JP6277611B2 - Epoxy resin molding material for device sealing and electronic component device - Google Patents

Description

  The present invention relates to an element sealing epoxy resin molding material 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 (Integrated Circuits). 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 device sealing.

  As electronic devices have become smaller, lighter, and higher performance in recent years, mounting density has increased, and electronic component devices have come to adopt surface mount packages instead of conventional pin insertion types. Yes. When a semiconductor device is attached 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 that the package was not directly exposed to high temperature. However, in the surface mount type package, the entire semiconductor device is processed by a solder bath, a reflow device or the like, so that it is directly exposed to a soldering temperature. As a result, when the package absorbs moisture, moisture absorption moisture rapidly expands during soldering, causing peeling of the adhesive interface, package cracking, and the like, which reduces the reliability of the package in the mounting process. there were.

  As measures to solve the above problems, in order to reduce moisture absorption inside the semiconductor device, there is a method in which the IC is sufficiently dried and used before being mounted on the moisture-proof packaging or wiring board of the IC. This method is time consuming and expensive. As another countermeasure, there is a method of increasing the content of the filler in the element sealing molding material (for example, see Patent Document 1).

Japanese Patent Laid-Open No. 06-224328

However, although this method reduces moisture absorption inside the semiconductor device, there is a problem that it causes a significant decrease in fluidity. If the fluidity of the element molding resin molding material is low, problems such as the occurrence of gold wire flow, voids, pinholes, etc. may occur during molding.
The present invention has been made in view of such a situation. An epoxy resin molding material for sealing an element capable of forming a cured product having high adhesion to a metal at high temperatures and excellent reflow resistance, and an element sealed thereby It is an object to provide an electronic component device provided.

The present invention relates to the following.
(1) An epoxy resin molding material for device encapsulation containing an epoxy resin having two or more epoxy groups in one molecule, a curing agent and a compound having a phthalocyanine structure.
(2) The epoxy resin molding material for device encapsulation according to item (1), wherein the compound having a phthalocyanine structure is at least one selected from the group consisting of metal-free phthalocyanine and copper (II) phthalocyanine.
(3) The epoxy resin molding material for element sealing according to item (1) or item (2), wherein the content of the compound having the phthalocyanine structure is 0.1% by mass to 1.0% by mass.
(4) The epoxy resin molding material for device encapsulation according to any one of Items (1) to (3), further containing a silane compound.
(5) The epoxy resin molding material for element sealing according to any one of Items (1) to (4), further containing a curing accelerator.
(6) The epoxy resin molding material for element sealing according to any one of Items (1) to (5), which further contains an inorganic filler.
(7) An electronic component device having an element and a cured product of the epoxy resin molding material for element sealing according to any one of Items (1) to (6) for sealing the element.
(8) A group consisting of an element having a copper or silver wiring on the surface, an epoxy resin having two or more epoxy groups in one molecule for sealing the element, a curing agent, metal-free phthalocyanine and copper (II) phthalocyanine And a cured product of an epoxy resin molding material for sealing an element containing at least one kind of compound having a phthalocyanine structure selected from the above.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin molding material for element sealing which can form the hardened | cured material with high adhesiveness with the metal in high temperature and excellent in reflow resistance, and an electronic component apparatus provided with the element sealed by this are provided. Is done.

Hereinafter, the epoxy resin molding material for element sealing and the electronic component device 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.
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 there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.

<Epoxy resin molding material for device sealing>
The epoxy resin molding material for device encapsulation of the present invention contains (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent and (C) a compound having a phthalocyanine structure. .
The epoxy resin molding material for sealing an element of the present invention has high adhesion to a metal at a high temperature. The reason is not clear, but is presumed as follows.
When the phthalocyanine structure contains eight nitrogen atoms, the nitrogen atoms can interact with the hydroxyl groups contained in the cured epoxy resin, such as hydrogen bonds. On the other hand, the nitrogen atom contained in the phthalocyanine structure can form a complex with the metal, and the surface of the metal wiring included in the electronic component device can interact with the nitrogen atom. Adhesion of hardened epoxy resin to the metal wiring surface is improved by interposing a compound having a phthalocyanine structure between the hydroxyl group contained in the hardened epoxy resin and the metal on the surface of the metal wiring. It is presumed that the nature will be higher.

  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 device encapsulation of the present invention contains (A) an epoxy resin having two or more epoxy groups in one molecule. The number of epoxy groups should just be 2 or more in 1 molecule, it is preferable that it is 2-10, and it is more preferable that it is 2-5.
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 for an epoxy resin molding material for device sealing. For example, a phenol novolac type Epoxy resins, orthocresol novolac type epoxy resins, triphenylmethane type epoxy resins and other phenolic compounds, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F and other phenolic compounds and α-naphthol, β-naphthol, dihydroxynaphthalene And at least one selected from the group consisting of naphthol compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like under an acidic catalyst. A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation; bisphenol which is an alkyl-substituted, aromatic-ring-substituted or unsubstituted diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, 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; Glycidylamine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin; Dicyclopentadiene type epoxy resin which is an epoxidized product of a co-condensation resin of an enol compound; Naphthalene type epoxy resin which is an epoxy resin having a naphthalene skeleton; Alkyl-substituted, aromatic ring-substituted or unsubstituted phenol compound or alkyl-substituted, aromatic ring-substituted Or, an aralkyl type epoxy resin obtained by epoxidizing a phenol aralkyl resin or a naphthol aralkyl resin synthesized from an unsubstituted naphthol compound and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; a trimethylolpropane type epoxy resin; a terpene modified epoxy resin And a linear aliphatic epoxy resin or alicyclic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid. These may be used alone or in combination of two or more. The Good.

