JP6528801B2 - Epoxy resin molding material for element sealing and electronic component device - Google Patents

Description

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

  Conventionally, epoxy resin molding materials are widely used in the field of sealing of electronic components such as transistors and integrated circuits (ICs). The reason for this is that the epoxy resin has well-balanced electrical properties, moisture resistance, heat resistance, mechanical properties, adhesion to the insert, and the like. In particular, the combination of an ortho-cresol novolac epoxy resin and a novolac phenol curing agent is excellent in the balance between them, and is the mainstream of the base resin of the molding material for element sealing.

  With the miniaturization, weight reduction and high performance of electronic devices in recent years, the mounting density has advanced, and surface mount type packages have been adopted for electronic component devices from the conventional pin insertion type. There is. When the semiconductor device is 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 the package is not directly exposed to high temperature. However, in the case of the surface mount type package, the entire semiconductor device is processed by a solder bath or a reflow apparatus, so that it is directly exposed to the soldering temperature. As a result, if the package absorbs moisture, the moisture absorption will swell rapidly during soldering, causing peeling of the bonding interface, package cracking, etc., and lowering the package reliability in the mounting process. there were.

  As a measure to solve the above problems, in order to reduce moisture absorption inside the semiconductor device, a method is used in which the IC is sufficiently dried prior to mounting on the moistureproof packaging of the IC or mounting on the wiring board. , These methods are time-consuming and expensive. As another measure, there is a method of increasing the content of the filler in the molding material for element sealing (see, for example, Patent Document 1).

Unexamined-Japanese-Patent No. 06-224328

However, in the method of increasing the content of the filler, although the moisture content inside the semiconductor device is reduced, there is a problem that the flowability is significantly reduced. If the flowability of the resin molding material for element sealing is low, problems such as the flow of a gold wire, the generation of voids, pinholes and the like may occur during molding.
The present invention has been made in view of such a situation, and has high adhesion to metal at high temperature, and an epoxy resin molding material for element sealing capable of forming a cured product excellent in reflow resistance, and an element sealed thereby. It is an object of the present invention to provide an electronic component device provided.

The present invention is as follows.
[1] For element sealing containing an epoxy resin having two or more epoxy groups in one molecule, a curing agent, and a compound having a functional group capable of reacting with the epoxy group in one molecule and a benzotriazole group Epoxy resin molding material.
[2] The epoxy resin for element sealing according to [1], wherein the functional group capable of reacting with the epoxy group is at least one selected from the group consisting of phenolic hydroxyl group, carboxy group, amino group, and mercapto group Molding material.
[3] The epoxy resin molding material for element sealing according to [1] or [2], wherein the melting point of the compound is 220 ° C. or less.
[4] The epoxy resin for element sealing according to any one of [1] to [3], wherein the compound has a functional group equivalent of 90 g / eq to 500 g / eq of the functional group capable of reacting with the epoxy group. Molding material.
[5] The epoxy resin molding material for element sealing according to any one of [1] to [4], wherein the functional group capable of reacting with the epoxy group is a phenolic hydroxyl group.
[6] The epoxy resin molding for device sealing according to any one of [1] to [5], wherein the number of functional groups capable of reacting with the epoxy group per benzotriazole group is one. material.
[7] The epoxy resin molding material for element sealing according to any one of [1] to [6], wherein the content of the compound is 0.1% by mass to 1.0% by mass in the total mass.
[8] An electronic component device comprising: a device; and a cured product of the sealing epoxy resin molding material according to any one of [1] to [7] for sealing the device.

  According to the present invention, there is provided an epoxy resin molding material for element sealing capable of forming a cured product having high adhesion to metal at high temperature and having excellent reflow resistance, and an electronic component device provided with the element sealed thereby. can do.

Hereinafter, the epoxy resin molding material for element sealing of this invention and an electronic component apparatus are demonstrated in detail.
In addition, the numerical range shown using "-" in this specification shows the range which includes the numerical value described before and after "-" as the minimum value and the maximum value, respectively. In the present invention, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. Means

<Epoxy resin molding material for element sealing>
The epoxy resin molding material for element sealing of the present invention has an epoxy resin having two or more epoxy groups in one molecule, a curing agent, and a functional group capable of reacting with the epoxy group and benzotriazole group in one molecule. And a compound. The epoxy resin molding material for element sealing may further contain other components, if necessary.

The epoxy resin molding material for device sealing is a compound having a functional group capable of reacting with an epoxy group and benzotriazole group in one molecule in addition to an epoxy resin having two or more epoxy groups in one molecule and a curing agent. In the case where a cured product is obtained by the curing treatment, the adhesiveness to metals at high temperatures is high. Although the reason is not clear, it is guessed as follows.
That is, the functional group in the compound having a functional group capable of reacting with an epoxy group and one benzotriazole group in one molecule reacts with the epoxy group in the epoxy resin. Thus, the compound is linked to the cured product of the epoxy resin, and the benzotriazole group of the compound is added to the surface of the cured product of the epoxy resin. On the other hand, since the nitrogen atom of the benzotriazole group of the compound can interact with the metal, the metal surface of the electronic component device can interact with the nitrogen atom. Since the compound has such a benzotriazole group and a functional group capable of reacting an epoxy group in one molecule, the element is sealed with the epoxy resin molding material for element sealing, and the curing treatment is performed. And the compound intervenes between the surface of the cured epoxy resin and the metal. As a result, it is presumed that the adhesion of the cured epoxy resin to the metal surface is improved, and the adhesion to the metal at high temperatures is enhanced.
Hereinafter, each component which comprises the epoxy resin molding material for element sealing of this invention is demonstrated.

-Epoxy resin-
The epoxy resin molding material for element sealing of the present invention contains an epoxy resin having two or more epoxy groups in one molecule. The number of epoxy groups may be two or more in one molecule, preferably 2 to 10, and more preferably 2 to 5.
The epoxy resin having two or more epoxy groups in one molecule used in the present invention is not particularly limited as long as it is generally used in an epoxy resin molding material for element sealing, and for example, a phenol novolac epoxy resin, Phenol such as ortho cresol novolac type epoxy resin, triphenylmethane type epoxy resin, cresol, xylenol, resorcinol, catechol, bisphenol A, phenol compound such as bisphenol A, and naphthol such as α-naphthol, β-naphthol, dihydroxynaphthalene Condensation of at least one selected from the group consisting of compounds with a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde or the like under acidic catalysis Is a novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by cocondensation; bisphenyl which is an alkyl-substituted, aromatic ring-substituted or unsubstituted diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S or thiodiphenol Type epoxy resin; biphenyl type epoxy resin which is diglycidyl ether such as alkyl substituted, aromatic ring substituted or unsubstituted biphenol; stilbene type epoxy resin; hydroquinone type epoxy resin; polybasic acid such as phthalic acid and dimer acid and epichlorohydrin Glycidyl ester type epoxy resin obtained by reaction; Glycidyl amine type epoxy resin obtained by reaction of epichlorohydrin with polyamine such as diaminodiphenylmethane, isocyanuric acid; Dicyclopentadiene and phenol Dicyclopentadiene type epoxy resin which is an epoxy compound of co-condensed resin of compound; naphthalene type epoxy resin which is epoxy resin having naphthalene skeleton; alkyl substituted, aromatic ring substituted or unsubstituted phenol compound or naphthol compound and dimethoxy paraxylene Or aralkyl type epoxy resins such as phenolaralkyl resins and naphtholaralkyl resins synthesized from bis (methoxymethyl) biphenyl; trimethylolpropane type epoxy resins; terpene-modified epoxy resins; and olefin bonds oxidized with peroxyacids such as peracetic acid These include linear aliphatic epoxy resins or alicyclic epoxy resins obtained by the above method, and one of these may be used alone, or two or more of these may be used in combination.

