JP2014005405A - Sealing epoxy resin molding material and electronic part device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing epoxy resin molding material which is excellent in both reflow resistance and flowability, and an electronic part device including an element sealed by the sealing epoxy resin molding material.SOLUTION: A sealing epoxy resin molding material includes (A) an epoxy resin, (B) a hardener, (C) a hardening accelerator, (D) an inorganic filler, and (E) a polycyclic aromatic compound, as an adhesion improver, including a nitrogen atom in a ring structure and having a hydroxy group.

Description

  The present invention relates to an epoxy resin molding material for sealing and an electronic component device.

  With recent reduction in size, weight, and performance of electronic devices, mounting density has been increasing. As a result, the electronic component apparatus has been changed from a conventional pin insertion type to a surface mount type package. Surface-mounted ICs, LSIs, etc. are thin and small packages in order to increase the mounting density and reduce the mounting height. For this reason, the area occupied by the package of the element has increased, and the thickness of the package has become very thin. Further, the surface mounting type package is different in mounting method from the conventional pin insertion type. That is, when the pins are attached to the wiring board, the conventional pin insertion type package is soldered from the back surface of the wiring board after the pins are inserted into the wiring board, so that the package is not directly exposed to high temperature. However, in the surface mount type package, the entire electronic component device is processed by a solder bus, a reflow device, or the like, so that the package is directly exposed to a soldering temperature (reflow temperature). As a result, when the package absorbs moisture, moisture due to moisture absorption rapidly expands during soldering, and the generated vapor pressure acts as a peeling stress, causing peeling between the element and lead frame inserts and the sealing material. In some cases, package cracks may occur and electrical characteristics may be poor. For this reason, development of the sealing material excellent in solder heat resistance (reflow resistance) is desired.

  In order to meet these demands, various studies have been made on epoxy resins as main materials. However, it has been difficult to balance physical properties by improving the epoxy resin alone, resulting in a decrease in heat resistance due to low moisture absorption and a decrease in curability associated with improved adhesion. Therefore, various epoxy resin modifiers have been studied from the above background.

  As an example of the modifier, attention is focused on improving the adhesion with an insert such as an element lead frame, and the use of a silane coupling agent is being studied. Specifically, an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent (for example, see Patent Document 1), and a sulfur atom-containing silane coupling agent for the purpose of further improving adhesion (for example, Patent Document 2). Use) is under consideration.

JP-A-11-147939 JP 2000-103940 A

  However, when an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent is used, the effect of improving adhesiveness may not be sufficient. In particular, the amino group-containing silane coupling agent described in Patent Document 1 has high reactivity, and when used in an epoxy resin molding material for sealing, fluidity when sealing is lowered. Furthermore, there is a problem in handling properties such as gelation of the silane coupling agent itself. Further, when the sulfur atom-containing silane coupling agent described in Patent Document 2 is used, the effect of improving the adhesion with noble metals such as Ag and Au is not sufficient, and the effect of improving the reflow resistance is also insufficient. .

  As described above, an epoxy resin molding material for sealing that sufficiently satisfies both reflow resistance and fluidity has not been obtained. The present invention has been made in view of such circumstances, and an electronic component device including an epoxy resin molding material for sealing excellent in both reflow resistance and fluidity, and an element sealed with the epoxy resin molding material for sealing It is a problem to provide.

  In order to solve the above-mentioned problems, the present invention provides an electronic component device including an epoxy resin molding material for sealing containing an adhesion improver having a specific structure and an element sealed with the epoxy resin molding material for sealing. provide. More specifically, it is as follows.

  (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, and (E) a nitrogen atom in the ring structure as an adhesion improver, and hydroxy An epoxy resin molding material for sealing containing a polycyclic aromatic compound having a group.

  The epoxy resin molding material for sealing according to <1>, wherein the (E) adhesion improver includes at least one selected from the group consisting of a quinoline compound, an isoquinoline compound, and a quinoxaline compound having a hydroxy group.

  The epoxy resin molding material for sealing according to <1>, wherein the (E) adhesion improver contains at least one quinoline compound having a hydroxy group.

  <1>-<3> An electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing of any one of <3>.

  ADVANTAGE OF THE INVENTION According to this invention, an electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing excellent in both reflow resistance and fluidity | liquidity and the said epoxy resin molding material for sealing can be provided. . Therefore, its industrial value is great.

  In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, in this specification, the amount of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.

  The sealing epoxy resin molding material of the present invention includes (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, and (E) an adhesion improver. A polycyclic aromatic compound having a nitrogen atom in the ring structure and having a hydroxy group. The epoxy resin molding material for sealing may contain other components as necessary.