  Among them, (A) the epoxy resin having two or more epoxy groups in one molecule is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted biphenol from the viewpoint of compatibility between fluidity and curability. It preferably contains a biphenyl type epoxy resin. From the viewpoint of curability, it is preferable to contain a novolac type epoxy resin. From the viewpoint of heat resistance and low warpage, it preferably contains at least one selected from the group consisting of naphthalene type epoxy resins and triphenylmethane type epoxy resins. From the viewpoint of achieving both fluidity and flame retardancy, it is preferable to contain a bisphenol F-type epoxy resin that is an alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol F diglycidyl ether. From the viewpoint of compatibility between fluidity and reflowability, it is preferable to contain a thiodiphenol 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 preferably contains 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 preferably contains a naphthol aralkyl type epoxy resin synthesized from an alkyl-substituted, aromatic ring-substituted or unsubstituted naphthol compound and dimethoxyparaxylene.

  The biphenyl type epoxy resin can be 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 Examples thereof include an epoxy resin mainly composed of methylbiphenyl. Among these, as the biphenyl type epoxy resin, an epoxy resin mainly composed of 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl is preferable. As such an epoxy resin, a product name YX-4000 manufactured by Japan Epoxy Resin Co., Ltd. is available as a commercial product. The content of the biphenyl type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.

The thiodiphenol type epoxy resin can be obtained by reacting a thiodiphenol compound with epichlorohydrin by a known method. Examples of such epoxy resins include epoxy resins mainly composed of diglycidyl ether of 4,4′-dihydroxydiphenyl sulfide, and 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, etc. Among them, the thiodiphenol type epoxy resin is mainly composed of diglycidyl ether of 2,2′-dimethyl-4,4′-dihydroxy-5,5′-di-t-butyldiphenyl sulfide. Epoxy resins are preferred. As such an epoxy resin, a commercial name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd. is available.
When the thiodiphenol type epoxy resin is contained, the content of the thiodiphenol type epoxy resin is preferably 20% by mass or more in the total amount of the epoxy resin in order to exert its performance, and 30% by mass or more is preferable. More preferred is 50% by mass or more.

The bisphenol F type epoxy resin is obtained by reacting a bisphenol F compound with epichlorohydrin by a known method. Examples of such an epoxy resin include an epoxy resin mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, and 4,4′-methylenebis (2,3,6-trimethylphenol). An epoxy resin mainly composed of diglycidyl ether, an epoxy resin mainly composed of 4,4′-methylenebisphenol diglycidyl ether, and the like. Among them, as the bisphenol F type epoxy resin, 4,4 ′ An epoxy resin mainly composed of diglycidyl ether of methylenebis (2,6-dimethylphenol) is preferable. As such an epoxy resin, a product name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. is available as a commercial product.
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, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance. 50 mass% or more is more preferable.

A novolac type epoxy resin can be easily obtained by reacting a novolak resin with epichlorohydrin. Especially, as a novolak-type epoxy resin, an ortho cresol novolak-type epoxy resin is preferable. As such an epoxy resin, a commercial name N-660 manufactured by DIC Corporation is available.
In the case of containing the novolac type epoxy resin, the content of the novolak type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance. The mass% or more is more preferable.

As a naphthalene type epoxy resin, DIC Corporation make brand name HP-4700 etc. can be obtained as a commercial item.
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, in the total amount of the epoxy resin in order to exhibit its performance. More preferably, it is 50 mass% or more.

As a triphenylmethane type epoxy resin, Nippon Kayaku brand name EPPN-502 or Japan Epoxy Resin brand name 1032H60 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, and preferably 30% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. Is more preferable, and it is further more preferable to set it as 50 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 by a known method. Moreover, the 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. It is done. Phenol aralkyl type epoxy resin is commercially available as Nippon Kayaku Co., Ltd. product name NC-2000L, and biphenylene skeleton-containing phenol aralkyl type epoxy resin is commercially available as Nippon Kayaku Co., Ltd. product name NC-3000S. .
When the phenol aralkyl type epoxy resin is contained, the content of the phenol aralkyl type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance. 50 mass% or more is more preferable.

A naphthol aralkyl type epoxy resin is 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. It is done. As such an epoxy resin, Nippon Steel Chemical Co., Ltd. trade name ESN-375 or Nippon Steel Chemical Co., Ltd. trade name ESN-175 can be given as commercial products.
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, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance. 50 mass% or more is more preferable.

