid derivative, and an isocyanuric acid derivative; phosphorus-and nitrogen-containing compounds such as cyclic phosphazene; and compounds containing metal elements such as aluminum hydroxide, magnesium hydroxide, composite metal hydroxides, zinc oxide, zinc stannate, zinc borate, acidified iron, acidified molybdenum, zinc molybdate, and dicyclopentadiene iron. The flame retardant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(silicon-containing Polymer)

The epoxy resin composition may contain a silicon-containing polymer from the viewpoint of reducing warpage. As the silicon-containing polymer, preferred are: having the following bonds (c) and (d) and ending with a group selected from R¹A hydroxyl group and an alkoxy group, and an epoxy equivalent of 500 to 4000 g/eq. Examples of the silicon-containing polymer include branched polysiloxanes called silicone resins.

[ solution 19]

Herein, R is¹Each independently represents a 1-valent hydrocarbon group having 1 to 12 carbon atoms. X represents a 1-valent organic group containing an epoxy group. R¹The hydrocarbon group shown may have a substituent. It can also be: the epoxy group contained in X undergoes a ring-opening reaction, and X becomes a 2-valent group.

As R in the bonds (c) and (d)¹Examples thereof include: alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, and the like; aryl groups such as phenyl, tolyl, xylyl, naphthyl, and biphenyl; aralkyl groups such as benzyl and phenethyl, among which methyl and phenyl are preferred.

In addition, X in the bond (d) is a 1-valent 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, X includes: 2, 3-epoxypropyl group, 3, 4-epoxybutyl group, 4, 5-epoxypentyl group, 2-epoxypropoxyethyl group, 3-epoxypropoxypropyl group, 4-epoxypropoxybutyl group, 2- (3, 4-epoxycyclohexyl) ethyl group, 3- (3, 4-epoxycyclohexyl) propyl group and the like, among which 3-epoxypropoxypropyl group is preferable.

Further, as for the terminal of the silicon-containing polymer, a polymer is selected fromFrom the viewpoint of storage stability of (2), R¹Each independently is preferably a hydroxyl group or an alkoxy group. Examples of the terminal alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

When the silicon-containing polymer has an epoxy group, the epoxy equivalent is preferably in the range of 500 to 4000g/eq, more preferably 1000 to 2500 g/eq. When the epoxy equivalent of the silicon-containing polymer is 500g/eq or more, the fluidity of the epoxy resin composition tends to be improved, and when the epoxy equivalent is 4000g/eq or less, the bleeding of the cured product on the surface tends to be suppressed, and the occurrence of molding failure tends to be reduced.

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 to 1.5% by mass, and more preferably 0.3 to 1.3% by mass. When the content is 0.2% by mass or more, the effect of reducing the warpage amount of the package tends to be improved, and when the content is 1.5% by mass or less, the curability tends to be improved.

(other Components)

The epoxy resin composition may contain at least 1 selected from the group consisting of a compound represented by the following composition formula (XXXIII) and a compound represented by the following composition formula (XXXIV) as required from the viewpoint of improving moisture resistance and high-temperature storage characteristics of a semiconductor element such as an IC.

[ solution 20]

Mg_1-xAl_x(OH)₂(CO₃)_x/2mH₂O (XXXIII)

(X is more than 0 and less than or equal to 0.5, and m is a positive number)

[ solution 21]

BiO_x(OH)_y(NO₃)_z (XXXIV)

(0.9≤x≤1.1、0.6≤y≤0.8、0.2≤z≤0.4)

The compound of formula (XXXIII) is commercially available under the trade name DHT-4A from Kyowa Kagaku K.K. Further, the compound of formula (XXXIV) is commercially available under the trade name IXE500 available from Toyo Synthesis K.K. Further, other anion exchangers may be added as necessary. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used, and examples thereof include hydrated oxides (Japanese-language: hydrated acid compounds) of elements such as magnesium, aluminum, titanium, zirconium, and antimony. As the anion exchanger, 1 kind of them may be used alone or 2 or more kinds may be used in combination.

