JP2017110234A - Epoxy resin molding material for sealing and electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing which can form a sealing body having excellent reflow resistance, and an electronic component device comprising an element sealed therewith.SOLUTION: An epoxy resin molding material for sealing has epoxy resin having two or more epoxy groups in one molecule, curing agent, and a carboxylic acid amide derivative having one or more phenolic hydroxyl group in one molecule. There is also provided an electronic component device comprising an element sealed with the epoxy resin molding material for sealing.SELECTED DRAWING: None

Description

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

  Conventionally, epoxy resin molding materials have been widely used in the field of sealing electronic components such as transistors and ICs. This is because the epoxy resin has a good balance of electrical properties, moisture resistance, heat resistance, mechanical properties, adhesiveness with inserts, and the like. In particular, the combination of an ortho-cresol novolac type epoxy resin and a novolac type phenol curing agent has an excellent balance between these, and has become the mainstream of the base resin of the molding material for sealing.

  With recent miniaturization, weight reduction, and high performance of electronic devices, mounting density has increased, and surface mount packages have become the mainstream in electronic component devices from conventional pin insertion types. When attaching an electronic component device to a wiring board, the conventional pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, so the package was not directly exposed to high temperatures. However, in the surface mount type package, the entire electronic component device is processed by a solder bath or a reflow device, so that the package is directly exposed to the soldering temperature. As a result, when the package absorbs moisture, moisture absorption rapidly expands during soldering, causing peeling of the adhesive interface and package cracks, resulting in a decrease in package reliability during mounting.

  As measures to solve the above problems, in order to reduce moisture absorption inside the semiconductor device, IC moisture-proof packaging, or a method of sufficiently drying the IC in advance before mounting on a wiring board is used. . However, these methods are time consuming and tend to be expensive. As another measure, there is a method of increasing the content of the filler contained in the sealing molding material (for example, see Patent Document 1). Although this method reduces moisture absorption inside the semiconductor device, there is a problem in that the fluidity of the molding material for sealing is greatly reduced. It is known that when the fluidity of the molding material for sealing is low, problems such as the occurrence of gold wire flow, voids, and pinholes may occur during molding.

Japanese Patent Laid-Open No. 06-224328

  The present invention has been made in view of such a situation, and provides an epoxy resin molding material for sealing capable of forming a sealing body excellent in reflow resistance, and an electronic component device including an element sealed thereby. Let it be an issue.

Specific means for solving the above problems are as follows.
<1> (A) An epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent, and (C) a carboxylic acid amide derivative having one or more phenolic hydroxyl groups in one molecule. This is an epoxy resin molding material for fastening.

<2> The sealing epoxy resin molding material according to <1>, wherein the content of the carboxylic acid amide derivative is 0.1% by mass or more and less than 1.0% by mass.

<3> (D) The epoxy resin molding material for sealing according to <1> or <2>, further containing a silane compound.

<4> (E) The epoxy resin molding material for sealing according to any one of <1> to <3>, further including a curing accelerator.

<5> (F) The sealing epoxy resin molding material according to any one of <1> to <4>, further including an inorganic filler.

<6> An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of <1> to <5>.

  ADVANTAGE OF THE INVENTION According to this invention, an electronic component apparatus provided with the epoxy resin molding material for sealing which can form the sealing body excellent in reflow resistance, and the element sealed by this can be provided.

<Epoxy resin molding material for sealing>
The sealing epoxy resin molding material of the present invention comprises (A) at least one epoxy resin having two or more epoxy groups in one molecule (hereinafter also simply referred to as “epoxy resin”), and (B) a curing agent. At least one kind and (C) at least one kind of carboxylic acid amide derivative having one or more phenolic hydroxyl groups in one molecule. The sealing epoxy resin molding material may further contain other components as necessary. Hereinafter, (C) a carboxylic acid amide derivative having one or more phenolic hydroxyl groups in one molecule is also simply referred to as “carboxylic amide derivative”.

  Since the epoxy resin molding material for sealing contains the carboxylic acid amide derivative in addition to the epoxy resin and the curing agent, the reflow resistance after curing is excellent. This can be considered as follows, for example. As the carboxylic acid amide group contained in the carboxylic acid amide derivative interacts with the metal, good adhesiveness is developed between the metal and the carboxylic acid amide derivative. On the other hand, the phenolic hydroxyl group contained in the carboxylic acid amide derivative reacts with the epoxy resin, and the carboxylic acid amide derivative is fixed to the cured epoxy resin. That is, the metal and the cured epoxy resin are bonded through the carboxylic acid amide derivative. Since such a bonded state has flexibility, it is presumed that the adhesiveness between the cured epoxy resin and the metal is improved even at a high temperature, and the reflow resistance after curing is excellent.