(E) Adhesion improver The adhesion improver contained in the sealing epoxy resin molding material of the present invention is a polycyclic aromatic compound having a nitrogen atom in the ring structure and a hydroxy group. The adhesion improver may be used alone or in combination of two or more.
By including the adhesion improver, an epoxy resin molding material for sealing excellent in both reflow resistance and fluidity can be obtained as shown in the results of Examples described later. On the other hand, an aromatic compound such as phenol, resorcinol and 2-naphthol which do not contain a nitrogen atom, hydroxypyridine which is not a polycyclic aromatic compound, and a polycyclic aromatic compound which does not contain a hydroxy group such as 2-methylquinoline When used in place of the property improver, the adhesiveness is not sufficiently improved, and the effect of improving the reflow resistance is not sufficient.

  The reason why the effect of the present invention can be obtained by including the adhesion improver is not clear, but the hydroxy group in the adhesion improver is bonded to the epoxy resin in the epoxy resin molding material for sealing, and further nitrogen. It is assumed that the polycyclic aromatic moiety containing atoms strongly interacts with the metal surface.

  The polycyclic aromatic part of the adhesion improver is not particularly limited as long as the effect of the present invention is achieved. Specific examples include indole, isoindole, purine, quinoline, isoquinoline, quinoxaline, quinolidine, cinnoline, pteridine, acridine, carbazole, naphthalidine, phthalidine and the like.

  Especially, it is preferable that the number of the nitrogen atoms contained in the ring structure of the said adhesive improvement agent is 1 or 2 from a viewpoint of industrial availability, compatibility, and fluidity | liquidity. In addition, from the viewpoint of reflow resistance and fluidity, the number of hydroxy groups contained in the adhesion improver is preferably 1 or 2, and more preferably 2.

  Therefore, the adhesion improver preferably contains at least one selected from the group consisting of a quinoline compound, an isoquinoline compound and a quinoxaline compound having a hydroxy group. Especially, it is preferable that the said adhesive improvement agent contains at least 1 sort (s) of the quinoline compound which has a hydroxyl group from a viewpoint of reflow resistance improvement.

  Specific examples of the adhesion improver include 2,4-quinolinediol, 2-hydroxyquinoline, 4-methyl-2-quinolinol, 2-methyl-4-quinolinol, and 2,4-dimethyl-7-quinolinol. 5,7-dimethyl-8-quinolinol, 1-hydroxyisoquinoline, 5-isoquinolinol, isoquinolin-6-ol, isoquinoline-1,5-diol, 2,3-quinoxaline diol, 2-hydroxyquinoxaline, etc. .

In addition to the hydroxy group, the adhesion improver may contain an aliphatic hydrocarbon group such as a methyl group, an ethyl group, or a butyl group, or an aromatic hydrocarbon group such as a phenyl group as a substituent. When the adhesion improver contains a substituent other than a hydroxy group, a methyl group or a phenyl group is preferable.
The molecular weight of the adhesion improver is not particularly limited, but is preferably 120 to 250 and more preferably 145 to 200 from the viewpoint of fluidity and reflow resistance.
The hydroxyl equivalent of the adhesion improver is not particularly limited, but is preferably 60 to 250, more preferably 72 to 200 from the viewpoints of moldability and reflow resistance.

The content of the adhesion improver in the epoxy resin molding material for sealing is not particularly limited, but is preferably 0.5% by mass to 20% by mass with respect to the total amount of the epoxy resin from the viewpoint of moldability and adhesiveness. 1.0 mass% to 15 mass% is more preferable, and 2 mass% to 10 mass% is more preferable. There exists a tendency for reflow resistance to improve more that the content rate with respect to the total amount of the epoxy resin of the said adhesive improvement agent is 0.5 mass% or more. Moreover, there exists a tendency which can suppress generation | occurrence | production of shaping | molding defects, such as a void, as it is 20 mass% or less. Furthermore, among the above preferred ranges, the greater the content, the more the adhesiveness tends to improve, and the reflow resistance tends to improve.

Whether or not the adhesion improver is contained in the sealing epoxy resin molding material can be confirmed, for example, by measuring the mass spectrum of the solvent extract.