  Further, from the viewpoint of compatibility of flame retardancy, reflow resistance and fluidity, it is preferable to contain the biphenyl type epoxy resin and the biphenylene skeleton-containing phenol aralkyl type epoxy resin, and the content ratio by mass is particularly preferably Biphenyl type epoxy resin / biphenylene skeleton-containing phenol aralkyl type epoxy resin is preferably 50/50 to 5/95, more preferably 40/60 to 10/90, and 30/70 to 15/85. More preferably. As a compound satisfying such a content mass ratio, Nippon Kayaku Co., Ltd. brand name CER-3000L etc. are available as a commercial item.

In addition to the above, (A) a naphthalene-modified novolac type epoxy resin can also be used as an epoxy resin having two or more epoxy groups in one molecule. An example of such a compound is trade name HP-5000 manufactured by DIC Corporation.
When the naphthalene-modified novolac type epoxy resin is contained, the content of the naphthalene-modified novolak type epoxy resin is preferably 20% by mass or more, and 30% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. More preferred is 50% by mass or more.

Furthermore, (A) a dicyclopentadiene type epoxy resin can also be used as an epoxy resin having two or more epoxy groups in one molecule. An example of such a compound is trade name HP-7200 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 in the total amount of the epoxy resin in order to exhibit its performance. More preferred is 50% by mass or more.

  Biphenyl type epoxy resin, thiodiphenol type epoxy resin, bisphenol F type epoxy resin, novolac 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 type epoxy resin and the dicyclopentadiene type epoxy resin may be used alone or in combination of two or more. When two or more of these epoxy resins are used in combination, the content is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more in the total amount of the epoxy resin.

(A) The epoxy equivalent of an 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 150 g / eq to 500 g / eq. Is more preferable.
(A) 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 more preferably 50 ° C to 130 ° C. Further preferred.
(A) When the 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 further 50 ° C to 130 ° C. preferable.

In addition, (A) 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.
Put a solid sample ((A) epoxy resin having two or more epoxy groups in one molecule) into a glass capillary tube, immerse it in silicone oil, and measure the melting point visually while raising the temperature of the silicone oil. If the temperature difference from the temperature at which the solid sample begins to melt to the temperature at which it melts can be determined as a single point, and the temperature difference can be determined as a single point, the solid sample Is determined to have a melting point. On the other hand, if the temperature difference cannot be determined as a single temperature, it is determined that the solid sample has a softening point.

  The content of the epoxy resin having two or more epoxy groups in one molecule (A) contained in the epoxy resin molding material for device encapsulation of the present invention is preferably 3% by mass to 15% by mass, and preferably 3% by mass to 12%. % By mass is more preferable, and 5% by mass to 12% by mass is more preferable.

-Curing agent-
The element sealing epoxy resin molding material of the present invention contains (B) a curing agent.
The (B) curing agent used in the present invention is not particularly limited as long as it is generally used for an epoxy resin molding material for device sealing. A phenol novolak resin, an orthocresol novolak resin, a triphenylmethane type phenol resin. From the group consisting of phenol compounds such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, thiodiphenol and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene A novolak-type phenolic resin obtained by condensing or co-condensing at least one selected with a compound having an aldehyde group such as formaldehyde, benzaldehyde, salicylaldehyde under an acidic catalyst; Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from dimethoxyparaxylene or bis (methoxymethyl) biphenyl; copolymer in which the phenol novolak structure and the phenol aralkyl structure are randomly, block, or alternately repeated Type phenol aralkyl resin; paraxylylene and / or metaxylylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; dicyclopentadiene modified phenol resin; cyclopentadiene modified phenol resin; These may be used alone or in combination of two or more.

  Especially, as (B) hardening | curing agent, a phenol aralkyl resin, a copolymerization type phenol aralkyl resin, and a naphthol aralkyl resin are preferable from a viewpoint of fluidity | liquidity, a flame retardance, and reflow resistance, and heat resistance, a low expansion coefficient, and low From the viewpoint of warpage, a triphenylmethane type phenol resin is preferable, and from the viewpoint of curability, a novolac 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, Inc. brand name XLC and Meiwa Kasei Co., Ltd. brand name MEH-7800 are mentioned as a commercial item. As a biphenylene skeleton containing phenol aralkyl resin, Meiwa Kasei Co., Ltd. brand name MEH-7851 is mentioned as a commercial item.
When the 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 more preferably 50% by mass in the total amount of the curing agent in order to exhibit the performance. The above is more preferable.
As a naphthol aralkyl resin, Nippon Steel Chemical Co., Ltd. brand name SN-475 or Nippon Steel Chemical Co., Ltd. brand name SN-170 is mentioned as a commercial item.
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 more preferably 50% by mass in the total amount of the curing agent in order to exhibit the performance. The above is more preferable.