  Hereinafter, the epoxy resin molding material for sealing of the present invention will be described in detail. In addition, the numerical value range shown using "to" in this specification shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

(C) Carboxylic acid amide derivative The said epoxy resin molding material for sealing contains at least 1 sort (s) of the carboxylic acid amide derivative which has 1 or more of phenolic hydroxyl groups in 1 molecule. The carboxylic acid amide derivative is not particularly limited as long as it is a compound having at least one carboxylic acid amide group and at least one phenolic hydroxyl group in the molecule. The number of phenolic hydroxyl groups possessed by the carboxylic acid amide derivative is preferably 1 to 2 and more preferably 1 from the viewpoint of reflow resistance. The number of amide groups contained in the carboxylic acid amide derivative is preferably 1 to 2, more preferably 1 from the viewpoint of reflow resistance.

  The carboxylic acid amide derivative is, for example, a compound in which a carboxylic acid amide group is directly bonded to an aromatic ring group having a phenolic hydroxyl group, and a linking group such as an alkylene group or an arylene group is added to the aromatic ring group having a phenolic hydroxyl group. The compound which the carboxylic acid amide group couple | bonded through may be sufficient. The aromatic ring group in the aromatic ring group having a phenolic hydroxyl group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and an aromatic ring or an aliphatic ring is condensed to the aromatic ring group. It may have a cyclic polycyclic structure.

  From the viewpoint of reflow resistance, the carboxylic acid amide derivative is preferably a compound in which a carboxylic acid amide group is directly bonded to an aromatic ring group having a phenolic hydroxyl group. A compound in which a carboxylic acid amide group is directly bonded is preferable.

  When the carboxylic acid amide derivative is an embodiment in which the carboxylic acid amide group is directly bonded to the aromatic ring group having a phenolic hydroxyl group, the aromatic ring group may be bonded to the carbonyl group of the carboxylic acid amide group. An embodiment in which the nitrogen atom of the carboxylic acid amide group is bonded to the ring group may be employed. Among these, from the viewpoint of reflow resistance, it is preferable that the carbonyl group of the carboxylic acid amide group is bonded to the aromatic ring group.

  Further, when the carboxylic acid amide derivative is an embodiment in which the carboxylic acid amide group is directly bonded to the aromatic ring group having a phenolic hydroxyl group, the bonding position of the carboxylic acid amide group with respect to the bonding position of the phenolic hydroxyl group in the aromatic ring group is particularly It is not limited, and any of ortho, meta, and para positions with respect to the phenolic hydroxyl group may be used.

  The carboxylic acid amide derivative may further have other substituents other than the phenolic hydroxyl group and the carboxylic acid amide group. Examples of the other substituent include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, and an aromatic heterocyclic group. Can do. The other substituents may further have a substituent if possible. Examples of the substituent of the other substituent include a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, and an aromatic group. A heterocyclic group etc. can be mentioned.

  The substitution position of other substituents in the carboxylic acid amide derivative is not particularly limited. It may be on an aromatic ring group having a phenolic hydroxyl group or on a nitrogen atom of a carboxylic acid amide group. Further, the number of substitution of other substituents is not particularly limited.

  When the carboxamide derivative has another substituent on the nitrogen atom of the carboxamide group, the other substituent is an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. It is preferable that The number of substituents on the nitrogen atom of the carboxylic acid amide group is preferably 1 from the viewpoint of reflow resistance.

  The molecular weight of the carboxylic acid amide derivative is not particularly limited. Among these, from the viewpoint of reflow resistance, it is preferably 137 to 500, and more preferably 137 to 350. The hydroxyl equivalent of the carboxylic acid amide derivative is not particularly limited. From the viewpoint of reflow resistance, it is preferably from 76 g / eq to 500 g / eq, more preferably from 90 g / eq to 350 g / eq. Here, the hydroxyl equivalent of the carboxylic acid amide derivative means the molecular weight of the carboxylic acid amide derivative per mole of the hydroxyl group contained in the carboxylic acid amide derivative.

  The carboxylic acid amide derivative has one or more phenolic hydroxyl groups in one molecule and has both sides of the amide group (—CO—NH—) (ie, carbonyl group and It is preferably a secondary carboxylic acid amide derivative in which an aromatic hydrocarbon group having 6 to 14 carbon atoms (more preferably a phenyl group or a naphthyl group) is bonded to a nitrogen atom).

  The melting point of the carboxylic acid amide derivative is not particularly limited. For example, from the viewpoint of reflowability, the melting point of the carboxylic acid amide derivative is preferably 50 ° C. to 300 ° C., and more preferably 100 ° C. to 250 ° C.

Specific examples of the carboxylic acid amide derivative are given below, but the present invention is not limited to these.
Specific examples of the carboxylic acid amide derivative include p-acetamidophenol, salicylamide, salicylanilide, 3-hydroxy-2-naphthamide, 3-hydroxy-2-naphthanilide, 3-hydroxy-N- (1-naphthyl) -2. -Naphthamide, 3-hydroxy-2'-methyl-2-naphthanilide, 3-hydroxy-2'-methoxy-2-naphthanilide, 2'-ethoxy-3-hydroxy-2-naphthanilide, 3-hydroxy-4'-methoxy 2-naphthoanilide, 3-hydroxy-N- (2-hydroxyethyl) -2-naphthamide, 2,4-dihydroxy-N- (2-hydroxyethyl) benzamide, their positional isomers, their substituents, etc. Can be mentioned.