The epoxy resin composition may contain, as other additives, a higher fatty acid metal salt, an ester wax, a polyolefin wax, a release agent such as polyethylene or acidified polyethylene, a coloring agent such as carbon black, a stress relaxation agent such as silicone oil or silicone rubber powder, if necessary.

< preparation of 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. The following methods can be mentioned as a general production method: a method in which raw materials of a predetermined compounding amount are sufficiently mixed by a mixer or the like, and then mixed or melt-kneaded by a grinding roll, an extruder, a kneader, a planetary mixer or the like, cooled, and, if necessary, deaerated and pulverized. The epoxy resin composition may be formed into a small piece (Japanese patent No. タブレット) having a size and a quality suitable for molding conditions, if necessary.

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

Examples of the electronic component device of the present embodiment including the element sealed with the epoxy resin composition of the present embodiment include the following electronic component devices: an electronic component device in which a semiconductor chip, an active element such as a transistor, a diode, or a thyristor, and an element such as a passive element such as a capacitor, a resistor, or a coil are mounted on a lead frame, a wired tape carrier, a wiring board, a supporting member such as glass or a silicon wafer, a mounting substrate, or the like, and a desired portion is sealed with the epoxy resin composition of the present embodiment.

Here, the mounting substrate is not particularly limited, and includes: an interposer (japanese: インターポーザ) substrate such as an organic substrate, an organic film, a ceramic substrate, or a glass substrate, a glass substrate for liquid crystal, a substrate for mcm (multi Chip module), a substrate for hybrid IC, or the like.

Examples of the electronic component device including such an element include a semiconductor device, and specifically, include: a resin-sealed IC such as dip (dual Inline Package), plcc (plastic led Chip carrier), qfp (Quad Flat Package), sop (outer line Package), SOJ (Small out line J-lead Package), tsop (thin out line Package), and tqfp (thin Quad Flat Package)) is fixed to a lead frame (island (japanese: アイランド) or a tab (japanese: タブ) and then a terminal portion of an element such as a bonding pad (japanese: ボンディングパッド) and a lead portion are connected by wire bonding or bump, followed by sealing by transfer molding using the epoxy resin composition of the present embodiment; tcp (tape carrier package) in which a semiconductor chip with a carrier is sealed with a lead bonded thereto by using the epoxy resin composition of the present embodiment; a semiconductor device having a die mounted thereon, such as cob (chip On board), cog (chip On glass), which is obtained by sealing a semiconductor chip connected to a wiring formed On a wiring board or glass by wire bonding, flip chip bonding, soldering, or the like, using the epoxy resin composition of the present embodiment; a hybrid IC in which a semiconductor chip, an active element such as a transistor, a diode, or a thyristor, a passive element such as a capacitor, a resistor, or a coil, and the like, which are connected to a wiring or the like formed on a wiring board or glass by wire bonding, flip chip bonding, or soldering, are sealed with the epoxy resin composition of the present embodiment; bga (ball Grid array), csp (Chip Size package), mcp (multi Chip package) and the like, in which a semiconductor Chip is mounted on an interposer substrate having terminals for connecting to an mcm (multi Chip module) motherboard, the semiconductor Chip is connected to wiring formed on the interposer substrate by bump or wire bonding, and the semiconductor Chip mounting side is sealed with the epoxy resin composition of the present embodiment. These semiconductor devices may be stacked (laminated) packages mounted on a mounting substrate in a state where 2 or more elements are stacked, or may be integrally molded packages in which 2 or more elements are sealed with an epoxy resin composition at a time.

Examples

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

[ Synthesis examples 1 to 4]

The specific epoxy resin can be synthesized in the following manner.

First, a phenol novolac resin as a raw material is reacted with a benzyl group-containing compound as a raw material using p-toluenesulfonic acid as an acid catalyst to obtain a specific phenol novolac resin. In this case, the hydroxyl equivalent weight is measured in the same manner as the method for measuring the hydroxyl equivalent weight in the curing agent, and the value of p in the general formula (1) is determined from the measured value.