  The phenol aralkyl resin and the naphthol aralkyl resin are preferably preliminarily mixed with acenaphthylene from the viewpoint of flame retardancy. Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Further, instead of acenaphthylene, a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins can be used. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out by heating. 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. If it is 60 ° C. or higher, there is a tendency that the moldability is not easily lowered due to oozing during molding, and if it is 150 ° C. or lower, compatibility with the resin tends to be improved. 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, (meth) acrylic acid ester, maleic anhydride, itaconic anhydride, fumaric acid, and fumaric acid ester. The content of these aliphatic olefins is preferably 20% by mass or less, more preferably 9% by mass or less, based on the total amount of the polymerization monomers.

  As a method of premixing part or all of the phenol aralkyl resin and naphthol aralkyl resin with acenaphthylene, the curing agent and acenaphthylene are finely pulverized and mixed with a mixer or the like in a solid state, and both components are dissolved. After being dissolved together in the solvent, it can be performed by a method of removing the solvent, a method of melting and mixing the curing agent and / or acenaphthylene at a temperature equal to or higher than the softening point, and a mixture in which both components are well mixed is obtained. A melt mixing method is preferable because it is obtained and contains less impurities. A premix (acenaphthylene-modified curing agent) is produced by the above method. The 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, more preferably 120 ° C to 200 ° C. In addition, in the melt mixing, if both are mixed well, the mixing time is not limited and is preferably 1 hour to 20 hours, more preferably 2 hours to 15 hours. When preliminarily mixing the curing agent and acenaphthylene, acenaphthylene may be polymerized or reacted with the curing agent during mixing.

  Examples of the triphenylmethane type phenol resin include commercially available product names HE-910 manufactured by Air Water Co., Ltd. and MEH-7500 manufactured by Meiwa Kasei Co., Ltd. When using a triphenylmethane type phenol resin, the content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

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

  As the copolymerization type phenol aralkyl resin, trade name HE-510 manufactured by Air Water Co., Ltd. is available as a commercial product. When a copolymeric phenol aralkyl resin is used, the content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

  As the dicyclopentadiene-modified phenol resin, a product name GDP-6085 manufactured by Gunei Chemical Co., Ltd. is commercially available. When using a dicyclopentadiene-modified phenol resin, the content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

The above phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene-modified phenol resin, triphenylmethane type phenol resin, novolac type phenol fat and copolymer type phenol aralkyl resin can be used alone or in combination of two or more. May be used in combination. The content in the case where two or more of the above resins are used in combination is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more in the total amount of the curing agent.
(B) When the curing agent is a phenol resin, the hydroxyl equivalent of the phenol resin is preferably 70 g / eq to 1000 g / eq, more preferably 75 g / eq to 700 g / eq, and further preferably 80 g / eq to 500 g / eq. preferable.
(B) When a hardening | curing agent has a softening point, 40 to 180 degreeC is preferable, as for this softening point, 45 to 150 degreeC is more preferable, and 50 to 130 degreeC is still more preferable.
(B) When a hardening | curing agent has melting | fusing point, 40 to 180 degreeC is preferable, as for this melting | fusing point, 45 to 150 degreeC is more preferable, and 50 to 130 degreeC is still more preferable.

Whether (B) the curing agent has a softening point or a melting point is determined as follows.
Put a solid sample ((B) curing agent) in a glass capillary tube, immerse it in silicone oil, and measure the melting point visually by increasing the temperature of the silicone oil. It is determined whether or not the temperature difference from the temperature at which the melting starts to the temperature at which the melting ends can be determined as a single temperature. If the temperature difference can be determined as the single temperature, it is determined that the solid sample has a melting point. On the other hand, if the temperature difference cannot be determined as a single temperature, it is determined that the solid sample has a softening point.

  In the present invention, (A) an epoxy resin having two or more epoxy groups in one molecule and (B) an equivalent ratio of the curing agent, that is, a ratio of the number of hydroxyl groups to the number of epoxy groups (number of hydroxyl groups in curing agent / in epoxy resin) The number of epoxy groups) is not particularly limited, and is preferably set in the range of 0.5 to 2.0, and more preferably 0.6 to 1.3 in order to suppress each unreacted component. In order to obtain an epoxy resin molding material for sealing an element having excellent moldability, it is more preferably set in the range of 0.8 to 1.2.

-Compound having phthalocyanine structure-
The epoxy resin molding material for device encapsulation of the present invention contains (C) a compound having a phthalocyanine structure.
In the present invention, the “compound having a phthalocyanine structure” includes substituted or unsubstituted metal-free phthalocyanine, substituted or unsubstituted metal phthalocyanine, substituted or unsubstituted metal-free naphthalocyanine, substituted or unsubstituted metal naphthalocyanine, and the like. Can be mentioned.

  (C) As a substituent contained in the compound which has a phthalocyanine structure, halogen atoms, such as a chlorine atom and a bromine atom, etc. are mentioned.

  Examples of the metal ion contained in the metal phthalocyanine include copper (II), manganese (II), iron (II), cobalt (II), nickel (II), zinc (II) and the like.