The content of the carboxylic acid amide derivative in the epoxy resin molding material for sealing is not particularly limited. The content of the carboxylic acid amide derivative is preferably 0.10% by mass or more and less than 1.00% by mass in the total mass of the epoxy resin molding material for sealing. When the content of the carboxylic acid amide derivative is 0.10% by mass or more, the reflow resistance tends to be further improved. Moreover, when the content of the carboxylic acid amide derivative is less than 1.00% by mass, the hardness of the formed resin cured product tends to be further improved.
Furthermore, the content of the carboxylic acid amide derivative is preferably 0.15% by mass or more, and more preferably 0.20% by mass or more, from the viewpoint of reflow resistance. In addition, the content of the carboxylic acid amide derivative is preferably 0.95% by mass or less, and more preferably 0.75% by mass or less, from the viewpoint of the hardness of the formed resin cured product.

  Moreover, the content ratio of the carboxylic acid amide derivative and the curing agent described later in the epoxy resin molding material for sealing is not particularly limited. From the viewpoint of reflow resistance and the hardness of the resin cured product to be formed, the ratio of the hydroxyl group equivalent of the carboxylic acid amide derivative to the hydroxyl equivalent of the curing agent is preferably 0.01 to 0.20, More preferably, it is 0.15.

(A) Epoxy resin The epoxy resin used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule, and is generally used for epoxy resin molding materials for sealing. It can be appropriately selected and used. Specific examples of the epoxy resin include phenol / novolak type epoxy resin, orthocresol / novolac type epoxy resin, epoxy resin having triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F And at least one selected from the group consisting of naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene, and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde. A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation under an acidic catalyst; alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol Epoxy resin which is diglycidyl ether such as A, bisphenol F, bisphenol S, biphenol, thiodiphenol; stilbene type epoxy resin; hydroquinone type epoxy resin; obtained by reaction of polybasic acid such as phthalic acid and dimer acid with epichlorohydrin Glycidyl ester type epoxy resin; Glycidylamine type epoxy resin obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin; Epoxidation product of dicyclopentadiene and phenols co-condensation resin (dicyclopentadiene type epoxy resin); Naphthalene Epoxy resin having a ring; phenol synthesized from at least one of phenols and naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Epoxy compounds of aralkyl type phenol resins such as aralkyl resins and naphthol / aralkyl resins; trimethylolpropane type epoxy resins; terpene modified epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid An alicyclic epoxy resin or the like. These may be used alone or in combination of two or more.

  Among these, 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). 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 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) from a heat resistant and low curvature viewpoint. Further, from the viewpoint of compatibility between fluidity and flame retardancy, bisphenol F type epoxy resin which is 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) is preferably contained. 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) is preferably contained. From the viewpoint of both curability and flame retardancy, phenol / aralkyl type epoxy resins synthesized from alkyl-substituted, aromatic-ring-substituted or unsubstituted phenol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl (eg Nippon Kayaku) It is preferable to contain the brand names NC-2000L, NC-3000S, CER-3000L). Also, from the viewpoint of both storage stability and flame retardancy, an epoxidized naphthol / aralkyl resin synthesized from alkyl-substituted, aromatic-ring-substituted or unsubstituted naphthols and dimethoxyparaxylene (for example, Nippon Steel Chemical Co., Ltd.) It is preferable that the product name ESN-375 and ESN-175) are contained. 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, a dihydroanthracene type epoxy resin (for example, trade name: YX-8800 manufactured by Mitsubishi Chemical Corporation) is preferable from the viewpoint of low warpage, and methoxy from the viewpoint of the balance between reflow resistance, curability and fluidity. A naphthalene type epoxy resin (trade name HP-5000 manufactured by DIC Corporation) is preferable.

  The epoxy resin molding material for sealing is, as a polyfunctional epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, thiodiphenol type epoxy resin At least one epoxy resin selected from the group consisting of epoxidized phenol / aralkyl resins, epoxidized naphthol / aralkyl resins, triphenylmethane type epoxy resins, dihydroanthracene type epoxy resins, and methoxynaphthalene type epoxy resins , Also referred to as “specific epoxy resin”).

  When the sealing epoxy resin molding material contains the specific epoxy resin, the content of the specific epoxy resin is preferably 20% by mass or more in the total amount of the epoxy resin in order to exert its performance, 30 The content is more preferably at least 50% by mass, and even more preferably at least 50% by mass.

  The said specific epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more type. When two or more specific epoxy resins are used in combination, the content of the specific epoxy resin is preferably 50% by mass or more in the total amount of the epoxy resin from the viewpoint of more effectively exhibiting the performance. More preferably, the content is at least 80% by mass, and even more preferably at least 80% by mass.

  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 g / eq to 1000 g / eq, and more preferably 150 g / eq 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, the softening point or melting point 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 50 ° C to 130 ° C. More preferably.

  The content of the epoxy resin in the sealing epoxy resin molding material is preferably 3% by mass to 15% by mass and preferably 5% by mass to 12% by mass from the viewpoints of moldability and reflow resistance. More preferred.