  Among them, as an epoxy resin having two or more epoxy groups in one molecule, a biphenyl type epoxy which is a diglycidyl ether of an alkyl-substituted, aromatic ring-substituted or unsubstituted biphenol from the viewpoint of coexistence of fluidity and curability It is preferable to contain a resin. From the viewpoint of curability, it is preferable to contain a novolac epoxy resin. From the viewpoint of heat resistance and low warpage, it is preferable to contain at least one selected from the group consisting of naphthalene type epoxy resins and triphenylmethane type epoxy resins. From the viewpoint of achieving both flowability and flame retardancy, it is preferable to contain a bisphenol F-type epoxy resin which is an alkyl-substituted, aromatic ring-substituted or unsubstituted diglycidyl ether of bisphenol F. From the viewpoint of achieving both flowability and reflowability, it is preferable to contain a thiodiphenyl type epoxy resin which is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted thiodiphenol. From the viewpoint of achieving both curability and flame retardancy, it is preferable to contain a phenol aralkyl type epoxy resin synthesized from an alkyl-substituted, aromatic ring-substituted or unsubstituted phenol compound and bis (methoxymethyl) biphenyl. From the viewpoint of achieving both storage stability and flame retardancy, it is preferable to contain a naphthol aralkyl type epoxy resin synthesized from an alkyl-substituted, aromatic ring-substituted or unsubstituted naphthol compound and dimethoxyparaxylene. From the viewpoint of low hygroscopicity, it is preferable to contain a dicyclopentadiene type epoxy resin.

  The biphenyl type epoxy resin is obtained by reacting a biphenol compound with epichlorohydrin by a known method. As such an epoxy resin, 4,4′-bis (2,3-epoxypropoxy) biphenyl, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetra The epoxy resin etc. which have a methylbiphenyl as a main component are mentioned. Especially, as a biphenyl type epoxy resin, the epoxy resin which has 4,4'-bis (2, 3- epoxy propoxy) -3, 3 ', 5, 5'- tetramethyl biphenyl as a main component is preferable. As such an epoxy resin, the commercial name YX-4000 by Japan Epoxy Resins Co., Ltd. is commercially available. The content of the biphenyl type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, in order to exert the performance.

  The thiodiphenyl type epoxy resin is obtained by reacting a thiodiphenol compound with epichlorohydrin by a known method. As such an epoxy resin, an epoxy resin containing diglycidyl ether of 4,4'-dihydroxydiphenyl sulfide as a main component, 2,2 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide Epoxy resin mainly composed of diglycidyl ether, epoxy resin mainly composed of diglycidyl ether of 2,2′-dimethyl-4,4′-dihydroxy-5,5′-di-t-butyldiphenyl sulfide Among them, as the thiodiphenyl type epoxy resin, an epoxy mainly composed of diglycidyl ether of 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di-t-butyldiphenyl sulfide is mentioned, among others. Resins are preferred. As such an epoxy resin, a trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd. is commercially available. When the thiodiphenylphenyl epoxy resin is contained, the content of the thiodiphenyl epoxy resin is preferably 20% by mass or more in the total amount of the epoxy resin to exhibit its performance, and 30% by mass or more is more preferable. Preferably, 50% by mass or more is more preferable.

  The bisphenol F-type epoxy resin is obtained by reacting a bisphenol F compound with epichlorohydrin by a known method. As such an epoxy resin, an epoxy resin containing diglycidyl ether of 4,4'-methylenebis (2,6-dimethylphenol) as a main component, 4,4'-methylenebis (2,3,6-trimethylphenol) And epoxy resins containing diglycidyl ether of 4,4'-methylene bisphenol as a main component, and the like. Among them, as bisphenol F-type epoxy resin, 4,4 'is exemplified. Epoxy resins based on diglycidyl ether of methylene bis (2,6-dimethylphenol) are preferred. As such an epoxy resin, commercially available trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. is available. When the bisphenol F-type epoxy resin is contained, the content of the bisphenol F-type epoxy resin is preferably 20% by mass or more, and more preferably 30% by mass or more in the total amount of the epoxy resin in order to exert its performance. And 50% by mass or more is more preferable.

  Novolak-type epoxy resins are easily obtained by reacting epichlorohydrin with novolak resins. Among them, ortho cresol novolac epoxy resin is preferable as the novolac epoxy resin. As such an epoxy resin, N-660 (trade name) manufactured by DIC Corporation is commercially available. When the novolac epoxy resin is contained, the content of the novolac epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and 50% by mass in the total amount of the epoxy resin in order to exert its performance. The above is more preferable.

  As a naphthalene type epoxy resin, the brand name HP-4700 etc. made by DIC Corporation are available. When the naphthalene type epoxy resin is contained, the content of the naphthalene type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and 50% by mass in the total amount of the epoxy resin to exhibit its performance. It is more preferable to make it% or more.

  As triphenylmethane type epoxy resin, Nippon Kayaku Co., Ltd. trade name EPPN-502 or Japan Epoxy Resin Co. Ltd. trade name 1032 H60 is available. When the triphenylmethane type epoxy resin is contained, the content of the triphenylmethane type epoxy resin is preferably 20% by mass or more in the total amount of the epoxy resin to exhibit its performance, and 30% by mass or more is more preferable. Preferably, it is more preferably 50% by mass or more.

  The phenol-aralkyl type epoxy resin can be obtained by reacting epichlorohydrin with a phenol-aralkyl resin synthesized from an alkyl-substituted, aromatic-ring-substituted or unsubstituted phenol compound and dimethoxyparaxylene according to a known method. In addition, a biphenylene skeleton-containing phenol aralkyl type epoxy resin is obtained by reacting epichlorohydrin with a phenol aralkyl resin synthesized from an alkyl-substituted, aromatic ring-substituted or unsubstituted phenol compound and bis (methoxymethyl) biphenyl by a known method. Be As such an epoxy resin, an epoxy compound of a phenol aralkyl resin is commercially available as Nippon Kayaku Co., Ltd. under the trade name NC-2000L, and an epoxy compound of a biphenylene skeleton-containing phenol aralkyl resin is commercially available as Nippon Kayaku Co., Ltd. The trade name NC-3000S is available. When the above-mentioned phenol aralkyl type epoxy resin is contained, the content of the phenol aralkyl type epoxy resin is preferably 20% by mass or more in the total amount of the epoxy resin to exhibit its performance, and more preferably 30% by mass or more 50 mass% or more is still more preferable.

  The naphthol aralkyl type epoxy resin can be obtained by reacting epichlorohydrin with a naphthol aralkyl resin synthesized from an alkyl-substituted, aromatic ring-substituted or unsubstituted naphthol compound and dimethoxyparaxylene or bis (methoxymethyl) biphenyl by a known method . As such an epoxy resin, as a commercial product, trade name ESN-375 manufactured by Nippon Steel Chemical Co., Ltd. or trade name ESN-175 manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned. When the naphthol aralkyl type epoxy resin is contained, the content of the naphthol aralkyl type epoxy resin is preferably 20% by mass or more, and more preferably 30% by mass or more in the total amount of the epoxy resin in order to exert its performance. 50 mass% or more is still more preferable.

  Moreover, it is preferable to contain the above-mentioned biphenyl type epoxy resin and biphenylene skeleton-containing phenol aralkyl type epoxy resin from the viewpoint of coexistence of flame retardancy, reflow resistance and flowability, and the content ratio is particularly preferably Biphenyl type epoxy resin / biphenylene skeleton-containing phenol aralkyl type epoxy resin = 50/50 to 5/95 is preferable, 40/60 to 10/90 is more preferable, and 30/70 to 15/85 Is more preferred. As a compound which satisfies such a content mass ratio, Nippon Kayaku Co., Ltd. trade name CER-3000L etc. are available as a commercial item.

  In addition to the above, as an epoxy resin having two or more epoxy groups in one molecule, a naphthalene modified novolac epoxy resin can also be used. Examples of such a compound include HP-5000, a trade name of DIC Corporation. When the naphthalene modified novolac epoxy resin is contained, the content of the naphthalene modified novolac epoxy resin is preferably 20% by mass or more in the total amount of the epoxy resin to exhibit its performance, and more preferably 30% by mass or more. And 50% by mass or more is more preferable.

  Furthermore, a dicyclopentadiene type epoxy resin can also be used as an epoxy resin which has two or more epoxy groups in 1 molecule. Examples of such a compound include HP-7200 (trade name) manufactured by DIC Corporation. When the dicyclopentadiene type epoxy resin is contained, the content of the dicyclopentadiene type epoxy resin is preferably 20% by mass or more, and more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exert its performance. And 50% by mass or more is more preferable.

  Biphenyl type epoxy resin, thiodiphenyl type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, naphthalene type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, mentioned above The naphthalene modified novolac epoxy resin and the dicyclopentadiene epoxy resin may be used singly or in combination of two or more. In the case of using two or more of these epoxy resins in combination, the total content of the epoxy resins is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more.