(A) Epoxy resin The epoxy resin molding material for sealing contains at least one epoxy resin. The said epoxy resin may be what is generally used for the epoxy resin molding material for sealing, and there is no restriction | limiting in particular. Of these, one containing two or more epoxy groups in one molecule is preferable. Specifically, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and other phenol compounds and α-naphthol, β-naphthol, Novolak resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of naphthol compounds such as dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst A novolak-type epoxy resin obtained by epoxidizing the above-mentioned phenol compound and an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde by condensation or cocondensation under an acidic catalyst. Triphenylmethane type epoxy resin obtained by epoxidizing the obtained triphenylmethane type phenolic resin; diglycidyl ether such as alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol A, bisphenol F, bisphenol S, biphenol, thiodiphenol Epoxy resin; biphenyl type epoxy resin that is diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted biphenol; stilbene type epoxy resin; hydroquinone type epoxy resin; by reaction of polybasic acid such as phthalic acid and dimer acid with epichlorohydrin Obtained glycidyl ester type epoxy resin; Glycidyl amine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin; Dicyclopentadiene Dicyclopentadiene type epoxy resin obtained by epoxidizing a co-condensation resin of a phenol compound; naphthalene type epoxy resin having a naphthalene ring; synthesized from at least one of a phenol compound and a naphthol compound and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Phenol / aralkyl type epoxy resins obtained by epoxidizing phenol / aralkyl resins, naphthol / aralkyl resins, etc .; aralkyl type epoxy resins such as naphthol / aralkyl type epoxy resins; trimethylolpropane type epoxy resins; terpene modified epoxy resins; A linear aliphatic epoxy resin obtained by oxidizing a peracid with a peracid such as peracetic acid; an alicyclic epoxy resin, and the like. These epoxy resins may be used alone or in combination of two or more.

  Among them, the epoxy resin is a biphenyl type epoxy resin which is diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted biphenol (for example, trade name: YX manufactured by Mitsubishi Chemical Corporation) from the viewpoint of compatibility between fluidity and curability. -4000, YL-6121H, etc.). Further, from the viewpoint of curability, it is preferable to contain a novolac type epoxy resin (for example, trade name: ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.). Moreover, it is preferable to contain the dicyclopentadiene type epoxy resin (for example, brand name: HP-7200 etc. by DIC Corporation) from a low hygroscopic viewpoint. Moreover, it is preferable to contain the naphthalene type epoxy resin (For example, Nippon Kayaku Co., Ltd. brand name: NC-7300 etc.) from a heat resistant and low curvature viewpoint. Further, from the viewpoint of compatibility between fluidity and flame retardancy, a bisphenol F type epoxy resin which is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol F (for example, trade name YSLV- manufactured by Nippon Steel Chemical Co., Ltd.) 80XY and the like). From the viewpoint of compatibility between fluidity and reflowability, a thiodiphenol-type epoxy resin which is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted thiodiphenol (for example, trade name: manufactured by Nippon Steel Chemical Co., Ltd .: YSLV-120TE etc.) are preferably contained. From the standpoint of achieving both curability and flame retardancy, phenol aralkyl is an epoxidized phenol aralkyl resin synthesized from alkyl-substituted, aromatic ring-substituted or unsubstituted phenol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl. Type epoxy resin (for example, Nippon Kayaku Co., Ltd. trade name NC-2000L, NC-3000S, CER-3000L, etc.) is preferably contained. From the viewpoint of both storage stability and flame retardancy, a naphthol / aralkyl type epoxy resin obtained by epoxidizing a naphthol / aralkyl resin synthesized from alkyl-substituted, aromatic ring-substituted or unsubstituted naphthols and dimethoxyparaxylene (for example, , Nippon Steel Chemical Co., Ltd. trade name ESN-375, ESN-175, etc.). Further, from the viewpoint of improving curability and Tg, a triphenylmethane type epoxy resin synthesized from phenol and salicylaldehyde (for example, trade name: EPPN-502H manufactured by Nippon Kayaku Co., Ltd.) is preferable.

  In addition to the above, from the viewpoint of low warpage, dihydroanthracene type epoxy resin (for example, trade name: YX-8800 manufactured by Mitsubishi Chemical Corporation) which is diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted anthracenes, From the viewpoint of the balance between reflow resistance, curability and fluidity, it is preferable to use a methoxynaphthalene type epoxy resin (such as DIC Corporation trade name HP-5000).

  The epoxy resin contained in the epoxy resin molding material for sealing of the present invention can be selected and used according to the purpose and production conditions. For example, a biphenylene skeleton-containing phenol / aralkyl epoxy resin, a methoxynaphthalene epoxy resin, a dicyclopentadiene epoxy resin, or the like can be used alone or in combination.

  When the epoxy resin contained in the epoxy resin molding material for sealing of the present invention includes the epoxy resin exemplified above, the content of the exemplified epoxy resin is 20% by mass or more in the total amount of the epoxy resin in order to exert its performance. It is preferable to be 30% by mass or more, and more preferably 50% by mass or more.

  The content of the epoxy resin as a whole is preferably 0.4% by mass to 28% by mass in the epoxy resin molding material for sealing from the viewpoint of balance of various properties such as moldability, reflow resistance and electrical reliability. 1.1 mass%-26 mass% are more preferable. When the content of the epoxy resin in the epoxy resin molding material for sealing is 28% by mass or less, the reflow resistance tends to be kept good. Moreover, there exists a tendency for fluidity | liquidity to be kept favorable as it is 0.4 mass% or more.