(B) Curing agent The epoxy resin molding material for sealing contains at least one curing agent. If the said hardening | curing agent is generally used for the epoxy resin molding material for sealing, there will be no restriction | limiting in particular. For example, selected from the group consisting of phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, thiodiphenol, aminophenol, and naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene. Selected from the group consisting of phenols and naphthols obtained by condensing or co-condensing at least one kind of a compound having an aldehyde group such as formaldehyde, benzaldehyde, and salicylaldehyde with an acidic catalyst. Aralkyl-type phenol resins such as phenol / aralkyl resins and naphthol / aralkyl resins synthesized from at least one kind and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; Copolymer-type phenol-aralkyl resin in which an enol-novolak structure and a phenol-aralkyl structure are randomly, blocked, or alternately repeated; paraxylylene-modified phenol resin; metaxylylene-modified phenol resin; melamine-modified phenol resin; terpene-modified phenol resin; Examples thereof include pentadiene-modified phenol resins; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins. These 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 names MEH-7851 and MEH-7800 manufactured by Meiwa Kasei Co., Ltd., trade name: XLC manufactured by Mitsui Chemicals) and naphthol are used. -At least 1 sort (s) chosen from the group which consists of aralkyl resin (For example, Nippon Steel Chemical Co., Ltd. brand name SN-475, SN-170) is preferable. Further, from the viewpoint of low hygroscopicity, dicyclopentadiene-modified phenolic resin (for example, trade name: DPP manufactured by Shin Nippon Petrochemical Co., Ltd.) is preferable. From the viewpoint of curability, novolak type phenol resins (for example, trade names: H-4 and H-100 manufactured by Meiwa Kasei Co., Ltd.) are preferable.

  The curing agent is at least one phenol resin selected from the group consisting of phenol-aralkyl resins, naphthol-aralkyl resins, dicyclopentadiene-modified phenol resins, and novolac-type phenol resins (hereinafter also referred to as “specific phenol resins”). It is preferable to contain.

Among the curing agents contained in the sealing epoxy resin molding material, the phenol / aralkyl resin and the naphthol / aralkyl resin are partially mixed with a polymerizable monomer such as acenaphthylene from the viewpoint of flame retardancy. Preferably it is. Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Moreover, it can also be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins instead of acenaphthylene. 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 is 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 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, esters thereof and the like.
The amount of these aliphatic olefins to be used is preferably 20% by mass or less, more preferably 9% by mass or less, based on the total amount of the polymerization monomer used for the preliminary mixing with the phenol / aralkyl resin and naphthol / aralkyl resin.

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 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 is obtained and impurities are less mixed.
The premix (acenaphthylene-modified curing agent) is produced by the above method. The melt mixing is not limited as long as the temperature is at least the softening point of at least one of the curing agent and acenaphthylene. Among these, 100 ° C to 250 ° C is preferable, and 120 ° C to 200 ° C is more preferable. Further, in the melt mixing, there is no limitation on the mixing time as long as both are mixed uniformly. Among these, 1 hour to 20 hours are preferable, and 2 hours to 15 hours are more preferable. When the curing agent and acenaphthylene are premixed, the acenaphthylene may polymerize or react with the curing agent during mixing.

  When the sealing epoxy resin molding material contains a specific phenol resin selected from the group consisting of the phenol-aralkyl resin, naphthol-aralkyl resin, dicyclopentadiene-modified phenol resin, and novolak-type phenol resin exemplified above. The content of the specific phenol resin is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent, from the viewpoint of more effectively exhibiting the performance.

  Any one of the specific phenol resins may be used alone, or two or more of them may be used in combination. When two or more kinds of the specific phenol resins are used in combination, the content is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more in the total amount of the curing agent. .

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

  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 2.0, more preferably 0.6 to 1.3. Further, in order to obtain an epoxy resin molding material for sealing excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

  Further, in the epoxy resin molding material for sealing, the equivalent ratio of (A) epoxy resin to (B) curing agent and (C) carboxylic acid amide derivative, that is, included in the total amount of the curing agent and carboxylic acid amide derivative with respect to the epoxy group The ratio of the number of hydroxyl groups (the number of hydroxyl groups of the curing agent and the carboxylic acid amide derivative / the number of epoxy groups in the epoxy resin) is not particularly limited. In order to suppress the amount of each unreacted component, it is preferably set in the range of 0.5 to 2.0, more preferably 0.6 to 1.3. Furthermore, in order to obtain a sealing epoxy resin molding material excellent in moldability and reflow resistance, it is more preferably set in a range of 0.8 to 1.2.

(D) Silane compound It is preferable that the epoxy resin molding material for sealing further contains at least one silane compound. By including a silane compound, fluidity, reflow resistance, and adhesion are further improved. The silane compound is not particularly limited as long as it is a compound having at least one silicon-carbon bond, and can be appropriately selected from compounds usually used as a silane coupling agent. The silane compound preferably has at least one functional group selected from the group consisting of epoxy groups, mercapto groups, amino groups, ureido groups, and vinyl groups.