The epoxy equivalent of the epoxy resin having two or more epoxy groups in one molecule is preferably 100 g / eq to 1000 g / eq, more preferably 150 g / eq to 1000 g / eq, and still more preferably 150 g / eq to 500 g / eq. .
When an epoxy resin having two or more epoxy groups in one molecule has a softening point, the melting point is preferably 40 ° C to 180 ° C, more preferably 45 ° C to 150 ° C, and still more preferably 50 ° C to 130 ° C.
When an epoxy resin having two or more epoxy groups in one molecule has a melting point, the melting point is preferably 40 ° C to 180 ° C, more preferably 45 ° C to 150 ° C, and still more preferably 50 ° C to 130 ° C.

Whether an epoxy resin having two or more epoxy groups in one molecule has a softening point or a melting point is determined as follows.
A solid sample (epoxy resin having two or more epoxy groups in one molecule) is put in a glass capillary, and it is dipped in silicone oil, and the melting point is measured by visual observation while raising the temperature of silicone oil. It is determined by measurement with a measuring instrument whether the temperature difference from the temperature at which the solid sample starts to melt to the temperature at which it melts can be determined at one point temperature, and if the temperature difference can be determined at one point temperature, the solid sample Judge to have. On the other hand, if the temperature difference can not be determined as a single temperature, it is determined that the solid sample has a softening point.

  3 mass% or more and 15 mass% or less are preferable, and, as for the content rate of the epoxy resin which has an epoxy group two or more in 1 molecule contained in the epoxy resin molding material for element sealing of this invention, 3 mass% or more 12 mass% The following are more preferable, and 5 mass% or more and 12 mass% or less are still more preferable.

-Curing agent-
The epoxy resin molding material for element sealing of the present invention contains a curing agent.
The curing agent used in the present invention is not particularly limited as long as it is generally used in an epoxy resin molding material for element encapsulation, and includes phenol novolac resin, ortho cresol novolac resin, triphenylmethane-type phenol resin and the like. Selected from the group consisting of phenol compounds such as phenol, cresol, resorcine, catechol, bisphenol A, bisphenol F, phenylphenol, thiodiphenol, aminophenol and the like and naphthol compounds such as .alpha.-naphthol, .beta.-naphthol and dihydroxynaphthalene Novolak type phenolic resin obtained by condensation or cocondensation of at least one type and a compound having an aldehyde group such as formaldehyde, benzaldehyde, salicylaldehyde and the like under an acidic catalyst; a phenol compound -Type phenol resin such as phenolaralkyl resin, naphtholaralkyl resin, etc. which is synthesized from the compound and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; copolymer type wherein phenol novolak structure and phenol aralkyl structure are repeated randomly, block or alternately Phenolic aralkyl resins; paraxylylene and / or metaxylylene modified phenolic resins; melamine modified phenolic resins; terpene modified phenolic resins; dicyclopentadiene modified phenolic resins; cyclopentadiene modified phenolic resins; polycyclic aromatic ring modified phenolic resins and the like; These may be used alone or in combination of two or more.

  Among them, as a curing agent, a phenol aralkyl resin, a copolymer type phenol aralkyl resin and a naphthol aralkyl resin are preferable from the viewpoint of flowability, flame retardancy and reflow resistance, and heat resistance, low expansion coefficient and low warpage From the viewpoint of triphenylmethane-type phenol resin is preferable, and from the viewpoint of curability, novolak-type phenol resin is preferable, and it is preferable to contain at least one of these phenol resins.

As a phenol aralkyl resin, Mitsui Chemicals Co., Ltd. trade name XLC and Meiwa Kasei Co. Ltd. trade name MEH-7800 are mentioned as a commercial item. As a biphenylene frame | skeleton containing phenol aralkyl resin, Meiwa Kasei Co., Ltd. trade name MEH-7851 is mentioned as a commercial item. When the above-mentioned phenol aralkyl resin is contained, the content of the phenol aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and 50% by mass or more in the total amount of the curing agent to exhibit its performance. Is more preferred.
As the naphthol aralkyl resin, commercially available products include trade name SN-475 manufactured by Nippon Steel Chemical Co., Ltd. and trade name SN-170 manufactured by Nippon Steel Chemical Co., Ltd. When the naphthol aralkyl resin is contained, the content of the naphthol aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and 50% by mass or more in the total amount of the curing agent to exhibit its performance. Is more preferred.

  It is preferable that a part or all of the above-mentioned phenol aralkyl resin and naphthol aralkyl resin be premixed with acenaphthylene from the viewpoint of flame retardancy. Acenaphthylene can be obtained by dehydrogenation of acenaphthene, but commercial products may be used. Also, instead of acenaphthylene, polymers of acenaphthylene or polymers of acenaphthylene and other aromatic olefins can be used. Examples of the method for obtaining the polymer of acenaphthylene or the polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, anionic polymerization and the like. Moreover, although a conventionally well-known catalyst can be used in the case of superposition | polymerization, it can also carry out by heating. At this time, the polymerization temperature is preferably 80 ° C to 160 ° C, and more preferably 90 ° C to 150 ° C. 60 degreeC-150 degreeC are preferable, and, as for the softening point of the polymer of acenaphthylene obtained or the polymer of acenaphthylene and other aromatic olefins, 70 degreeC-130 degreeC are more preferable. If the temperature is 60 ° C. or more, the decrease in moldability due to the exudation at the time of molding tends not to occur, and if the temperature is 150 ° C. or less, the compatibility with the resin tends to be improved. Other aromatic olefins to be copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinyl naphthalene, vinyl biphenyl, their alkyl-substituted products and the like. In addition to the above-described aromatic olefins, aliphatic olefins may be used in combination as long as the effects of the present invention are not impaired. Examples of aliphatic olefins include (meth) acrylic acid, (meth) acrylic acid esters, maleic anhydride, itaconic anhydride, fumaric acid, fumaric acid esters and the like. The content of these aliphatic olefins is preferably 20% by mass or less, and more preferably 9% by mass or less, based on the total amount of the polymerization monomers.

  As a method of pre-mixing a part or all of the above-mentioned phenol aralkyl resin and naphthol aralkyl resin with acenaphthylene, a method of finely pulverizing a curing agent and acenaphthylene respectively and mixing them in a solid state with a mixer etc. It can be carried out by a method of removing the solvent after co-dissolving in a solvent, a method of melting and mixing both at a temperature above the softening point of the curing agent and / or acenaphthylene, etc. It is preferable to use a melt mixing method which is obtained and is less contaminated with impurities. A premix (acenaphthylene modified curing agent) is produced by the method described above. Melt mixing is not limited as long as the temperature is equal to or higher than the softening point of the curing agent and / or acenaphthylene, preferably 100 ° C. to 250 ° C., and more preferably 120 ° C. to 200 ° C. In addition, as long as the both are well mixed, the mixing time is not limited, and the mixing time 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 react with the polymerization or curing agent during mixing.

  As a triphenylmethane type phenol resin, Air Water Co., Ltd. trade name HE-910 and Meiwa Kasei Co., Ltd. trade name MEH-7500 are mentioned as a commercial item. When using a triphenylmethane type phenol resin, its content is preferably 30% by mass or more, and more preferably 50% by mass or more in the total amount of the curing agent in order to exert its performance.

  As a novolac type phenol resin, Meiwa Kasei Co., Ltd. trade name H-100 etc. are mentioned as a commercial item. When using a novolak type phenolic resin, its content is preferably 30% by mass or more, and more preferably 50% by mass or more, in the total amount of the curing agent in order to exert its performance.

  Commercially available copolymerized phenol aralkyl resins are commercially available under the trade name HE-510 manufactured by Air Water Co., Ltd. When a copolymerized phenol aralkyl resin is used, the content thereof is preferably 30% by mass or more, and more preferably 50% by mass or more in the total amount of the curing agent in order to exert its performance.

  As a dicyclopentadiene modified phenolic resin, the product name GDP-6085 etc. by Gunei Chemical Co., Ltd. is available as a commercial item. When a dicyclopentadiene modified phenolic resin is used, the content thereof is preferably 30% by mass or more, and more preferably 50% by mass or more in the total amount of the curing agent in order to exert its performance.