  As the compound having a (C) phthalocyanine structure used in the present invention, it is preferable to use at least one selected from the group consisting of metal-free phthalocyanine and copper (II) phthalocyanine from the viewpoint of easy availability. The metal-free phthalocyanine and copper (II) phthalocyanine are particularly preferably unsubstituted from which no substituent is bonded from the viewpoint of easy availability. In addition, when at least one selected from the group consisting of metal-free phthalocyanine and copper (II) phthalocyanine is used as the compound having a (C) phthalocyanine structure, it is excellent in adhesion to a metal containing copper or silver on the surface. preferable.

  Copper (II) phthalocyanine has a plurality of crystal states such as α-type and β-type, and may be either a purified product or a mixture thereof. In particular, it is preferable to use β-type copper (II) phthalocyanine (also known as Pigment Blue 15: 3) having a stable crystal state. As for the content rate of the compound which has the (C) phthalocyanine structure used in this invention, 0.1 mass%-1.0 mass% are preferable in the epoxy resin molding material for element sealing. If it is 0.1 mass% or more, the adhesiveness with the metal at high temperature tends to be improved, and if it is 1.0 mass% or less, the hardness of the epoxy resin molding material for device encapsulation tends to be improved.

The compound having a (C) phthalocyanine structure in the epoxy resin molding material for device encapsulation is quantified by the following method in a state before curing.
The element sealing epoxy resin molding material is dispersed in a solvent, and components (inorganic filler, colorant, etc.) insoluble in the solvent are removed from the dispersion. By analyzing the solution obtained by removing components insoluble in the solvent using high performance liquid chromatography (HPLC), the compound having (C) a phthalocyanine structure is detected and quantified.

  In the present invention, the content ratio of (A) an epoxy resin having two or more epoxy groups in one molecule and (C) a compound having a phthalocyanine structure is (A) having two or more epoxy groups in one molecule. The compound (C) having a phthalocyanine structure is preferably 1 part by mass to 20 parts by mass, more preferably 2 parts by mass to 15 parts by mass, and more preferably 3 parts by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. More preferably, it is a part.

-Silane compound-
The element sealing epoxy resin molding material of the present invention may contain (D) a silane compound.
(D) As the silane compound, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, mercaptosilane such as γ-mercaptopropyltrimethoxysilane, aminosilane such as γ-anilinopropyltrimethoxysilane, methyltrimethoxysilane And alkyl silanes such as γ-isocyanatopropyltrimethoxysilane, and vinyl silanes such as vinyltrimethoxysilane. These may be used alone or in combination of two or more.

  When (D) the silane compound is contained, the content of the (D) silane compound is preferably 0.06% by mass to 2% by mass in the epoxy resin molding material for device sealing from the viewpoint of moldability and fluidity. 1 mass%-0.75 mass% is more preferable, and 0.2 mass%-0.7 mass% is further 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 not to occur.

-Curing accelerator-
The epoxy resin molding material for element sealing of the present invention may contain (E) a curing accelerator.
As (E) hardening accelerator used by this invention, it is generally used with 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. 0.0] cycloamidine compounds such as undecene-7; maleic anhydride, 1,2-benzoquinone, 1,4-benzoquinone, diphenoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-cycloamidine compound 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 Compounds with intramolecular polarization formed by adding compounds with π bonds such as compounds, diazophenylmethane, and phenolic resins Tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2 -Imidazole compounds such as heptadecylimidazole and their derivatives; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; Phosphorus compound having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, phenol resin; Tetrasubstituted phosphonium tetrasubstituted borates such as ruphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate; and 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, etc. And tetraphenylboron salts thereof and derivatives thereof. These may be used alone or in combination of two or more.

  The third phosphine used in the adduct of an organic phosphine compound and a quinone compound is not particularly limited, and is dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, 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) ) Phosphine, tris (2,6-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4-me Kishifeniru) phosphine, tertiary phosphines are exemplified with an aryl group such as tris (4-ethoxyphenyl) phosphine, triphenylphosphine is preferable in view of moldability.

  In addition, the quinone compound used for the adduct of the tertiary 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.

  In the case of containing (E) a curing accelerator, the content of (E) the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, and (A) an epoxy group in one molecule 0.1 parts by mass to 10 parts by mass, preferably 0.3 parts by mass to 5 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin having 2 or more, (B) curing agent and (C) the compound having a phthalocyanine structure. Part 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, the curing rate does not become too fast and a good molded product tends to be obtained.

-Inorganic filler-
The element sealing epoxy resin molding material of the present invention may contain (F) an inorganic filler.
The (F) 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 used as an epoxy resin molding material for device sealing. If it is generally used, it will not be restrict | limited. Inorganic fillers include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, fosterite, steatite, spinel, Examples thereof include powders such as mullite and titania, beads formed by spheroidizing these, and glass fibers. These may be used alone or in combination of two or more. Among these, as the (F) inorganic filler, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The shape of the filler is preferably spherical from the viewpoint of fluidity and mold wear during molding. In particular, spherical fused silica is preferable from the viewpoint of a balance between cost and performance.