The epoxy equivalent of the epoxy resin is not particularly limited. Among these, from the viewpoint of balance of various properties such as moldability, reflow resistance and electrical reliability, it is preferably 100 to 1000 (g / eq), more preferably 150 to 500 (g / eq).
The softening point or melting point of the epoxy resin is not particularly limited. Among these, from the viewpoint of moldability and reflow resistance, it is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability at the time of producing an epoxy resin molding material for sealing, it is more preferably 50 ° C. to 130 ° C. .

(B) Curing agent The epoxy resin molding material for sealing contains at least one curing agent. The said hardening | curing agent may be what is generally used for the epoxy resin molding material for sealing, and there is no restriction | limiting in particular. Specifically, a group consisting of phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, thiodiphenol, aminophenol and the like, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene A novolak-type phenol resin obtained by condensing or co-condensing at least one selected from formaldehyde or acetaldehyde with an acidic catalyst; a phenol compound and a compound having an aldehyde group such as benzaldehyde or salicylaldehyde as an acidic catalyst A triphenylmethane type phenol resin obtained by condensation or cocondensation below; at least one selected from the group consisting of a phenol compound and a naphthol compound, and dimethoxyparaxylene or Phenol / aralkyl resins synthesized from bis (methoxymethyl) biphenyl; Aralkyl-type phenol resins such as naphthol / aralkyl resins; Copolymeric phenols in which the phenol novolac structure and the phenol / aralkyl structure are randomly, block, or alternately repeated -Aralkyl resin; paraxylylene modified phenol resin; metaxylylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; dicyclopentadiene modified phenol resin; cyclopentadiene modified phenol resin; These curing agents may be used alone or in combination of two or more.

  Among them, from the viewpoint of fluidity, flame retardancy, and reflow resistance, phenol aralkyl resins (for example, trade name MEH-7851, manufactured by Meiwa Kasei Co., Ltd., trade name: XLC, etc. manufactured by Mitsui Chemicals) and naphthol aralkyl are used. Resins (for example, trade names SN-475 and SN-170 manufactured by Nippon Steel Chemical Co., Ltd.) are preferable. From the viewpoint of low hygroscopicity, dicyclopentadiene-modified phenolic resins (for example, trade name: DPP manufactured by Nippon Petrochemical Co., Ltd.) are preferable. Further, from the viewpoint of curability, a novolak type phenol resin (for example, trade name: H-4 manufactured by Meiwa Kasei Co., Ltd.) is preferable. The curing agent preferably contains at least one of these phenol resins.

Among the curing agents, the phenol / aralkyl resin and the naphthol / aralkyl resin are preferably preliminarily mixed with acenaphthylene from the viewpoint of imparting flame retardancy. Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Further, instead of acenaphthylene, a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins can be used. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out only by heat without using a catalyst. In this case, the polymerization temperature is preferably 80 ° C to 160 ° C, and more preferably 90 ° C to 150 ° C. The softening point of the resulting polymer of acenaphthylene or the polymer of acenaphthylene and another aromatic olefin is preferably 60 ° C to 150 ° C, more preferably 70 ° C to 130 ° C.
When the polymer has a softening point of 60 ° C. or higher, seepage during molding tends to be suppressed and moldability tends to be improved. Moreover, it exists in the tendency for compatibility with an epoxy resin and a hardening | curing agent to improve that it is 150 degrees C or less.

Examples of other aromatic olefins to be copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, and alkyl-substituted products thereof. In addition to the above-mentioned aromatic olefins, aliphatic olefins can be used in combination as long as the effects of the present invention are not hindered. Examples of the aliphatic olefin include (meth) acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid and esters thereof.
The use amount of these aliphatic olefins is preferably 20% by mass or less, more preferably 9% by mass or less, based on the total amount of the polymerization monomers.

As a method of premixing part or all of the curing agent with acenaphthylene, the curing agent and acenaphthylene are finely pulverized and mixed in a solid state with a mixer or the like, or both components are uniformly dissolved in a solvent that dissolves them. After that, the method can be performed by a method of removing the solvent, a method of melt-mixing both at a temperature equal to or higher than the softening point of at least one of the curing agent and acenaphthylene. Among them, the melt mixing method is preferable because a uniform mixture can be obtained and impurities are hardly mixed.
A premix (acenaphthylene-modified curing agent) is produced by the above method. The temperature at the time of melt mixing is not limited as long as it is higher than the softening point of at least one of the curing agent and acenaphthylene, but is preferably 100 ° C to 250 ° C, more preferably 120 ° C to 200 ° C. The time for melt mixing is not particularly limited as long as the two are uniformly mixed, but is preferably 1 hour to 20 hours, and more preferably 2 hours to 15 hours. When the curing agent and acenaphthylene are premixed, the acenaphthylene may polymerize or react with the curing agent during mixing.