The above-mentioned phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene modified phenol resin, triphenylmethane type phenol resin, novolak type phenol resin and copolymer type phenol aralkyl resin are two or more types even if any one type is used alone. May be used in combination. In the case of using two or more of these resins in combination, the total content of the curing agents is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more.
The hydroxyl group equivalent of the curing agent is preferably 70 g / eq to 1000 g / eq, more preferably 75 g / eq to 700 g / eq, and still more preferably 80 g / eq to 500 g / eq.
When the curing agent has a softening point, the softening point is preferably 40 ° C to 180 ° C, more preferably 45 ° C to 150 ° C, and still more preferably 50 ° C to 130 ° C.
When the curing agent has a melting point, the melting point is preferably 40 ° C to 180 ° C, more preferably 45 ° C to 150 ° C, and still more preferably 50 ° C to 130 ° C.

In addition, it is judged as follows whether a hardening agent has a softening point or melting | fusing point.
A solid sample (hardening agent) is placed in a glass capillary, and it is immersed in silicone oil, and the melting point is measured by a melting point measurement system of a method of measuring the melting point visually while raising the temperature of silicone oil. It is determined whether or not the temperature difference from the temperature to the temperature at which the melting ends can be determined as a single point temperature, and when the temperature difference can be determined as a single point temperature, it is determined that the solid sample has a melting point. On the other hand, if the temperature difference can not be determined as a single temperature, it is determined that the solid sample has a softening point.

  In the present invention, the equivalent ratio of the epoxy resin having two or more epoxy groups in one molecule to the curing agent, that is, the ratio of the number of hydroxyl groups to the number of epoxy groups (number of hydroxyl groups in curing agent / number of epoxy groups in epoxy resin) is There is no particular limitation, and it is preferable to set in the range of 0.5 to 2.0, and more preferably 0.6 to 1.3, in order to reduce the amount of each unreacted component. In order to obtain the epoxy resin molding material for element sealing which is excellent in moldability, it is still more preferable to set to the range of 0.8-1.2.

-Compound having functional group capable of reacting with epoxy group and benzotriazole group in molecule-
The epoxy resin molding material for element sealing according to the present invention comprises a compound having a functional group capable of reacting with an epoxy group in one molecule and a benzotriazole group (hereinafter sometimes referred to as a “specific compound”). contains.
The functional group capable of reacting with the epoxy group in the specific compound means a functional group capable of ring-opening the epoxy group to form a covalent bond. At least a part of the specific compound is covalently bonded by opening the epoxy group in a cured product obtained by curing the epoxy resin. In the specific compound, one or more functional groups capable of reacting with an epoxy group and a benzotriazole group can be independently present.

  The benzotriazole group is a group obtained by removing one hydrogen atom from the benzotriazole compound which may have a substituent. The position at which the hydrogen atom is removed is not particularly limited, and may be a carbon atom or a nitrogen atom.

  When the benzotriazole compound has a substituent, examples of the substituent include an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a heteroaryl group, a nitro group, a cyano group and the like, and the above as the benzotriazole group From the viewpoint of arrangement with respect to the skeleton of the epoxy resin, an alkyl group having 1 to 6 carbon atoms is preferable. When the benzotriazole compound has a substituent, the number of substituents is not particularly limited, and is preferably 1 or 2. The benzotriazole compound may further form a fused ring. The fused ring may be an aromatic ring or an aliphatic ring, and may be a hydrocarbon ring or a heterocyclic ring. The benzotriazole compound is preferably unsubstituted in view of the arrangement of the benzotriazole group with respect to the skeleton of the epoxy resin.

  One or more functional groups capable of reacting with the epoxy group may be present in one molecule, and a plurality of functional groups may be present. The number of functional groups in the specific compound is preferably one from the viewpoint of reducing the high temperature elastic modulus. In addition, one benzotriazole group may be present in one molecule, or a plurality of benzotriazole groups may be present in one molecule. The number of the functional groups per one benzotriazole group of the specific compound can be 1 or 2 in terms of fixation to the resin after thermoforming or post curing. If the number of the functional groups per one benzotriazole group of the specific compound is 1 or more, the specific compound which has not reacted tends to disappear, and if 2 or less, the high temperature elastic modulus tends to be reduced. More preferably, the number of the functional groups per one benzotriazole group of the specific compound is one.

  As a functional group which can react with an epoxy group, a phenolic hydroxyl group, a carboxy group, an amino group, a mercapto group etc. can be mentioned. Among them, the functional group capable of reacting with an epoxy group is preferably at least one selected from the group consisting of a phenolic hydroxyl group, a carboxy group and an amino group, from the viewpoint of low corrosiveness to metals, It is more preferable that it is at least one selected from the group consisting of phenolic hydroxyl group and amino group from the viewpoint of flowability of the molding epoxy resin molding material, and from the viewpoint of reduction of elastic modulus in high temperature region, phenolic hydroxyl group It is further preferred that

  The phenolic hydroxyl group which is a functional group capable of reacting with an epoxy group is a group obtained by removing one hydrogen atom other than the hydrogen atom contained in the phenolic hydroxyl group from the phenol compound which may have a substituent. The phenolic compound can have one or more substituents. The substituent which the phenol compound may have includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 14 carbon atoms, A C6-C14 heteroaryl group, a nitro group, a cyano group etc. can be mentioned. The alkyl group, alkenyl group or alkoxy group in the substituent may be linear or branched, and is branched from the viewpoint of adhesion to a metal at high temperature or low hygroscopicity Is preferred. Examples of the branched alkyl group, alkenyl group or alkoxy group include alkyl groups having 3 to 20 carbon atoms, alkenyl groups having 3 to 20 carbon atoms, and alkoxy groups having 3 to 20 carbon atoms. More preferably, it is at least one selected from the group consisting of an alkyl group of 3 to 20 and an alkoxy group of 3 to 20 carbon atoms, and an alkyl group of 3 to 10 carbon atoms and an alkoxy group of 3 to 10 carbon atoms More preferably, it is at least one selected from the group consisting of When two or more substituents are present, the substituents bonded to adjacent positions among the above substituents may be bonded to each other to form a condensed ring together with the benzene ring of the phenol compound, and the condensation formed The ring may be a heterocycle having a nitrogen atom, a sulfur atom or the like.

  The substituent of the phenolic compound can be present in the ortho, meta or para position with respect to the phenolic hydroxyl group, and is preferably in the para position in view of the arrangement of the benzotriazole group with respect to the skeleton of the epoxy resin.

  The specific compound may have a functional group capable of reacting with an epoxy group (hereinafter sometimes simply referred to as "functional group") and a benzotriazole group in the molecule, and the bonding manner is not particularly limited. For example, the functional group and the benzotriazole group may be linked by a single bond, and the functional group and the benzotriazole group may be linked via a divalent organic group.

  As a divalent organic group which connects the said functional group and a benzotriazole group, a C1-C6 alkylene group, a C6-C14 arylene group, etc. can be mentioned. When the divalent organic group is an alkylene group or an arylene group, the alkylene group or the arylene group may further have a substituent. Examples of the substituent in the alkylene group include an alkenyl group, an alkoxy group, an aryl group, a heteroaryl group, a nitro group, a cyano group and the like, and in addition thereto, a benzotriazole group and a functional that can react with an epoxy group. Groups can be mentioned. Examples of the substituent in the arylene group include an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a heteroaryl group, a nitro group, a cyano group and the like, and in addition to these, a reaction with a benzotriazole group and an epoxy group Mention may be made of functional groups which may be.

  When the functional group is a carboxy group, an amino group or a mercapto group, as the specific compound, in terms of the arrangement of the benzotriazole group with respect to the skeleton of the epoxy resin, between the benzotriazole group and the functional group Is preferably a single bond. When the specific compound is a benzotriazole compound having a carboxy group as the functional group, the linking position of the carboxy group may be any, and among them, the carboxy group is linked to the benzene ring constituting the benzotriazole ring These compounds are preferred in that they are relatively easy to obtain. When the specific compound is a benzotriazole compound having a mercapto group as the functional group, the linking position of the mercapto group may be any, and among them, it is linked to the nitrogen atom at the 1 or 2 position of the benzotriazole group These compounds are preferred in that they are relatively easy to obtain. When the specific compound is a benzotriazole compound having an amino group as the functional group, the linking position of the amino group may be any, and among them, it is linked to the nitrogen atom at position 1 or 2 of the benzotriazole group These compounds are preferred in that they are relatively easy to obtain.