  Examples of the silane compound include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacrylate. Roxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysila Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylethoxysilane, vinyltriacetoxysilane, γ-mercapto Propyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, isocyanatepropyltrimethoxysilane, isocyanine Topropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, triphenyl Methoxysilane, triphenylethoxysilane, triphenylsilanol, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-anilinopropyl Trimethoxysilane, γ-anilinopropyltriethoxysilane, 2-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilane Ru-N- (1,3-dimethyl-butylidene) propylamine, N- (3-triethoxysilylpropyl) phenylimine, 3- (3- (triethoxysilyl) propylamino) -N, N-dimethylpropionamide Silane compounds such as N-triethoxysilylpropyl-β-alanine methyl ester, 3- (triethoxysilylpropyl) dihydro-3,5-furandone, bis (trimethoxysilyl) benzene, 1H-imidazole, 2- Reaction of imidazole compounds such as alkylimidazole, 2,4-dialkylimidazole and 4-vinylimidazole with γ-glycidoxypropylalkoxysilane such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane Imidazole-based silane compounds And the like. These may be used alone or in combination of two or more.

  When the sealing epoxy resin molding material contains a silane compound, the content of the silane compound is 0.06% by mass or more in the total mass of the sealing epoxy resin molding material from the viewpoint of moldability and fluidity. The amount is preferably less than 2% by mass, more preferably 0.1% by mass or more and less than 0.75% by mass, and further preferably 0.2% by mass or more and less than 0.7% by mass. When the content of the silane compound is 0.06% by mass or more, the fluidity tends to be further improved. Moreover, there exists a tendency which can suppress more effectively generation | occurrence | production of molding defects, such as a void, as it is less than 2 mass%.

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

  When the sealing epoxy resin molding material contains a coupling agent other than the silane compound, the content is 0.06 in the total mass of the sealing epoxy resin molding material from the viewpoint of moldability and adhesiveness. The mass% is preferably 2% by mass or more, more preferably 0.1% by mass or more and less than 0.75% by mass, and further preferably 0.2% by mass or more and less than 0.7% by mass. When the content of the silane coupling agent is 0.06% by mass or more, the fluidity tends to be further improved. Moreover, there exists a tendency which can suppress more effectively generation | occurrence | production of molding defects, such as a void, as it is less than 2 mass%.

(E) Curing accelerator It is preferable that the epoxy resin molding material for sealing further contains at least one curing accelerator. By including a curing accelerator, reflow resistance, moldability, and curability are further improved. The curing accelerator is not particularly limited as long as it is a compound capable of accelerating the curing reaction of the epoxy resin, and can be appropriately selected from commonly used compounds. Examples of the curing accelerator include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, 5,6-dibutylamino-1,8. -Cycloamidine compounds such as diazabicyclo [5.4.0] undecene-7; these cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3 -Quinone compounds such as dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone , A compound having an intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane or phenol resin; benzyldimethylamine, Tertiary amine compounds such as liethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of these tertiary amine compounds, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazole compounds such as imidazole and 2-heptadecylimidazole; derivatives of these imidazole compounds, organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine; Phosphorus compounds having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, and phenol resin to these organic phosphine compounds Tetra-substituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate; 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetra Examples thereof include tetraphenylboron salts such as phenylborate; derivatives of these tetrasubstituted phosphonium / tetrasubstituted borates and tetraphenylboron salts. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of moldability, an adduct of a tertiary phosphine compound and a quinone compound is preferably used. There is no restriction | limiting in particular as a tertiary phosphine compound used for the adduct of a tertiary phosphine compound and a quinone compound. For example, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butyl Phenyl) phosphine, tris (isopropylphenyl) phosphine, tris (tert-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, tris (2,4,6- Aryl groups such as trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine Tertiary phosphine having the like. Of these, triphenylphosphine is preferable from the viewpoint of moldability. Moreover, there is no restriction | limiting in particular as a quinone compound used for the adduct of a tertiary phosphine compound and a quinone compound. For example, o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone and the like can be mentioned. Of these, p-benzoquinone is preferred from the viewpoints of moisture resistance and storage stability.

  When the sealing epoxy resin molding material contains a curing accelerator, the content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved. (A) epoxy resin, (B) curing agent and (C) 0.1 part by mass or more and less than 10 parts by mass is preferable with respect to 100 parts by mass in total, and 0.3 part by mass or more and 5 parts by mass Less than is more preferable. When the content of the curing accelerator is 0.1 parts by mass or more, it tends to be able to be cured in a shorter time. Moreover, when it is less than 10 mass parts, it will suppress that a cure rate becomes quick too much, and there exists a tendency for a better molded article to be obtained.

(F) Inorganic filler It is preferable that the said epoxy resin molding material for sealing further contains at least 1 sort (s) of an inorganic filler. By further including an inorganic filler, moisture absorption reduction, linear expansion coefficient reduction, thermal conductivity improvement, and strength improvement are more effectively achieved. The inorganic filler is not particularly limited as long as it is generally used for an epoxy resin molding material for sealing. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, Examples thereof include powders such as titania, beads formed by spheroidizing these, and glass fibers. These 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. Furthermore, the shape of the inorganic filler is preferably spherical from the viewpoint of fluidity during molding and mold wear. In particular, spherical fused silica is preferable from the viewpoint of a balance between cost and performance.