  When the epoxy resin molding material for sealing contains the phenol / aralkyl resin exemplified above, naphthol / aralkyl resin, dicyclopentadiene modified phenol resin, novolac type phenol resin, the content of these exemplified phenol resins is In order to exhibit performance, it is preferable to set it as 30 mass% or more in the whole quantity of hardening | curing agent, and 50 mass% or more is more preferable.

  Any one of the above exemplified curing agents may be used alone, or two or more may be used in combination. The content of the above exemplified curing agents (the total when two or more are used) is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 80% by mass or more in the total amount of the curing agent. preferable.

The hydroxyl equivalent of the curing agent is not particularly limited. Among them, from the viewpoint of balance of various properties such as moldability, reflow resistance and electrical reliability, it is preferably 70 to 1000 (g / eq), more preferably 80 to 500 (g / eq). .
The softening point or melting point of the curing agent is not particularly limited. Among these, from the viewpoint of moldability and reflow resistance, it is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when producing an epoxy resin molding material for sealing, it is more preferably 50 ° C. to 130 ° C. .

  In the sealing epoxy resin molding material, the equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the epoxy group (number of hydroxyl groups in curing agent / in epoxy resin) The number of epoxy groups is not particularly limited. In order to suppress each unreacted component to be small, 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 molding material for sealing which is more excellent in moldability and solder reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

(C) Curing accelerator The epoxy resin molding material for sealing contains at least one curing accelerator. As a hardening accelerator, what is generally used with the epoxy resin molding material for sealing may be used, and there is no limitation in particular. Specifically, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 5,6-dibutylamino-1, Cycloamidine compounds such as 8-diazabicyclo [5.4.0] undec-7-ene; these cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2 , 3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc. Compound having intramolecular polarization formed by adding a compound having π bond such as quinone compound, diazophenylmethane, phenol resin, etc .; benzyldimethylamine, trie Tertiary amine compounds such as noramine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; derivatives of these tertiary amine compounds; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazole compounds such as heptadecylimidazole; derivatives of these imidazole compounds; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; A phosphorus compound having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, or a phenol resin to the compound; Tetra-substituted phosphonium / tetra-substituted borate such as nylphosphonium tetraphenyl borate, tetraphenylphosphonium ethyl triphenyl borate, tetrabutylphosphonium tetrabutyl borate; 2-ethyl-4-methylimidazole / tetraphenyl borate, N-methylmorpholine / tetraphenyl Examples thereof include tetraphenylboron salts such as borates; derivatives of these tetrasubstituted phosphonium / tetrasubstituted borates and tetraphenylboron salts. These curing accelerators may be used alone or in combination of two or more.

Among these, the curing accelerator is preferably an adduct of a tertiary phosphine compound and a quinone compound from the viewpoint of curability and fluidity, and an adduct of triphenylphosphine and benzoquinone or an adduct of tributylphosphine and benzoquinone. More preferred. From the viewpoint of storage stability, an adduct of a cycloamidine compound and a phenol resin is preferable, and a novolak-type phenol resin salt of diazabicycloundecene is more preferable.
60 mass% or more is preferable in the hardening accelerator whole quantity, and, as for the content rate of the hardening accelerator illustrated above, 80 mass% or more is more preferable.

  There is no restriction | limiting in particular as a tertiary phosphine used for the said adduct of a tertiary phosphine and a quinone compound. Specifically, 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, tris (4-ethoxyphenyl) Tertiary phosphine having an aryl group of phosphines, and the like. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferable.

  Moreover, there is no restriction | limiting in particular as a quinone compound used for the adduct of a tertiary phosphine and a quinone compound. Specific examples include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. From the viewpoint of moisture resistance or storage stability, p-benzoquinone is preferred.

  The content of the curing accelerator is not particularly limited as long as the effect of promoting the curing is achieved, but is 0 with respect to 100 parts by mass of the total amount of (A) epoxy resin and (B) curing agent. 1 mass part-10 mass parts are preferable, and 0.3 mass part-5 mass parts are more preferable. When it is 0.1 part by mass or more, it can be cured in a shorter time. Further, when the amount is 10 parts by mass or less, the curing rate is prevented from becoming too fast, and a better molded product tends to be obtained.

(D) Inorganic filler The said epoxy resin molding material for sealing contains at least 1 sort (s) of an inorganic filler. By including the inorganic filler, effects such as moisture absorption suppression, linear expansion coefficient reduction, thermal conductivity improvement, and strength improvement can be obtained. The inorganic filler may be one generally used for an epoxy resin molding material for sealing, and is not particularly limited. Specifically, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, fosterite, steatite, spinel, mullite , Powders such as titania, or beads formed by spheroidizing these, glass fibers, and the like. These inorganic fillers may be used alone or in combination of two or more.
Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient. Alumina is preferred from the viewpoint of high thermal conductivity. The shape of the inorganic filler is preferably spherical from the viewpoint of fluidity during molding and mold wear.
As the inorganic filler, spherical fused silica is particularly preferable from the viewpoint of a balance between cost and performance.