  A compound having a phenolic hydroxyl group and a benzotriazole group as a functional group capable of reacting with an epoxy group in one molecule (hereinafter, sometimes referred to as "phenol derivative having a benzotriazole group" as a specific compound) In the above case, in view of the arrangement of the benzotriazole group with respect to the skeleton of the epoxy resin, it is preferable that a single bond be between the benzene ring to which the phenolic hydroxyl group is bonded and the benzotriazole group. In the phenol derivative having a benzotriazole group, the bonding position of the benzotriazole group in the benzene ring to which the phenolic hydroxyl group is bonded may be any position of meta position, para position and ortho position, relative to the skeleton of the epoxy resin The ortho position is preferred in view of the arrangement of the benzotriazole group. When the phenol derivative having a benzotriazole group is a compound having one benzotriazole group and one hydroxyphenyl group, it has a structure in which a nitrogen atom at position 1 of the benzotriazole group is bonded to a hydroxyphenyl group. It may be one having a structure in which a nitrogen atom at position 2 of a benzotriazole group is bonded to a hydroxyphenyl group. The phenol derivative having the benzotriazole group has a structure in which a nitrogen atom at the 2-position of the benzotriazole group is bonded to a hydroxyphenyl group, in terms of the arrangement of the benzotriazole group with respect to the skeleton of the epoxy resin preferable.

  When the phenol derivative having a benzotriazole group has a plurality of benzotriazole groups, each of the benzotriazole groups may be linked by a single bond to a benzene ring to which a phenolic hydroxyl group is linked, and is linked via a linking group It may be It does not restrict | limit especially as a coupling group, A C1-C6 alkylene group, a C6-C14 arylene group, etc. can be mentioned. The linking group may further have a substituent. Examples of the substituent in the linking group include the same as the substituents described as the substituent in the divalent organic group.

  As a specific example of the compound in which the phenol derivative having a benzotriazole group has a plurality of benzotriazole groups, a dimer or a trimer or more of a benzotriazolyl phenol, two benzotriazolyl phenyl groups are carbon The compound etc. which couple | bonded through several 1-6 alkylene groups can be mentioned.

  The phenol derivative having a benzotriazole group is a branched chain as a substituent of a benzene ring having an unsubstituted benzotriazole group and having a phenolic hydroxyl group bonded thereto in terms of arrangement of the benzotriazole group with respect to the skeleton of the epoxy resin Derivative of a phenol ring having one or more alkyl groups or alkoxy groups, and a substituent of a benzene ring having an unsubstituted benzotriazole group at an ortho position to the phenolic hydroxyl group and to which the phenolic hydroxyl group is bonded It is more preferable that it is a phenol derivative which has one or more branched alkyl groups or alkoxy groups as

  Examples of the phenol derivative having a benzotriazole group include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole and 2- (2-hydroxy-3,5-di-t-pentylphenyl)-. 2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- 4 Methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2,2'-methylenebis [6- ( 2H-benzotriazol-2-yl) -4-t-octylphenol], 6- (2H-benzotriazol-2-yl)- -T-Octyl-6'-t-butyl-4'-methyl-2,2'-methylene bisphenol, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- (2- Hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-s-butyl-5-t-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-) t-Butyl-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (2-hydroxy-) 3,5-di-t-butylphenyl) -5-chloro-2H-benzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) pheny ] -2H- benzotriazole, etc., and their positional isomers thereof. These phenol derivatives having a benzotriazole group may be those further substituted by an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a heteroaryl group, a nitro group, a cyano group or the like (hereinafter referred to as a substituted compound) Good. These can be used singly or in combination of two or more.

  Among them, 2- (2-hydroxy-3,5-di-t-pentylphenyl) -2H-benzotriazole, 2- (2- (2-hydroxy-3,5-di-t-pentylphenyl) -2) from the viewpoint of reducing the high temperature elastic modulus or the adhesiveness with metal at high temperature. 2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- ( 2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-s-butyl-5-tert-butylphenyl) -2H-benzotriazole, etc., and positional isomers thereof And their substitution products are preferred.

When a specific compound has a carboxy group as a functional group which can react with the said epoxy group, 4-benzotriazole carboxylic acid, 5-benzotriazole carboxylic acid etc. are mentioned as a compound which has a carboxy group and a benzotriazole group.
When the specific compound has a mercapto group as a functional group capable of reacting with the epoxy group, examples of the compound having a mercapto group and a benzotriazole group include 1-mercapto-1H-benzotriazole, 2-mercapto-2H-benzotriazole, etc. Can be mentioned.
When the specific compound has an amino group as a functional group capable of reacting with the epoxy group, examples of the compound having an amino group and a benzotriazole group include 1-amino-1H-benzotriazole, 2-amino-2H-benzotriazole, etc. Can be mentioned.

  The melting point of the specific compound is preferably 220 ° C. or less from the viewpoint of adhesion to metal and reflow resistance. If the melting point of the specific compound is 220 ° C. or less, there is a tendency that unreacted substances do not segregate due to the heat treatment in the molding step of the epoxy resin molding material for element sealing. The melting point of the specific compound is more preferably 200 ° C. or less in order to ensure melting during heat treatment in the molding step and subsequent curing. The lower limit of the melting point of the specific compound is not particularly limited, but can generally be 40 ° C. or higher.

  The functional group equivalent of the functional group of the specific compound is 90 g / eq to 500 g / m in terms of the strength after thermoforming or post curing of the epoxy resin molding material for element encapsulation and the fixation of the benzotriazole group to the resin. It is preferable that it is eq, It is more preferable that it is 150 g / eq-450 g / eq, It is still more preferable that it is 200 g / eq-400 g / eq. If the functional group equivalent of the functional group of the specific compound is 90 g / eq or more, a certain strength tends to be maintained after heat molding or post curing, and if it is 500 g / eq or less, high concentration of benzotriazole group Tend to be able to be fixed to epoxy resin.

  When the specific compound is a phenol derivative having a benzotriazole group, the hydroxyl equivalent of the phenol derivative having a benzotriazole group is the strength of the epoxy resin molding material for element sealing after thermoforming or post curing and the resin of the benzotriazole group From the viewpoint of immobilization onto the pigment, it is preferably 100 g / eq to 500 g / eq, more preferably 150 g / eq to 450 g / eq, and still more preferably 200 g / eq to 400 g / eq. If the hydroxyl equivalent of the phenol derivative having a benzotriazole group is 100 g / eq or more, a certain strength tends to be maintained after heat molding and post curing, and if it is 500 g / eq or less, the benzotriazole group has a high concentration Tend to be able to be fixed to epoxy resin.

  In the present invention, when the specific compound is a phenol derivative having a benzotriazole group, an equivalent ratio of an epoxy resin to a curing agent and a phenol derivative having a benzotriazole group, that is, a curing agent for the number of epoxy groups and the benzotriazole group The ratio of the number of hydroxyl groups in the phenol derivative (having the number of hydroxyl groups in the curing agent and the phenol derivative having the benzotriazole group / the number of epoxy groups in the epoxy resin) is not particularly limited. It is preferable to set to the range of 0.5-2.0, and 0.6-1.3 are more preferable. In order to obtain an epoxy resin molding material for sealing which is excellent in moldability, it is more preferable to set in the range of 0.8 to 1.2.

  The content of the specific compound in the epoxy resin molding material for element encapsulation is preferably 0.1% by mass or more and 1.0% by mass or less, and is 0.15% by mass or more and 0.95% by mass or less More preferably, the content is 0.2% by mass or more and 0.75% by mass or less. If it is 0.1% by mass or more, the adhesiveness with metal at high temperature tends to be further improved, and if it is 1.0% by mass or less, the reduction of the hardness of the epoxy resin molding material for element sealing can be suppressed. Tend.

-Silane compound-
The epoxy resin molding material for element sealing of the present invention may contain a silane compound.
The silane compounds include epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, aminosilanes such as γ-anilinopropyltrimethoxysilane, and alkyls such as methyltrimethoxysilane Examples thereof include silane, isocyanate silane such as γ-isocyanatopropyltrimethoxysilane, and vinylsilane such as vinyltrimethoxysilane. One of these may be used alone, or two or more of these may be used in combination.