  When the sealing epoxy resin molding material contains an inorganic filler, the content of the inorganic filler is sealed from the viewpoint of flame retardancy improvement, moldability improvement, moisture absorption reduction, linear expansion coefficient reduction, and strength improvement. 70 mass% or more and less than 95 mass% are preferable in the total mass of the epoxy resin molding material for a resin. There exists a tendency for a flame retardance to improve more as the content rate of an inorganic filler is 70 mass% or more. Moreover, there exists a tendency for fluidity | liquidity to improve that it is less than 95 mass%.

(G) Other additives (anion exchanger)
The sealing epoxy resin molding material may contain an anion exchanger as required. By including the anion exchanger, the moisture resistance and high temperature storage characteristics of the sealed IC chip and the like are further improved. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Examples thereof include hydrotalcites and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth. These may be used alone or in combination of two or more. Among 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 the formula (I), X is a number that satisfies 0 <X ≦ 0.5, and m is 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 capable of capturing anions such as halogen ions. (A) 0.1 mass part or more and less than 30 mass parts are preferable with respect to 100 mass parts of epoxy resins, and 1 mass part or more and less than 5 mass parts are more preferable.

(Release agent)
The sealing epoxy resin molding material may contain a release agent as necessary. Examples of the releasing agent include oxidized or non-oxidized polyolefin. Specific 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, PE, and PED series manufactured by Hoechst Co., Ltd. Other release agents other than oxidized or non-oxidized polyolefins include 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.

When the sealing epoxy resin molding material contains a release agent, the content of the release agent is preferably 0.01 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the epoxy resin (A). The amount is more preferably 1 part by mass or more and less than 5 parts by mass, and further preferably 0.5 part by mass or more and less than 3 parts by mass. There exists a tendency for sufficient releasability to be acquired as it is 0.01 mass part or more. Moreover, there exists a tendency for the adhesive fall to be suppressed as it is less than 10 mass parts.
When the release agent contains an oxidized or non-oxidized polyolefin and another release agent, the content is 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) epoxy resin. Less than part by mass is preferable, and 0.5 part by mass or more and less than 3 parts by mass is more preferable.

(Flame retardants)
The epoxy resin molding material for sealing can contain a conventionally known flame retardant as necessary. Examples of flame retardants include brominated epoxy resins; inorganic substances such as antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, and zinc oxide; red phosphorus and phosphoric acid coated with thermosetting resins such as phenol resins Phosphorus compounds such as esters; nitrogen-containing compounds such as melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, cyanuric acid derivatives and isocyanuric acid derivatives; phosphorus and nitrogen-containing compounds such as cyclophosphazene; aluminum hydroxide, water Compounds containing metal elements such as magnesium oxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, and composite metal hydroxide represented by the following composition formula (II) Such as things.
^{_{p (M 1 a O b)}} · q (M 2 c O d) · r (M 3 e O f) · mH 2 O (II)
In formula (II), M ¹ , M ² and M ³ represent different metal elements, and a, b, c, d, e, f, p, q and m each independently represent a positive number. r represents 0 or a positive number.

M ¹ , M ² and M ^{3 in the} composition formula (II) are not particularly limited as long as they are different metal elements. 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, M ² is zinc or nickel, and r = 0. The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1. Further, a, b, c, d, e, and f are appropriately selected according to M ¹ , M ^2, and M ³ . 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).

  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. (A) 1 mass part or more and less than 30 mass parts are preferable with respect to 100 mass parts of epoxy resins, and 2 mass parts or more and less than 15 mass parts are more preferable.

(Colorants, etc.)
The sealing epoxy resin molding material may further contain a colorant such as carbon black, organic dye, organic pigment, titanium oxide, red lead, bengara and the like. Furthermore, as other additives, a stress relaxation agent such as silicone oil or silicone rubber powder can be blended as necessary.

<Method for producing epoxy resin molding material for sealing>
The method for producing the sealing epoxy resin molding material is not particularly limited, and any method may be used as long as various components constituting the sealing epoxy resin molding material 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. Specifically, a predetermined amount of the above-mentioned components are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, etc. that have been heated to 70 ° C. to 140 ° C., cooled, and then pulverized. Can be obtained. Moreover, it is easy to use if it is tableted with dimensions and masses that meet the molding conditions.