  (F) When containing an inorganic filler, the content of the (F) inorganic filler is from the viewpoint of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction and strength improvement, and epoxy resin molding for device encapsulation. 70 mass%-95 mass% in a material are 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)
In addition, an anion exchanger can be blended with the epoxy resin molding material for sealing an element of the present invention, if necessary, for the purpose of improving the moisture resistance and high temperature storage characteristics of an element such as an IC. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Examples of the anion exchanger include hydrotalcite; a hydrous oxide of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth; These may be used alone or in combination of two or more.

  When an anion exchanger is contained, 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) An epoxy group is contained in one molecule. 0.1 to 30 parts by mass is preferable with respect to 100 parts by mass of the epoxy resin having two or more, and 1 to 5 parts by mass is more preferable.

(Release agent)
The epoxy resin molding material for element sealing of the present invention may contain a release agent as necessary. Examples of the mold release agent include 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 10,000, such as trade name H4, PE, and PED series manufactured by Clariant Japan.
When the release agent is contained, the release agent is preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (A) having two or more epoxy groups in one molecule. It is more preferable to use 1 part by mass to 5 parts by mass. If it is 0.01 mass part or more, there exists a tendency for mold release to become sufficient, and if it is 10 mass parts or less, there exists a tendency for the adhesive fall to be suppressed.
Examples of mold release agents other than the above include carnauba wax, montanic acid ester, montanic acid, and stearic acid. These may be used alone or in combination of two or more. When these other release agents are used in combination with oxidized or non-oxidized polyolefin, the total content thereof is (A) based on 100 parts by mass of epoxy resin having two or more epoxy groups in one molecule. 0.1 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 sealing an element of the present invention can contain a conventionally known flame retardant as necessary. Examples of flame retardants include brominated epoxy resins; antimony trioxide; red phosphorus; red phosphorus and phosphorus coated with inorganic substances such as aluminum hydroxide, magnesium hydroxide, zinc oxide and / or thermosetting resins such as phenol resins. Phosphorus compounds such as acid esters; melamine, melamine derivatives, melamine-modified phenolic resins, compounds containing a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives; phosphorus and nitrogen-containing compounds such as cyclophosphazene; aluminum hydroxide, Examples thereof include compounds containing metal elements such as magnesium hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. These may be used alone or in combination of two or more.
When the flame retardant is contained, the content of the flame retardant is not particularly limited, and (A) 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. 2 parts by mass to 15 parts by mass is more preferable.

(Colorants, etc.)
Moreover, the epoxy resin molding material for element sealing of the present invention may contain a colorant such as carbon black, organic dye, organic pigment, titanium oxide, red lead, or 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 device sealing-
The epoxy resin molding material for device encapsulation of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, a method of mixing the components of the epoxy resin molding material for sealing an element of the present invention with a mixer or the like, melt-kneading with a mixing roll, an extruder or the like, and cooling and pulverizing can be mentioned. Specifically, it can be obtained by a method of stirring or mixing the above-described components, kneading with a kneader, roll, extruder or the like that has been heated to 70 ° C. to 140 ° C., cooling, and pulverizing. . It is easy to use if it is tableted with dimensions and mass that match the molding conditions.

<Electronic component device>
The electronic component device of the present invention includes an element and a cured product of the epoxy resin molding material for element sealing of the present invention that seals the element.
The electronic component device of the present invention includes a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, and other supporting members, an active element such as a semiconductor chip, transistor, diode, thyristor, capacitor, resistor, coil Examples thereof include an electronic component device in which an element such as a passive element is mounted and a necessary part is sealed with the epoxy resin molding material for element sealing of the present invention. 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 epoxy resin molding for device sealing of the present invention is performed. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outlet), which are sealed by transfer molding using materials. general resin-encapsulated ICs such as package (package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), and tape carrier A semiconductor chip connected to a bump by a TCP (Tape Carrier Package) encapsulated with an epoxy resin molding material for element encapsulation of the present invention, wiring formed on a wiring board or glass, wire bonding, flip chip bonding, soldering COB (Chip On) in which active elements such as semiconductor chips, transistors, diodes, thyristors, etc. and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the epoxy resin molding material for element sealing of the present invention. Board) Module, hybrid IC, multi-chip module, after mounting an element on the surface of an organic substrate on which a wiring board connection terminal is formed on the back, and connecting the element and the wiring formed on the organic substrate by bump or wire bonding In 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.
As a method for sealing an element using the epoxy resin molding material for element sealing of the present invention, a low-pressure transfer molding method is generally used, but an injection molding method, a compression molding method, or the like may be used.

The electronic component device according to the present invention includes an element having a wiring with copper or silver on the surface, (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent, and none. And a cured product of the epoxy resin molding material for device encapsulation of the present invention containing at least one compound having a (C) phthalocyanine structure selected from the group consisting of metal phthalocyanine and copper (II) phthalocyanine, Also good.
When the epoxy resin molding material for device encapsulation of the present invention contains at least one selected from the group consisting of metal-free phthalocyanine and copper (II) phthalocyanine as the compound having (C) phthalocyanine structure, The epoxy resin molding material for element sealing shows excellent adhesiveness to the wiring whose surface is copper or silver. Therefore, the epoxy resin molding material for device encapsulation of the present invention containing at least one selected from the group consisting of (C) a phthalocyanine structure and a metal-free phthalocyanine and copper (II) phthalocyanine has a surface of copper or silver This is particularly effective for sealing an electronic component device including an element having the above wiring. In addition, the wiring whose surface is copper or silver includes copper wiring, silver wiring, wiring in which silver plating is performed on the surface of copper wiring, and the like.