  The content of the silane compound is preferably 0.06% by mass to 2% by mass in the epoxy resin molding material for element encapsulation from the viewpoint of moldability and fluidity, and more preferably 0.1% by mass to 0.75% by mass, 0.2 mass%-0.7 mass% are still more preferable. If it is 0.06 mass% or more, fluidity tends to be secured, and if it is 2 mass% or less, molding defects such as voids tend to be less likely to occur.

-Hardening accelerator-
The epoxy resin molding material for element sealing of the present invention may contain a curing accelerator.
As a hardening accelerator used by this invention, it is generally used by the epoxy resin molding material for element sealing, and there is no limitation in particular. For example, 1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5.4 .0] Cycloamidine compounds such as undecene-7; and cycloamidine compounds such as maleic anhydride, 1,2-benzoquinone, 1,4-benzoquinone, diphenoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3- Quinones such as dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and anthraquinone A compound, a compound having an intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane or a phenol resin; Tertiary amine compounds such as dimethyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and derivatives thereof; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, Imidazole compounds such as 2-heptadecyl imidazole and derivatives thereof; organic phosphine compounds such as tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, diphenyl phosphine, phenyl phosphine and the like; A phosphorus compound having an intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above-mentioned quinone compound, diazophenylmethane, a phenol resin, etc. Tetrasubstituted phosphonium tetrasubstituted borates such as phosphonium tetraphenylborate, tetraphenylphosphonium ethyl triphenylborate, tetrabutylphosphonium tetrabutylborate and the like; and 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate and the like Tetraphenylboron salts and their derivatives are included. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a tertiary phosphine used for the adduct of an organic phosphine compound and a quinone compound etc., Dibutylphenyl phosphine, butyl diphenyl phosphine, ethyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (t-butylphenyl) phosphine, tris (2,4-dimethylphenyl) ) Phosphines, tris (2,6-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4- Kishifeniru) phosphine, tertiary phosphines are exemplified with an aryl group such as tris (4-ethoxyphenyl) phosphine, triphenylphosphine is preferable in view of moldability.

  The quinone compound used for the adduct of the third phosphine and the quinone compound is not particularly limited, and examples thereof include 1,2-benzoquinone, 1,4-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone and the like. From the viewpoint of moisture resistance or storage stability, 1,4-benzoquinone is preferred.

  The content of the curing accelerator is not particularly limited as long as the curing promoting effect is achieved, and an epoxy resin having two or more epoxy groups in one molecule, a curing agent, and one molecule are included. 0.1 parts by mass to 10 parts by mass is preferable, and 0.3 parts by mass to 5 parts by mass is more preferable with respect to a total amount of 100 parts by mass with a compound having a functional group capable of reacting with an epoxy group and a benzotriazole group. 0.5 to 4 parts by mass is more preferable. If it is 0.1 parts by mass or more, it can be cured in a short time, and if it is 10 parts by mass or less, there is a tendency that a good molded product can be obtained without the curing speed being too fast.

-Inorganic filler-
The epoxy resin molding material for element sealing of the present invention may contain an inorganic filler.
The inorganic filler used in the present invention is contained in a molding material for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, and is generally used for an epoxy resin molding material for element sealing. There is no particular limitation as long as As the inorganic filler, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, forsterite, steatite, spinel, Powders such as mullite and titania, or beads obtained by spheroidizing them, glass fibers and the like can be mentioned. One of these may be used alone, or two or more of these may be used in combination. Among them, fused silica is preferable as the inorganic filler from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. The shape of the filler is preferably spherical from the viewpoint of flowability during molding and mold abradability. Spherical fused silica is preferred from the viewpoint of the balance between cost and performance.

  When the inorganic filler is contained, the content of the inorganic filler is 70% by mass in the epoxy resin molding material for element sealing from the viewpoint of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction and strength improvement 95 mass% is preferable. If it is 70 mass% or more, the flame retardancy tends to be improved, and if it is 95 mass% or less, the fluidity tends to be improved.

-Other ingredients-
(Anion exchanger)
Further, in the epoxy resin molding material for element sealing of the present invention, an anion exchanger can be blended as needed for the purpose of improving the moisture resistance and the high-temperature leaving characteristic of the element such as IC. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. As the anion exchanger, hydrotalcite; hydrous oxide of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth; and the like can be mentioned. One of these may be used alone, or two or more of these may be used in combination.

  When the anion exchanger is contained, the content of the anion exchanger is not particularly limited as long as it is an amount sufficient to capture an anion such as a halogen ion, but two epoxy groups are contained in one molecule. 0.1 mass part-30 mass parts are preferable with respect to 100 mass parts of epoxy resins which have more than, and 1 mass part-5 mass parts are more preferable.

(Release agent)
A mold release agent may be contained in the epoxy resin molding material for element sealing of the present invention as needed. The release agent may include an oxidized or non-oxidized polyolefin. Examples of the oxidized or non-oxidized polyolefin include low molecular weight polyethylene having a number average molecular weight of about 500 to 10000, such as Clariant's trade name H4, PE, PED series and the like.
When the release agent is contained, the release agent is preferably used in an amount of 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin having two or more epoxy groups in one molecule. It is more preferable to use part to 5 parts by mass. If the amount is 0.01 parts by mass or more, the releasability tends to be sufficient, and if the amount is 10 parts by mass or less, the decrease in adhesiveness tends to be suppressed.
Moreover, as a mold release agent other than the above, carnauba wax, montanic acid ester, montanic acid, stearic acid etc. are mentioned. These may be used alone or in combination of two or more. When these other release agents are used in combination with the oxidized or non-oxidized polyolefin, the total content thereof is 0.2 parts by weight per 100 parts by weight of the epoxy resin having two or more epoxy groups in one molecule. 1 mass part-10 mass parts are preferable, and 0.5 mass part-3 mass parts are more preferable.

(Flame retardants)
The epoxy resin molding material for element sealing of the present invention can contain a conventionally known flame retardant as required. Flame retardants include brominated epoxy resin; antimony trioxide; red phosphorus; inorganic substances such as aluminum hydroxide, magnesium hydroxide and zinc oxide, and / or red phosphorus and phosphorus coated with thermosetting resins such as phenol resin, etc. Phosphorus compounds such as acid esters; Melamine, melamine derivatives, melamine-modified phenolic resin, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives, isocyanuric acid derivatives; phosphorus and nitrogen-containing compounds such as cyclophosphazene; aluminum hydroxide, Compounds containing a metal element such as magnesium hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron and the like can be mentioned. One of these may be used alone, or two or more of these may be used in combination. When the flame retardant is contained, the content of the flame retardant is not particularly limited, and 1 part by mass to 30 parts by mass is preferable with respect to 100 parts by mass of the epoxy resin having two or more epoxy groups in one molecule, and 2 parts by mass -15 mass parts is more preferable, and 3 mass parts-10 mass parts are still more preferable.

(Colorant etc.)
Moreover, the epoxy resin molding material for element sealing of this invention may contain coloring agents, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara. Furthermore, as other additives, stress relaxation agents such as silicone oil and silicone rubber powder can be contained as required.

-Preparation of epoxy resin molding material for element sealing-
The epoxy resin molding material for element sealing of the present invention can be prepared by any method as long as various components can be dispersed and mixed uniformly. As a general method, there can be mentioned a method in which components of a predetermined blending amount are mixed by a mixer or the like, melt-kneaded by a mixing roll, an extruder or the like, and cooled and pulverized. Specifically, it is obtained by a method such as stirring or mixing predetermined amounts of the components described above, kneading with a kneader, roll, extruder, etc. which has been heated to 70 ° C. to 140 ° C. in advance, followed by cooling and crushing. be able to. It is easy to use if it is tableted by the dimension and mass which suit molding conditions.