The average particle diameter of the inorganic filler is not particularly limited. Among these, from the viewpoint of moldability, the thickness is preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm. In addition, the average particle diameter of an inorganic filler is measured as a volume average particle diameter using a laser diffraction scattering system particle size distribution measuring apparatus.
The specific surface area of the inorganic filler is not particularly limited. Among them from the viewpoints of moldability and ^strength, is preferably 0.5m ² / g~12m 2 / ^g, and more preferably 1m ² / g~5m 2 / g. The specific surface area of the inorganic filler is measured from the nitrogen adsorption ability at 77K according to JIS Z 8830.

  The content of the inorganic filler is not particularly limited as long as the effect of the present invention is achieved. Among these, from the viewpoint of improvement in flame retardancy, moldability, hygroscopicity and strength, and reduction in linear expansion coefficient, 70% by mass to 95% by mass in the epoxy resin molding material for sealing is preferable. From the viewpoint of reducing the coefficient, 85% by mass to 95% by mass is more preferable. There exists a tendency for a flame retardance and reflow resistance to improve that the content rate of an inorganic filler is 70 mass% or more. Moreover, there exists a tendency which is excellent in fluidity | liquidity in it being 95 mass% or less.

(Other ingredients)
The sealing epoxy resin molding material may contain components such as a coupling agent, an anion exchanger, an adhesion promoter, a release agent, a flame retardant, a colorant, a thermoplastic resin, and a stress relaxation agent as necessary. Good.

  The sealing epoxy resin molding material can contain a coupling agent as necessary from the viewpoint of improving the adhesion between the resin component and the inorganic component in the molding material. As the coupling agent, a silane coupling agent is preferable from the viewpoint of handling properties and balance of various properties. Specific examples include various alkoxysilane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, phenylsilane, ureidosilane, methacrylsilane, and vinylsilane. The kind and number of organic functional groups other than the alkoxysilyl group and alkoxysilyl group in the silane coupling agent can be selected as necessary.

  The sealing epoxy resin molding material may contain a conventionally known coupling agent other than the silane compound from the viewpoint of improving the adhesion between the resin component and the inorganic component in the molding material. Examples of coupling agents other than silane compounds include titanate coupling agents, aluminum chelate compounds, and aluminum / zirconium compounds. These coupling agents may be used alone or in combination of two or more.

  When the sealing epoxy resin molding material contains a coupling agent, the total content is preferably 0.06% by mass to 2% by mass in the sealing epoxy resin molding material from the viewpoints of moldability and adhesiveness. 0.1 mass%-0.75 mass% are more preferable, and 0.2 mass%-0.7 mass% are still more preferable. There exists a tendency for adhesiveness to improve more that the total content rate is 0.06 mass% or more. Moreover, there exists a tendency which can suppress generation | occurrence | production of shaping | molding defects, such as a void, as it is 2 mass% or less.

  The sealing epoxy resin molding material may contain an anion exchanger as required from the viewpoint of improving the moisture resistance and high temperature storage characteristics of the sealed element. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Specific examples include hydrotalcites and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. These anion exchangers may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (I) is preferable.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (I)
In formula (I), 0 <X ≦ 0.5, and m represents a positive number.

  When the sealing epoxy resin molding material contains an anion exchanger, the content of the anion exchanger is not particularly limited as long as it is a sufficient amount to capture anions such as halogen ions. Especially, 0.1 mass part-30 mass parts are preferable with respect to 100 mass parts of (A) epoxy resins, and 1 mass part-5 mass parts are more preferable.

  From the viewpoint of further improving the adhesiveness, the sealing epoxy resin molding material can use a compound other than the adhesion improver as an adhesion promoter as necessary. Specifically, derivatives such as imidazole, triazole, tetrazole, triazine, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline and the like, derivatives thereof, aliphatic acid amide compounds, dithiocarbamates And thiadiazole derivatives. These adhesion promoters may be used alone or in combination of two or more.

  The sealing epoxy resin molding material may contain a release agent as necessary. Examples of the release agent include oxidized or non-oxidized polyolefin, carnauba wax, montanic acid ester, montanic acid, stearic acid, and the like. These release agents may be used alone or in combination of two or more. Examples of the oxidized or non-oxidized polyolefin include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as trade name H4 manufactured by Hoechst Corporation, PE, and PED series.

  When the epoxy resin molding material for sealing contains a release agent, the content of the release agent is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the (A) epoxy resin, More preferably, it is 0.1-5 mass parts. There exists a tendency for favorable mold release property to be acquired as the said content is 0.01 mass part or more. Moreover, there exists a tendency for adhesiveness to improve that it is 10 mass parts or less.