<Electronic component device>
The electronic component device of the present invention includes an element sealed with the sealing epoxy resin molding material. Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers and other support members, semiconductor chips, transistors, diodes, thyristors and other active elements, capacitors, resistors, coils and other passive components. Examples thereof include an electronic component device obtained by mounting an element such as an element and sealing a necessary portion with the sealing epoxy resin molding material. Specifically, as such an electronic component device, a semiconductor element is fixed on a lead frame, a terminal portion of a device such as a bonding pad and a lead portion are connected by wire bonding or bump, and then the sealing epoxy of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Out Package), which are sealed by transfer molding using a resin molding material. -Lead package, TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc. A semiconductor chip connected to a bump with a sealing epoxy resin molding material is sealed with TCP (Tape Carrier Package), wiring formed on a wiring board or glass, by wire bonding, flip chip bonding, soldering, 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, element is mounted on the surface of organic substrate with wiring board connection terminal formed on the back side, and the element and the wiring formed on the organic substrate are connected by bump or wire bonding, then the sealing BGA (B with element sealed with epoxy resin molding material ll 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.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

(Examples 1-40 and Comparative Examples 1-40)
Each component shown below is mix | blended by the mass part shown in following Table 1-Table 10, roll knead | mixing on the conditions for kneading | mixing temperature of 80 degreeC and kneading | mixing time of 10 minutes, Examples 1-40 and Comparative Examples 1-40 An epoxy resin molding material for sealing was prepared. In addition, "-" in a table | surface shows having not mix | blended.
(A) Epoxy resin Epoxy resin 1: Biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name YX-4000 manufactured by Mitsubishi Chemical Corporation)
Epoxy resin 2: Phenol aralkyl type epoxy resin containing a biphenylene skeleton having an epoxy equivalent of 240 and a softening point of 96 ° C. (trade name CER-3000L manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 3: phenol equivalent 238, phenol aralkyl type epoxy resin having a softening point of 55 ° C. (trade name NC-2000L manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 4: Ortho-cresol novolak type epoxy resin having an epoxy equivalent of 202 and a softening point of 60 ° C. (trade name N-660, manufactured by DIC Corporation)
Epoxy resin 5: naphthalene-modified novolac type epoxy resin having an epoxy equivalent of 250 and a softening point of 58 ° C. (trade name HP-5000, manufactured by DIC Corporation)
Epoxy resin 6: dicyclopentadiene type epoxy resin having an epoxy equivalent of 258 and a softening point of 60 ° C. (trade name HP-7200, manufactured by DIC Corporation)

(B) Curing agent Curing agent 1: Phenol aralkyl resin having a hydroxyl equivalent weight of 175 and a softening point of 70 ° C (trade name MEH-7800, manufactured by Meiwa Kasei Co., Ltd.)
Curing agent 2: Phenol novolak resin (trade name H-100, manufactured by Meiwa Kasei Co., Ltd.) having a hydroxyl group equivalent of 106 and a softening point of 83 ° C.

(C) Carboxamide derivative ・ Carboxamide derivative 1: salicylanilide (melting point: 136 ° C.)
Carboxamide derivative 2: 3-hydroxy-2-naphthanilide (melting point 247 ° C.)
Carboxamide derivative 3: 3-hydroxy-N- (1-naphthyl) -2-naphthamide (melting point 222 ° C.)
Carboxylic acid amide derivative 4: 3-hydroxy-N- (2-hydroxyethyl) -2-naphthamide (melting point 146 ° C.)
Carboxamide derivative 5: 2,4-dihydroxy-N- (2-hydroxyethyl) benzamide (melting point 164 ° C.)
Carboxamide derivative 6: salicylamide (melting point 140 ° C.)
Carboxamide derivative 7: 3-hydroxy-2-naphthamide (melting point: 217 ° C.)
Carboxamide derivative 8: p-acetamidophenol (melting point 170 ° C.)

Materials used in place of carboxylic acid amide derivatives in comparative examples: Phenol 1: phenol, phenol 2: o-cresol, phenol 3: 2-naphthol, phenol 4: resorcinol, non-phenolic carboxylic acid amide 1: benzanilide Non-phenolic carboxylic acid amide 2: 2-naphthanilide Non-phenolic carboxylic acid amide 3: Benzamide

(D) Silane compound-Silane compound 1: γ-glycidoxypropyltrimethoxysilane (E) curing accelerator-Curing accelerator 1: betaine-type adduct of triphenylphosphine and p-benzoquinone (F) inorganic filler Inorganic filler 1: spherical fused silica having a volume average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g (other additive components)
・ Montanic acid ester (HW-E manufactured by Clariant Japan Co., Ltd.)
・ Carbon black (MA-600 manufactured by Mitsubishi Chemical Corporation)

<Evaluation>
The epoxy resin molding materials for sealing of Examples and Comparative Examples obtained above were evaluated by the following various characteristic tests (1) to (6). The evaluation results are shown in Tables 11 to 20 below. The epoxy resin molding material for sealing was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds unless otherwise specified. Further, post-curing was performed at 180 ° C. for 5 hours.

(1) Spiral flow Using a spiral flow measurement mold according to EMMI-1-66, an epoxy resin molding material for sealing 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) Water absorption rate The disk molded in (2) was post-cured under the above conditions, left for 168 hours under the conditions of 85 ° C. and 60% RH, and measured the mass change before and after being left to measure the water absorption rate (mass %) = {(Disc mass after leaving -disc mass before leaving) / disc mass before leaving} × 100.