<Electronic component device>
The electronic component device of the present invention comprises a device and a cured product of the epoxy resin molding material for device sealing that seals the device, and has other components as necessary.
The electronic component device of the present invention includes a lead frame, a tape carrier with wiring, a wiring board, glass, a support member such as a silicon wafer, a semiconductor chip, an active element such as a transistor, a diode or a thyristor, a capacitor, a resistor, a coil And the like, and an electronic component device and the like in which necessary parts are sealed with the epoxy resin molding material for element sealing of the present invention. In such an electronic component device, the semiconductor element is fixed on a lead frame, and the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding or bumps, and then the epoxy resin molding for element sealing of the present invention is formed. Material is sealed by transfer molding etc., Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package (SOP), Small Outline J-lead (SOJ) general resin-sealed ICs such as TPP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc .; (Tape Carrier Package) in which a semiconductor chip connected to the semiconductor chip by a bump is sealed with the epoxy resin molding material for element sealing of the present invention; wire bonding, flip chip bonding, solder to wiring formed on a wiring board or glass COB (Chip On) in which an active element such as a semiconductor chip, a transistor, a diode, or a thyristor and / or a passive element such as a capacitor, a resistor, or a coil are sealed with the epoxy resin molding material for element sealing of the present invention. Board) Module, hybrid IC, multi-chip module; after mounting the element on the surface of the organic substrate with the terminal for wiring board connection on the back surface, connecting the element and the wiring formed on the organic substrate by bump or wire bonding , The epoxy resin molding material for element sealing of the present invention BGA sealing the child (Ball Grid Array), CSP (Chip Size Package); and the like. Moreover, the epoxy resin molding material for element sealing of this invention can be used effectively also for a printed circuit board.
Although a low pressure transfer molding method is generally used as a method of sealing an element using the epoxy resin molding material for element sealing of the present invention, an injection molding method, a compression molding method or the like may be used.

  Since the epoxy resin molding material for element sealing of the present invention contains a compound having a functional group capable of reacting with an epoxy group and a benzotriazole group in one molecule, the epoxy resin molding material for element sealing of the present invention is It exhibits excellent adhesion to members whose surface is a metal, particularly a metal containing copper or silver, such as wiring. Therefore, the epoxy resin molding material for element sealing of the present invention is particularly effective for sealing an electronic component device provided with an element having a wiring of copper or silver on the surface. In addition, wiring whose surface is copper or silver, copper wiring, silver wiring, wiring whose silver plating was given to the wiring surface of copper, etc. are mentioned.

  EXAMPLES The present invention will next be described by way of examples, but the scope of the present invention is not limited to these examples.

  The following components are compounded in parts by mass shown in Tables 1 to 12 below, roll kneading is performed under conditions of kneading temperature 80 ° C., kneading time 10 minutes, and Examples 1 to 43 and Comparative Examples 1 to Comparative Example Forty-three epoxy resin molding materials for element sealing were produced. In addition, the blank in the table represents "no blending".

The following was used as an epoxy resin which has 2 or more of epoxy groups in 1 molecule.
Epoxy resin 1: Biphenyl type epoxy resin having an epoxy equivalent of 196 g / eq and a melting point of 106 ° C. (trade name YX-4000 manufactured by Japan Epoxy Resins Co., Ltd., number of epoxy groups contained in one molecule: 2)
・ Epoxy resin 2: A composition having a mass ratio of a biphenyl type epoxy resin having a softening point of 96 ° C./biphenyl skeleton-containing phenol aralkyl type epoxy resin = 20/80 with a softening point of 96 ° C. (manufactured by Nippon Kayaku Co., Ltd., trade name CER -3000 L, number of epoxy groups contained in one molecule: 2 to 5)
Epoxy resin 3: Epoxide of phenol aralkyl resin having an epoxy equivalent of 238 g / eq and a softening point of 55 ° C. (Nippon Kayaku Co., Ltd., trade name NC-2000 L, number of epoxy groups contained in one molecule: 2 to 6) 5 pieces)
· Epoxy resin 4: Ortho cresol novolac epoxy resin having an epoxy equivalent of 202 g / eq and a softening point of 60 ° C (manufactured by DIC Corporation, trade name N-660, number of epoxy groups contained in one molecule: 2 to 5) )
Epoxy resin 5: Naphthalene-modified novolac epoxy resin having 250 g / eq of epoxy equivalent and softening point of 58 ° C (manufactured by DIC Corporation, trade name HP-5000, number of epoxy groups contained in one molecule: 2 to 5) )
Epoxy resin 6: Dicyclopentadiene type epoxy resin having an epoxy equivalent of 258 g / eq and a softening point of 60 ° C. (manufactured by DIC Corporation, trade name HP-7200, number of epoxy groups contained in one molecule: 2 to 5) )

The following were used as a curing agent.
Hardener 1: Phenolic aralkyl resin having a hydroxyl equivalent of 175 g / eq and a softening point of 70 ° C. (manufactured by Meiwa Kasei Co., Ltd., trade name MEH-7800)
Curing agent 2: Novolak type phenol resin having a hydroxyl equivalent of 106 g / eq and a softening point of 83 ° C. (manufactured by Meiwa Kasei Co., Ltd., trade name H-100)

The following compounds were used as a compound having a functional group capable of reacting with an epoxy group and a benzotriazole group in one molecule.
-Benzotriazole-phenol compound 1: 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole (SEESORB 701, manufactured by Cipro Chemical Industries, Ltd., melting point: 130 ° C, hydroxyl equivalent: 225 g / eq)
-Benzotriazole-phenol compound 2: 2- (2-hydroxy-3,5-di-t-pentylphenyl) -2H-benzotriazole (SEESORB 704, manufactured by Cipro Chemical Industries, Ltd., melting point: 80 ° C, hydroxyl equivalent: 352 g / eq)
・ Benzotriazole-phenolic compound 3: 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol (SEESORB 706, Cipro Chemical Industries, Ltd.) Product, melting point: 164 ° C., hydroxyl equivalent: 388 g / eq)
-Benzotriazole-phenol compound 4: 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole (SEESORB 707, manufactured by Cipro Chemical Industries, Ltd., melting point: 75 ° C, hydroxyl equivalent: 339 g / eq)
Benzotriazole-phenol compound 5: 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4-t-octylphenol] (JF-832, manufactured by Johoku Chemical Co., Ltd., melting point: 195 ° C., Hydroxy group equivalent: 329 g / eq)
・ Benzotriazole-phenol compound 6: 6- (2H-benzotriazol-2-yl) -4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol (JAST-500 , Johoku Chemical Co., Ltd., melting point: 107 ° C., hydroxyl equivalent: 250 g / eq)
-Benzotriazole-phenol compound 7: 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole (SEESORB 709, manufactured by Cipro Chemical Industries, Ltd., melting point: 104 ° C, hydroxyl equivalent: 323 g / eq)
Benzotriazole-phenol compound 8: 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -2H-benzotriazole (JF-79, manufactured by Johoku Chemical Co., Ltd., melting point: 140 ° C., hydroxyl equivalent: 281 g / eq)
-Benzotriazole-thiol compound 1: 2-mercapto-2H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 130 ° C., functional group equivalent: 151 g / eq)
-Benzotriazole-amine compound 1: 2-amino-2H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 122 ° C., functional group equivalent: 134 g / eq)
-Benzotriazole-carboxylic acid compound 1: 5-benzotriazole carboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 260 ° C., functional group equivalent: 163 g / eq)

Further, in the comparative example, the following materials were used as a material used in place of the compound having a functional group capable of reacting with an epoxy group and a benzotriazole group in one molecule.
-Phenolic compound 1: Phenol-Phenolic compound 2: o-cresol-Phenolic compound 3: 2-naphthol-Phenolic compound 4: Resorcinol-benzotriazole compound 1: 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., melting point : 97 ° C)
-Benzotriazole compound 2: 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 80 ° C.)
-Benzotriazole compound 3: 1-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 64 ° C.)

The following were used as silane compounds.
-Silane compound 1: (gamma)-glycidoxy propyl trimethoxysilane As a hardening accelerator, the following were used.
Hardening accelerator 1: Betaine-type adduct of triphenylphosphine and p-benzoquinone As the inorganic filler, the following were used.
Inorganic filler 1: Spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² / g As other additives, montanic acid ester (trade name: HW-E, manufactured by Clariant), carbon black Brand name: MA-600, manufactured by Mitsubishi Chemical Corporation) was used.