  The said epoxy resin molding material for sealing can contain a conventionally well-known flame retardant as needed from a viewpoint of the flame retardance improvement of a molding material. Specifically, red phosphorus and phosphorus coated with inorganic materials such as brominated epoxy resin, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, and zinc oxide, and / or thermosetting resins such as phenol resin. Phosphorus compounds such as acid esters, melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, Examples thereof include magnesium hydroxide and a composite metal hydroxide represented by the following composition formula (II).

^{_{p (M 1 a O b)}} · q (M 2 c O d) · m (H 2 O) (II)
In the formula (VI), M ¹ and M ² represent different metal elements, and a, b, c, d, p, q, and m represent positive numbers.

M ¹ and M ² in the above formula (II) is not particularly limited as long as the different metal element from each other. From the viewpoint of flame retardancy, M ¹ is selected from metal elements belonging to the third period metal element, group IIA alkaline earth metal element, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA M ² is preferably selected from Group IIIB to IIB transition metal elements, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is iron. More preferably, it is selected from cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferable that M ¹ is magnesium and M ² is zinc or nickel. The molar ratio of p and q is not particularly limited. It is preferable that p / q is 1/99 to 1/1.
The metal element is classified into a long-period periodic table in which the typical element is the A group and the transition element is the B group (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987). (Reduced plate 30th printing).

  Examples of other flame retardants include compounds containing metal elements such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. These flame retardants may be used alone or in combination of two or more.

  When the sealing epoxy resin molding material contains a flame retardant, the content of the flame retardant is not particularly limited. Especially, 1-30 mass parts is preferable with respect to 100 mass parts of (A) epoxy resin, and 2-15 mass parts is more preferable.

  The sealing epoxy resin molding material may contain a colorant such as carbon black, organic dye, organic pigment, titanium oxide, red lead, bengara and the like. Further, as other additives, polyphenylene ether, thermoplastic resins such as indene oligomers which are copolymer resins of indenes such as indene and alkylindene, and styrenes and phenols such as styrene and alkylstyrene, silicone oil Or a stress relaxation agent such as silicone rubber powder can be included as required.

  The sealing epoxy resin molding material can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general method, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, and then cooled and pulverized. For example, a predetermined amount of the above-mentioned components can be uniformly stirred and mixed, and can be obtained by a method such as kneading, cooling, and pulverizing with a kneader, roll, extruder, etc. that have been heated to 70 to 140 ° C. in advance. . It is easy to use if it is tableted with dimensions and mass that match the molding conditions.

  The sealing epoxy resin molding material is preferably a solid at normal temperature and pressure. There is no restriction | limiting in the shape of a solid, Any shapes, such as a powder form, a granular form, and a tablet form, may be sufficient.

<Electronic component device>
The electronic component device of the present invention includes an element sealed with the sealing epoxy resin molding material, and includes other components as necessary.
As an electronic component device including an element sealed with the sealing epoxy resin molding material, a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, a semiconductor chip, a transistor, a diode An electronic component device in which an active element such as a thyristor and an element such as a passive element such as a capacitor, a resistor, and a coil are mounted and a necessary portion is sealed with the sealing epoxy resin molding material.

  As a specific example of an electronic component device, a semiconductor element is fixed on a lead frame, and after connecting a terminal part and a lead part of an element such as a bonding pad by wire bonding or a bump, the sealing epoxy resin molding material DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outlet Package) ), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc. TCP (Tape Carrier Package) in which the semiconductor chip connected to the rear with a bump is sealed with the sealing epoxy resin molding material; wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module, hybrid in which active elements such as connected semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the above-mentioned epoxy resin molding material IC, multichip module; the element is mounted on the surface of the organic substrate on which the terminals for connecting the wiring board are formed on the back surface, the element and the wiring formed on the organic substrate are connected by bump or wire bonding, and then the sealing BGA with elements sealed with epoxy resin molding material (Ball Grid Array), CSP (Chip Size Package), and the like. Moreover, the epoxy resin molding material for sealing can also be used effectively for a printed circuit board.

  As a method for sealing an element using the sealing epoxy resin molding material, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used. The conditions for sealing the element can be appropriately selected according to the configuration of the sealing epoxy resin molding material.

  EXAMPLES Next, although an Example demonstrates this invention concretely, the scope of the present invention is not limited to these Examples. Unless otherwise specified, “part” and “%” are based on mass.

[Preparation of epoxy resin molding material for sealing]
(Examples 1-9, Comparative Examples 1-8)
The following components were blended in the amounts (unit: parts by mass) shown in Tables 1 to 4 below, and roll kneading was carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. Examples 1 to 9 and Comparative Example 1 8 to 8 epoxy resin molding materials for sealing were prepared. Note that the blank in the table represents “no formulation”.