Next, the specific phenol novolac resin obtained above was epoxidized with epichlorohydrin. The epoxy equivalent, softening point and 150 ℃ melt viscosity of the obtained resin are shown in table 1 below. In the specific epoxy resin obtained, R in the general formula (1)₂Is benzyl (R)₃Is a hydrogen atom).

[ Table 1]

[ examples 1 to 4, comparative examples 1 to 8]

The following components were mixed in the amounts shown in tables 2 and 3, respectively, and roll-kneaded at a kneading temperature of 80 ℃ for 10 minutes to prepare examples 1 to 4 and comparative examples 1 to 8.

(epoxy resin)

Epoxy resin 1: an epoxy resin having an epoxy equivalent of 240g/eq, a softening point of 55 ℃, a compound represented by the general formula (1), and p of 0.6

Epoxy resin 2: an epoxy resin having an epoxy equivalent of 263g/eq, a softening point of 58 ℃, a compound represented by the general formula (1), and p of 0.9

Epoxy resin 3: an epoxy resin having an epoxy equivalent of 264g/eq, a softening point of 60 ℃, a compound represented by the general formula (1), and p of 1.0

Epoxy resin 4: an epoxy resin having an epoxy equivalent of 265g/eq, a softening point of 61 ℃, a compound represented by the general formula (1), and p of 1.1

Epoxy resin 5: copolymer of 2-methoxynaphthalene and o-cresol novolak-type epoxy resin having an epoxy equivalent of 251g/eq, a softening point of 60 ℃ C. (trade name HP-5000, manufactured by DIC Co., Ltd.)

Epoxy resin 6: an o-cresol novolac type epoxy resin having an epoxy equivalent of 190g/eq, a melting point of 59 ℃ and a trade name of N-500P-1 (DIC Co., Ltd.)

(curing agent)

Curing agent 1: phenol aralkyl resin having a hydroxyl group equivalent of 175g/eq and a softening point of 70 ℃ (product name: MEH-7800 SS, manufactured by Minghe Kaisha)

Curing agent 2: novolac phenol resin having a hydroxyl equivalent of 106g/eq and a softening point of 82 ℃ (trade name HP-850N, Hitachi chemical Co., Ltd.)

(curing accelerators)

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

(coupling agent)

Epoxy silane: gamma-glycidoxypropyltrimethoxysilane

(inorganic Filler)

Spherical fused silica: average particle diameter of 14.5 μm and specific surface area of 2.8m²/g

(other additives)

Barcela wax (Clariant Co., Ltd.)

Carbon Black (Mitsubishi chemical corporation, 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 were obtained by the following tests. The results are shown in tables 4 and 5.

(1) Spiral flow (index of fluidity)

Using a mold for measuring spiral flow according to EMMI-1-66, an epoxy resin composition was molded by a transfer molding machine under conditions of a mold temperature of 180 ℃, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and a flow distance (cm) was obtained.

(2) Hot hardness

The epoxy resin composition was molded under the molding conditions of the above (1) into a disk having a diameter of 50mm × a thickness of 3mm, and immediately after molding, the measurement was carried out using a Shore D durometer.

(3) Flame retardancy

The flame retardancy of the epoxy resin composition was evaluated by the UL-94 test method by molding the epoxy resin composition under the molding conditions of the above (1) using a mold for molding a test piece having a thickness of 1/32 inches (0.8mm), and further, by post-curing at 180 ℃ for 5 hours.

(4) Reflow resistance

(4.1) Cu lead frame

An 80-pin flat package (QFP) (lead frame material: copper alloy, die pad portion upper surface, and lead tip silver plating product) having an external dimension of 20mm × 14mm × 2mm, on which a 8mm × 10mm × 0.4mm silicon wafer was mounted, was produced by molding and post-curing under the condition of (3) above using an epoxy resin composition, humidified under the condition of 85 ℃ and 85% RH, and after a predetermined time, reflow treatment was performed under the condition of 240 ℃ and 10 seconds to visually observe the presence or absence of cracks, and the number of packages in which cracks were generated was evaluated with respect to the number of packages tested (5 packages).