In this example, the epoxy equivalent is obtained by dissolving precisely weighed epoxy resin in methyl ethyl ketone, adding acetic acid and tetraethylammonium bromide solution, and then performing potentiometric titration under the condition of 25 ° C. with perchloric acid standard solution. Measured by An indicator may be used during this titration. In the present embodiment, the details are measured in accordance with JIS K 7236: 2009.
In this example, the hydroxyl equivalent is obtained by heating and refluxing the precisely weighed curing agent in pyridine-acetic anhydride mixed solution to acetylate the phenolic hydroxyl group, and the solution after reaction with sodium hydroxide at 25 ° C. It is measured by back titration. In the present embodiment, the details are measured in accordance with JIS K 0070: 1992.

In this example, the softening point is measured by the ring and ball method. In the ring and ball method, a resin was set on a support ring in a water bath, a ball of 3.5 ± 0.05 g was placed at the center of the ring, and the bath temperature was increased at a rate of 5 ± 0.5 ° C. per minute. After that, the weight of the ball is used to measure the temperature when the resin is sunk. In the present embodiment, the details are measured in accordance with JIS K7234: 1986.
In addition, melting point put a solid sample in a glass capillary, immerse it in silicone oil, and measure the melting point visually while raising the temperature of silicone oil (MP-21: Yamato Scientific Co., Ltd. Manufactured by company).

  The epoxy resin molding material for element sealing of an Example and a comparative example was evaluated by the various characteristic test of following (1)-(6). The evaluation results are shown in Tables 13 to 24 below. In addition, molding of the epoxy resin molding material for element sealing was performed 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. In addition, post curing was performed at 180 ° C. for 5 hours.

(1) Spiral flow Using a mold for spiral flow measurement according to EMMI-1-66, an epoxy molding material for element sealing was molded under the above conditions, and the flow distance (cm) was determined.
(2) Thermal hardness The epoxy resin molding material for element sealing is molded into a disk of 50 mm in diameter × 3 mm in thickness under the above conditions, and immediately after molding, it is a Shore D hardness tester (HD-1120 (type manufactured by Uejima Mfg. Co., Ltd.) It measured using D).

(3) Water absorption rate The disk molded by (2) is post-cured under the above conditions, left for 168 hours under conditions of 85 ° C., 60% RH, and measuring the mass change before and after standing, the water absorption rate (mass) %) = {(Disc weight after leaving-disc weight before leaving) / disc weight before leaving} × 100 was evaluated.
(4) Elastic modulus at 260 ° C (high temperature bending test)
A three-point bending test in accordance with JIS K 6911: 2006 was performed using a bending tester (Tensilon manufactured by A & D), and a bending elastic modulus (E) was determined while maintaining at 260 ° C. in a thermostatic chamber. The measurement was performed under the conditions of a head speed of 1.5 mm / min using a test piece formed of an epoxy resin molding material for element sealing into 10 mm × 70 mm × 3 mm under the above conditions.

(5) Measurement of adhesion to metal at 260 ° C (shear strength measurement)
An epoxy resin molding material for element sealing is molded into a copper plate or a silver-plated copper plate to a size of 4 mm in the bottom, 3 mm in the top and 4 mm in height under the above conditions, and post-cured by a bond tester (series 4000 manufactured by Dage Corporation) The shear adhesion was measured at a shear rate of 50 μm / s while maintaining the temperature of various copper plates at 260 ° C.

(6) Reflow resistance 80-pin flat package of external dimensions 20mm x 14mm x 2mm equipped with a silicone chip of 8mm x 10mm x 0.4mm (Lead frame material: Copper alloy, die pad upper surface and lead tip silver plated product ) Is molded and post-cured using the epoxy resin molding material for element sealing under the above conditions, and left for 1 week under the conditions of 85 ° C., 60% RH, and then Examples 1 to 16 and Comparative Example 1 to Comparative Example 16 at 240 ° C., Examples 17 to 20, Examples 25 to 32, Examples 41 to 43, and Comparative Examples 17 to 20, Comparative Examples 25 to 32 and Comparative Examples 41 to 43 are reflowed at 220 ° C. in Examples 21 to 24, Example 33 to 40 and Comparative Examples 21 to 24 and Comparative Examples 33 to 40 at 220 ° C. The presence or absence of peeling at the interface between the frame was observed by an ultrasonic flaw detector (Hitachi Construction Machinery Co., Ltd. HYE-FOCUS), was evaluated by peeling occurs Packages for the test number of packages (5).

  The characteristics of the above (1) to (6) are compared with examples and comparative examples in the same combination of epoxy resin and curing agent. For example, Example 1 to Example 16 and Comparative Example 1 to Comparative Example 16 in which epoxy resin 1 and 2 and curing agent 1 are combined, and Example 17 to Example in which epoxy resin 1 and 3 and curing agent 1 are combined 20 and Comparative Examples 17 to 20, Examples 21 to 24 and Comparative Examples 21 to 24 which are combinations of epoxy resins 1 and 4 and curing agent 2 and combinations of epoxy resins 1 and 5 and curing agent 1 Example 25 to Example 28 and Example 41 to 43, and Comparative Example 25 to Comparative Example 28 and Comparative Example 41 to 43, which are combinations of epoxy resins 1 and 6 and curing agent 1 Example 29 to Example 32 And Comparative Examples 29 to 32, Example 3 to Example 36 and Comparative Example 33 to Comparative Example 36, which are combinations of epoxy resins 1 and 5 and curing agent 2, and combinations of epoxy resins 1 and 6 and curing agent 2 Ah Comparing Comparative Examples 37 to Comparative Example 40 Example 37 to Example 40.

  As seen in Tables 13 to 24, in the examples to which the phenol derivative having a benzotriazole group was added, the shear adhesion (silver and copper) at 260 ° C. was higher than that of the comparative example, and 1 at 85 ° C., 60% RH. In the reflow treatment after being left for a week, no peeling occurs at the interface between the resin and the frame, and the reflow resistance is excellent.

  Among them, the examples using benzotriazole-phenol compounds 2 and 7 having a branched substituent in the hydroxyphenyl group show relatively higher adhesion than those using other benzotriazole-phenol compounds. The

  On the other hand, in the comparative example using the epoxy resin molding material for element sealing which does not contain the phenol derivative which has a benzotriazole group, compared with an example, 260 ° C shear adhesive force (silver and copper) is equivalent below 85 It was shown that, in the reflow treatment after being left for 1 week under the conditions of 60 ° C. and 60% RH, peeling at the interface between the resin and the frame occurred in all the packages, and the reflow resistance was inferior.

  As described above, a device sealing containing an epoxy resin having two or more epoxy groups in one molecule, a curing agent, and a compound having a functional group capable of reacting with the epoxy group in one molecule and a benzotriazole group It has been found that the epoxy resin molding material for use has high adhesion to metals at high temperatures, and can form a cured product having excellent reflow resistance.

Claims (8)

An epoxy resin having two or more epoxy groups in one molecule, a curing agent, and a compound having a functional group capable of reacting with the epoxy group in one molecule and a benzotriazole group ,
It said compound wherein as a functional group capable of reacting with an epoxy group, at least 1 Tsuoyu to element encapsulating epoxy resin molding material is selected from the group consisting of amino and mercapto groups. The epoxy resin molding material for element sealing according to claim 1, further comprising an inorganic filler. An epoxy resin having two or more epoxy groups in one molecule, a curing agent, and a compound having a functional group capable of reacting with the epoxy group in one molecule and a benzotriazole group ,
The compound has a group obtained by removing one hydrogen atom other than a hydrogen atom contained in a phenolic hydroxyl group from a phenol compound having an alkoxy group having 1 to 20 carbon atoms,
Furthermore, the epoxy resin molding material for element sealing which contains an inorganic filler by the content rate of 70 mass% or more in the epoxy resin molding material for element sealing. The melting point of the said compound is 220 degrees C or less, The epoxy resin molding material for element sealing of any one of Claims 1-3 . The epoxy resin molding material for element sealing according to any one of claims 1 to 4 , wherein the compound has a functional group equivalent of 90 g / eq to 500 g / eq of the functional group capable of reacting with the epoxy group. The epoxy resin molding material for element sealing according to any one of claims 1 to 5 , wherein the compound has one functional group capable of reacting with the epoxy group per one benzotriazole group. The content rate of the said compound is 0.1 mass% or more and 1.0 mass% or less in the total mass, The epoxy resin molding material for element sealing of any one of Claims 1-6 . The electronic component apparatus provided with an element and the hardened | cured material of the epoxy resin molding material for element sealing of any one of Claims 1-7 which seals the said element.