(A) The following was used as an epoxy resin.
Epoxy resin 1: epoxy equivalent 241 with a softening point of 96 ° C. Biphenylene skeleton-containing phenol aralkyl type epoxy resin (trade name CER-3000L, manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 2: Methoxynaphthalene type epoxy resin having an epoxy equivalent of 250 and a softening point of 58 degrees (trade name HP-5000, manufactured by DIC Corporation)
Epoxy resin 3: epoxy equivalent 258, dicyclopentadiene type epoxy resin having a softening point of 60 degrees (trade name HP-7200, manufactured by DIC Corporation)

  (B) As the curing agent, a phenol aralkyl resin having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. (trade name: Millex XLC, manufactured by Mitsui Chemicals, Inc.) was used.

(C) As a hardening accelerator, the betaine type adduct of triphenylphosphine and p-benzoquinone was used.
(D) As the inorganic filler, spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² / g was used.

(E) As the adhesion improver, the following was used.
Adhesion improver (E) -1: 2-hydroxyquinoline Adhesion improver (E) -2: 2,4-dihydroxyquinoline

  As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane was used.

The following were used as other additives except (E).
Additive-1: Phenol Additive-2: Resorcinol Additive-3: 2-hydroxypyridine Additive-4: 2-naphthol Additive-5: 2-Methylquinoline

  As other additive components, carnauba wax and carbon black were used.

[Evaluation of epoxy resin molding material for sealing]
The characteristics of the epoxy resin molding materials for sealing produced in Examples 1 to 9 and Comparative Examples 1 to 8 were evaluated by the following characteristic tests (1) to (5). The evaluation results are shown in Tables 1 to 4 below. The epoxy resin molding material for sealing was molded by a transfer molding machine at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds unless otherwise specified. Further, if necessary, post-curing was performed at 180 ° C. for 5 hours.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, the sealing epoxy molding material was molded under the above conditions, and the flow distance (cm) was determined.
(2) Hardness under heat The epoxy resin molding material for sealing is molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D hardness meter (HD-1120 (type D )).
(3) 260 ° C. Shear Adhesive Force An epoxy resin molding material for sealing was molded into a silver-plated copper plate with a bottom diameter of 4 mm, a top diameter of 3 mm, and a height of 4 mm under the above conditions, and post-cured under the above conditions. Thereafter, using a series 4000 manufactured by Daisy Japan Co., Ltd., the shear adhesive strength (MPa) was determined at a shear rate of 50 μm / s while keeping the temperature of the copper plate at 260 ° C.
(4) Water absorption rate The disk molded in the above (2) was post-cured under the above conditions. Then, the obtained disc was left for 168 hours under the conditions of 85 ° C. and 60% RH, and the mass change before and after being left was measured. The water absorption was calculated from the measurement result by the following formula,
Water absorption rate (% by mass) = (mass of disc after being left−disc mass before being left) / mass of disc before being left × 100
(5) Reflow resistance 80 mm flat package (QFP) with external dimensions of 20 mm x 14 mm x 2 mm with 8 mm x 10 mm x 0.4 mm silicon chip (Lead frame material: copper alloy, die pad top surface and lead tip silver plating Processed product) was molded under the above conditions using an epoxy resin molding material for sealing, and post-cured under the above conditions. The obtained package was humidified for 168 hours at 85 ° C. and 85% RH. After that, reflow treatment is performed under conditions of a predetermined temperature (245 ° C., 255 ° C., 265 ° C.) and 10 seconds, the presence of cracks outside the package is visually observed, and the presence or absence of peeling inside the package is detected by an ultrasonic flaw detector (Hitachi Observation was performed with HYE-FOCUS manufactured by Construction Machinery Co., Ltd. The reflow resistance was evaluated by the total number of packages in which either cracks or peeling occurred with respect to the number of test packages (10).

  As shown in Tables 1 to 4, Comparative Examples 1 to 8 that do not contain an adhesion improver have particularly low evaluation of reflow resistance at 255 ° C. or higher and low evaluation of fluidity (spiral flow). On the other hand, Examples 1-9 which are the same as a comparative example except an adhesive improvement agent and a mixing | blending composition partly differing have favorable fluidity | liquidity and are excellent also in reflow resistance.

Claims (4)

  (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, and (E) a nitrogen atom in the ring structure as an adhesion improver, and hydroxy An epoxy resin molding material for sealing containing a polycyclic aromatic compound having a group.   The epoxy resin molding material for sealing according to claim 1, wherein the (E) adhesion improver contains at least one selected from the group consisting of a quinoline compound, an isoquinoline compound and a quinoxaline compound having a hydroxy group.   The epoxy resin molding material for sealing according to claim 1, wherein the (E) adhesion improver contains at least one quinoline compound having a hydroxy group.   An electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing of any one of Claims 1-3.