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

  The following components are blended in parts by mass shown in Tables 1 to 6 below, and roll kneading is carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. Examples 1 to 24 and Comparative Examples 1 to 1 24 element sealing epoxy resin molding materials were produced. Note that the blank in the table indicates no blending.

(A) As an epoxy resin having two or more epoxy groups in one molecule, the following was used.
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 Resin Co., Ltd., number of epoxy groups contained in one molecule: 2)
-Epoxy resin 2: Epoxy equivalent 240 g / eq, softening point 96 ° C biphenyl type epoxy resin / biphenylene skeleton-containing phenol aralkyl type epoxy resin = 20/80 mass ratio composition (trade name CER- manufactured by Nippon Kayaku Co., Ltd. 3000L, the number of epoxy groups contained in one molecule: 2 to 5)
Epoxy resin 3: phenol aralkyl type epoxy resin having an epoxy equivalent of 238 g / eq and a softening point of 55 ° C. (trade name NC-2000L, manufactured by Nippon Kayaku Co., Ltd., number of epoxy groups contained in one molecule: 2 to 5 )
-Epoxy resin 4: Ortho-equivalent novolak epoxy resin having an epoxy equivalent of 202 g / eq and a softening point of 60 ° C (trade name N-660, manufactured by DIC Corporation, number of epoxy groups contained in one molecule: 2 to 5)
Epoxy resin 5: naphthalene-modified novolak type epoxy resin having an epoxy equivalent of 250 g / eq and a softening point of 58 ° C. (trade name HP-5000, manufactured by DIC Corporation, 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. (product name HP-7200, manufactured by DIC Corporation, number of epoxy groups contained in one molecule: 2 to 5)

(B) As the curing agent, the following was used.
Curing agent 1: phenol aralkyl resin having a hydroxyl group equivalent of 175 g / eq and a softening point of 70 ° C. (trade name MEH-7800 manufactured by Meiwa Kasei Co., Ltd.)
Curing agent 2: Phenol novolak resin having a hydroxyl group equivalent of 106 g / eq and a softening point of 83 ° C. (trade name H-100, manufactured by Meiwa Kasei Co., Ltd.)

(C) As the compound having a phthalocyanine structure, at least one of metal-free phthalocyanine and copper (II) phthalocyanine was used. Copper (II) phthalocyanine used β type. In the table, at least one of metal-free phthalocyanine and copper (II) phthalocyanine is collectively referred to as a phthalocyanine compound.
Moreover, the material used instead of the compound which has a phthalocyanine structure in a comparative example is as follows.
-Phenol compound 1: Phenol-Phenol compound 2: o-cresol-Phenol compound 3: Resorcinol

(D) As the silane compound, silane compound 1: γ-glycidoxypropyltrimethoxysilane, (E) As the curing accelerator, curing accelerator 1: betaine-type adduct of triphenylphosphine and p-benzoquinone, (F) As the inorganic filler, an 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 was used. As other additive components, montanic acid ester and carbon black were used.

In this example, the epoxy equivalent is measured by dissolving a precisely weighed epoxy resin in methyl ethyl ketone, adding acetic acid and a tetraethylammonium bromide acetic acid solution, and then performing potentiometric titration with a perchloric acid acetic acid standard solution. An indicator may be used for this titration. In this embodiment, details are measured according to JIS K7236: 2009.
In this example, the hydroxyl group equivalent is measured by heating and refluxing a precisely weighed curing agent in a pyridine-acetic anhydride mixed solution to acetylate the phenolic hydroxyl group, and back titrating the solution after the reaction with sodium hydroxide. The In the present embodiment, details are measured in accordance with JIS K0070: 1992.
In this example, the softening point is measured by the ring and ball method. In the ring and ball method, a resin is set on a support ring in a water bath, and a ball of 3.5 ± 0.05 g is placed in the center of the ring to raise the bath temperature at a rate of 5 ± 0.5 ° C. per minute. After that, the temperature when the resin sags due to the weight of the sphere is measured. In this embodiment, details are measured in accordance with JIS K7234: 1986.
The melting point is determined by placing a solid sample in a glass capillary tube, immersing it in silicone oil, and measuring the melting point visually while raising the temperature of the silicone oil (MP-21: Yamato Scientific Co., Ltd.). Measured by company).