(4.2) PPF lead frame

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

(5) Moisture resistance

An epoxy resin composition was molded and post-cured under the conditions described in (3) above to prepare a flat package (QFP) of 80 pins having an external dimension of 20mm × 14mm × 2.7mm, which was a test silicon wafer having an external dimension of 6mm × 6mm × 0.4mm and mounted with an aluminum wiring having a line width of 10 μm and a thickness of 1 μm applied to a silicon oxide film having a thickness of 5 μm, and after pretreatment, the package was humidified and after a predetermined time, the defect in the broken line due to corrosion of the aluminum wiring was examined, and the result was evaluated as the number of defective packages with respect to the number of test packages (10).

The pretreatment was carried out by humidifying the flat package at 85 ℃ and 85% RH for 72 hours, and then carrying out a vapor phase reflow process at 215 ℃ for 90 seconds. The subsequent humidification was carried out under the conditions of 0.2MPa and 121 ℃.

(6) High temperature standing property

A 5mm × 9mm × 0.4mm silicon wafer for test, in which aluminum wiring having a line width of 10 μm and a thickness of 1 μm was applied to a 5 μm thick silicon oxide film, was mounted on a 42 alloy partially silver-plated lead frame using a silver paste, and was molded and post-cured under the above-described condition (3) using an epoxy resin composition to prepare a 16-pin dip (dual Inline package) in which a bonding pad of a chip and an inner lead were connected by an Au wire at 200 ℃ using a thermionic (japanese: サーモニック) type wire bonder, which was stored in a high-temperature bath at 200 ℃, and after a predetermined time, the wafer was taken out and subjected to a conduction test to evaluate the high-temperature standing characteristics with respect to the number of defective packages for conduction of the test packages (10).

[ Table 4]

[ Table 5]

In comparative examples 5 and 7 which did not contain the compound represented by the general formula (1), the moldability was poor because the hardness was low when heated. In comparative examples 6 and 8, reflow resistance was poor and flame retardancy did not reach V-0.

In comparative examples 1 to 4 in which no specific curing agent was used, the spiral flow was small and the moldability was poor as compared with examples 1 to 4. In addition, in comparative examples 1 to 4 in which no specific curing agent was used, reflow resistance of the Cu lead frame (particularly 72h and 96h) was slightly inferior to that of examples 1 to 4 in which a specific curing agent was used.

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

The disclosure of Japanese patent application 2016-091768 filed on 28/4/2016 is hereby incorporated by reference in its entirety into the present specification.

All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as when each document, patent application, and technical standard is specifically and individually described.

Claims

1. An epoxy resin composition comprising:

a curing agent comprising at least 1 selected from the group consisting of a biphenylene type phenol aralkyl resin, a phenol aralkyl resin and a triphenylmethane type phenol resin,

the epoxy equivalent of the epoxy resin is 255 g/eq-270 g/eq,

R₁each independently represents a hydrogen atom or a C1-6 monovalent hydrocarbon group, R₂Represents a substituent represented by the formula (a), m represents a number of 0 to 20, p represents 0.9 to 2.0, R₃Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

2. The epoxy resin composition of claim 1, further comprising a curing accelerator.

3. The epoxy resin composition according to claim 2, wherein the curing accelerator comprises an adduct of a tertiary phosphine compound and a quinone compound.

4. The epoxy resin composition according to any one of claims 1 to 3, further comprising an inorganic filler.

5. The epoxy resin composition according to claim 4, wherein the content of the inorganic filler is 60 to 95% by mass.

6. The epoxy resin composition according to any one of claims 1 to 3, further comprising a coupling agent.

7. The epoxy resin composition of claim 6, wherein the coupling agent comprises a silane coupling agent having a secondary amino group.

8. An electronic component device, comprising:

element, and

a cured product of the epoxy resin composition according to any one of claims 1 to 7, which seals the element.