(4) Elastic modulus at 260 ° C (high temperature bending test)
A three-point bending test according to JIS K 6911 was performed using a bending tester (A & D Tensilon), and the flexural modulus (E) was determined while maintaining the temperature at 260 ° C. in a thermostatic bath. The measurement was performed under the condition of a head speed of 1.5 mm / min using a test piece obtained by molding the epoxy resin molding material for sealing into 10 mm × 70 mm × 3 mm under the above conditions. The flexural modulus (E) is defined by the following formula.

(5) Measurement of adhesive strength with metal at 260 ° C (measurement of shear strength)
The sealing epoxy resin molding material was molded on a copper plate or a silver-plated copper plate under the above conditions to have a bottom surface size of 4 mmφ, a top surface size of 3 mmφ, and a height of 4 mm, and then post-cured to prepare a measurement sample. The obtained measurement sample was subjected to measurement of shear adhesion at a shear rate of 50 μm / s using a bond tester (Daisy series 4000) while maintaining the temperature of various copper plates at 260 ° C.

(6) Reflow resistance 80 mm flat package with outer dimensions of 20 mm x 14 mm x 2 mm mounted with 8 mm x 10 mm x 0.4 mm silicone chip (Lead frame material: copper alloy, die pad top surface and lead tip silver plated product) ) Was molded under the above conditions using an epoxy resin molding material for sealing, and then post-cured.
After standing for 1 week under the conditions of 85 ° C. and 60% RH, Examples 1 to 16 and Comparative Examples 1 to 16 are 240 ° C., Examples 17 to 20, 25 to 32 and Comparative Examples 17 to 20, 25 to 32. Is 230 ° C., and Examples 21 to 24, 33 to 40 and Comparative Examples 21 to 24 and 33 to 40 are each subjected to reflow treatment at 220 ° C. to determine whether the resin / frame interface is peeled off. (HYE-FOCUS manufactured by Hitachi Construction Machinery Co., Ltd.) was observed and evaluated by the number of delamination generation packages for five test packages.

  The characteristics of the above (1) to (6) are compared with Examples and Comparative Examples with the same combination of epoxy resin and curing agent. For example, Examples 1-16 and Comparative Examples 1-16, which are combinations of Epoxy Resin 1 and 2 / Curing Agent 1, Examples 17-20 and Comparative Examples 17-, which are combinations of Epoxy Resin 1 and 3 / Curing Agent 1, 20. Examples 21 to 24 and Comparative Examples 21 to 24, which are combinations of Epoxy Resin 1 and 4 / Curing Agent 2, Examples 25 to 28 and Comparative Examples 25 to 25, which are combinations of Epoxy Resin 1 and 5 / Curing Agent 1 28, Examples 29-32 and Comparative Examples 29-32, which are combinations of Epoxy Resin 1 and 6 / Curing Agent 1, Examples 33-36 and Comparative Examples 33-, which are combinations of Epoxy Resin 1 and 5 / Curing Agent 2 36, Examples 37 to 40, which are combinations of epoxy resin 1 and 6 / curing agent 2, are compared with Comparative Examples 37 to 40.

Tables 11 to 20 show that examples in which a carboxylic acid amide derivative having one or more phenolic hydroxyl groups in one molecule is added have a 260 ° C. shear adhesive force (silver and copper) as compared with a comparative example in which this is not added. It can be seen that in the reflow treatment after standing for 1 week under the conditions of 85 ° C. and 60% RH, no peeling of the resin / frame interface occurs and the reflow resistance is excellent.
In Examples 1-8, 10-12, and 14-16, in which the ratio of the carboxylic acid amide derivative having one or more phenolic hydroxyl groups in one molecule is 0.1% by mass or more and less than 1.0% by mass, It can be seen that the force is stronger and the hot hardness is greater.
Furthermore, in place of the epoxy resin and the curing agent used in Examples 1 to 16, also in Examples 17 to 40 using different types of epoxy resin and the curing agent, regardless of the type of the epoxy resin and the curing agent, etc., 260 ° C shear adhesive strength (silver and copper) is high, and the resin / frame interface does not peel off during reflow treatment after standing for 1 week at 85 ° C and 60% RH, and has excellent reflow resistance. I understand.

  On the other hand, a comparative example having a composition different from that of the present invention does not satisfy the object of the present invention. In the reflow treatment after leaving for 1 week at 85 ° C. and 60% RH at 260 ° C. shear adhesive strength (silver and copper), which is equal to or less than that of the examples, the resin / frame interface peeling is observed in all packages. It can be seen that it is inferior in reflow resistance.

Claims (6)

(A) an epoxy resin having two or more epoxy groups in one molecule;
(B) a curing agent;
(C) a carboxylic acid amide derivative having one or more phenolic hydroxyl groups in one molecule;
An epoxy resin molding material for sealing containing   The epoxy resin molding material for sealing according to claim 1, wherein the content of the carboxylic acid amide derivative is 0.1% by mass or more and less than 1.0% by mass.   (D) The epoxy resin molding material for sealing according to claim 1 or 2, further comprising a silane compound.   (E) The epoxy resin molding material for sealing according to any one of claims 1 to 3, further comprising a curing accelerator.   (F) The epoxy resin molding material for sealing according to any one of claims 1 to 4, further comprising an inorganic filler.   An electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing of any one of Claims 1-5.