  The epoxy resin molding materials for device encapsulation of Examples and Comparative Examples were evaluated by the following various characteristic tests (1) to (6). The evaluation results are shown in Tables 7 to 12 below. In addition, the epoxy resin molding material for element 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 molding material for device sealing was molded under the above conditions, and the flow distance (cm) was determined.
(2) Hardness upon heating An epoxy resin molding material for element sealing is molded into a disk 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 Ueshima Seisakusho Co., Ltd.) D)).
(3) A disk molded at a water absorption rate (2) is post-cured under the above conditions, left for 168 hours at 85 ° C. and 60% RH, and the mass change before and after being left is measured to determine 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 K6911: 2006 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 element sealing epoxy resin molding material into 10 mm × 70 mm × 3 mm under the above conditions.

(5) Measurement of adhesive strength with metal at 260 ° C (measurement of shear strength)
An epoxy resin molding material for device sealing is formed 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 of 3 mmφ, and a height of 4 mm, post-cured, and by a bond tester (Daisy series 4000). While maintaining the temperature of various copper plates at 260 ° C., the shear adhesive strength (MPa) was measured at a shear rate of 50 μm / s.
(6) Reflow resistance 80mm flat package with outer dimensions of 20mm x 14mm x 2mm mounted with 8mm x 10mm x 0.4mm silicone chip (Lead frame material: copper alloy, die pad top surface and lead tip silver plated product) ) Was molded and post-cured using the epoxy resin molding material for device sealing under the above-mentioned conditions, and allowed to stand for 1 week at 85 ° C. and 60% RH, then Examples 1 to 8 and Comparative Example 1 to Comparative Example 8 is 240 ° C., Example 9 to Example 12, Example 17 to Example 20, Comparative Example 9 to Comparative Example 12 and Comparative Example 17 to Comparative Example 20 are 230 ° C., and Example 13 to Example 16, Example 21 to Example 24, Comparative Example 13 to Comparative Example 16, and Comparative Example 21 to Comparative Example 24 were subjected to reflow treatment at 220 ° C., and ultrasonic waves were used to determine the presence or absence of delamination at the interface between the resin and the frame. Was observed in wounds apparatus (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 with the same combination of epoxy resin and curing agent. For example, Examples 1 to 8 which are combinations of epoxy resins 1 and 2 and curing agent 1, and Comparative Examples 1 to 8, Examples 9 to Examples which are combinations of epoxy resins 1 and 3 and curing agent 1 12 and Comparative Example 9 to Comparative Example 12, Epoxy Resins 1 and 4 and Curing Agent 2, Example 13 to Example 16, Comparative Example 13 to Comparative Example 16, Epoxy Resins 1 and 5 and Curing Agent 1 Examples 19 to 20 and Comparative Examples 19 to 20, which are combinations of Examples 17 to 18 and Comparative Examples 17 to 18, Epoxy Resins 1 and 6 and Curing Agent 1, are Epoxy Resin 1 5 and 5 and a combination of curing agent 2 Examples 21 to 22 and Comparative Examples 21 to 22 and epoxy resins 1 and 6 and combinations of curing agent 2 to Examples 23 to 24 and Comparative Example 23 Comparative Example 24 Compared.
As shown in Tables 7 to 12, the examples to which the compounds having a phthalocyanine structure were added had higher 260 ° C. shear adhesive strength (silver and copper) than the comparative examples, and were allowed to stand for 1 week at 85 ° C. and 60% RH. In the subsequent reflow treatment, no peeling occurs at the interface between the resin and the frame, and the reflow resistance is excellent.

  The 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 standing for 1 week at 85 ° C. and 60% RH, the peeling at the interface between the resin and the frame is all the same in comparison with the examples, where the 260 ° C. shear adhesive strength (silver and copper) is the same or less. Occurs in the package and has poor reflow resistance.

Claims (9)

Containing an epoxy resin having two or more epoxy groups in one molecule, a curing agent and a compound having a phthalocyanine structure;
The epoxy resin, biphenyl type epoxy resin and Na Futaren modified novolac-type epoxy resins and epoxy resin molding material for element encapsulation containing.   The epoxy resin molding material for element sealing according to claim 1, wherein the content of the naphthalene-modified novolac epoxy resin is 20% by mass or more based on the total amount of the epoxy resin.   The epoxy resin molding material for device encapsulation according to claim 1 or 2, wherein the compound having a phthalocyanine structure is at least one selected from the group consisting of metal-free phthalocyanine and copper (II) phthalocyanine. The content rate of the compound which has the said phthalocyanine structure is 0.1 mass%-1.0 mass%, 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 , further comprising a silane compound. The epoxy resin molding material for element sealing of any one of Claims 1-5 which further contains a hardening accelerator. The epoxy resin molding material for element sealing according to any one of claims 1 to 6 , further comprising an inorganic filler. Elements,
The cured product of the epoxy resin molding material for device sealing according to any one of claims 1 to 7 , which seals the device,
An electronic component device. An element having a copper or silver wiring on the surface;
Containing at least one compound having a phthalocyanine structure selected from the group consisting of an epoxy resin having two or more epoxy groups in one molecule for sealing the element, a curing agent, and a metal-free phthalocyanine and copper (II) phthalocyanine. , the epoxy resin is a cured product of the element encapsulating epoxy resin molding material comprising a biphenyl type epoxy resin and Na Futaren modified novolac-type epoxy resins,
An electronic component device.