JP2008115364A - Epoxy resin composition and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition which is free from the occurrence of peeling or cracking after a reflow process in a packaging process and to provide an electronic component device provided with an elemental component sealed by the epoxy resin composition. <P>SOLUTION: The epoxy resin composition for sealing a plated lead frame package contains (A) an epoxy resin and (B) a curing agent wherein (B) the cuing agent contains a curing agent represented by general formula (I) and a curing agent represented by general formula (II). In the formula (I), n represents an integer of 0-10 and in the formula (II), n represents an integer of 0-14. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  Conventionally, in the field of element sealing of electronic component devices such as transistors, ICs, and LSIs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts.

  In recent years, electronic devices are also being developed in the automobile field. Electronic devices for automobiles are often required to have higher reliability in terms of reliability such as heat resistance than so-called consumer applications such as personal computers and home appliances. In order to increase the heat resistance of the electronic device, a technique such as increasing the glass transition point of the epoxy resin molding material for sealing can be used.

  In epoxy resin molding materials for sealing, halogenated resins such as decabromo and antimony compounds have been used as flame retardants in the past, but in recent years there has been a movement to regulate the amount of these compounds from the viewpoint of environmental protection. There is a demand for non-halogenation (non-bromo) and non-antimony. In addition, it is known that a bromo compound has an adverse effect on the high temperature storage characteristics of a plastic encapsulated IC. From this viewpoint, reduction of the amount of bromo resin is desired.

  As a method for achieving flame retardancy without using brominated resin or antimony oxide, a method of adding an organic phosphorus compound (for example, see Patent Document 1), a method of adding a metal hydroxide (for example, a patent) Reference 2), and a proposal of a method of adding a curing accelerator or a coupling agent having a specific structure to an epoxy resin and a curing agent having a specific structure (for example, refer to Patent Documents 3 and 4). ing.

In recent years, 42 alloy alloys or copper alloys that have been previously plated with nickel-palladium-gold (Ni-Pd-Au) or the like have been used as lead frames for electronic devices. However, there is a concern that the use of such a plated lead frame lowers the adhesion between the sealing epoxy resin molding material and the lead frame and causes peeling after the reflow process. In particular, a method of containing a disulfide compound in a sealing epoxy resin molding material as a means for improving adhesion to a lead frame plated with nickel-palladium-gold (Ni-Pd-Au) in advance in a copper alloy (for example, Patent Documents 5, 6, and 7).
JP 9-235449 A Japanese Patent Laid-Open No. 9-241383 JP 2003-171530 A JP 2004-99837 A JP 2004-285316 A Japanese Patent Laid-Open No. 2005-2221 JP 2006-28476 A

  However, when a disulfide compound is included in the epoxy resin molding material for sealing, the adhesion with a lead frame in which a copper alloy is previously plated with nickel-palladium-gold (Ni-Pd-Au) or the like is improved, The problem of cracking after the package reflow process has not been solved. That is, the present invention is a lead frame in which a copper alloy is pre-plated with nickel-palladium-gold (Ni-Pd-Au) or the like while ensuring high flame resistance without using brominated epoxy resin or antimony oxide. It is an object of the present invention to provide an epoxy resin composition that does not cause peeling and cracking after a reflow process in a package using the above, and an electronic component device including an element sealed by the epoxy resin composition.

The present invention relates to the following.
1. (A) An epoxy resin, (B) a curing lead, and (B) a plated lead frame containing a curing agent represented by the general formula (I) and a curing agent represented by the general formula (II). Epoxy resin composition for package sealing.

（（Ｉ）式中で、ｎは０〜１０の整数を示す。）

(In the formula (I), n represents an integer of 0 to 10.)

（（ＩＩ）式中で、ｎは０〜１４の整数を示す。）

(In the formula (II), n represents an integer of 0 to 14.)

  2. (A) The epoxy resin composition of claim | item 1 in which an epoxy resin contains the epoxy resin represented by general formula (III).

（（ＩＩＩ）式中で、Ｒ^１〜Ｒ^９は全てが同一でも異なっていてもよく、水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数６〜１０のアリール基、及び、炭素数７〜１０のアラルキル基から選ばれる。ｎは０〜１０の整数を示す。ｉは０〜４の整数を示す）

(In formula (III), R ^{1 to} R ⁹ may all be the same or different, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms. And an aryl group having 7 to 10 carbon atoms, n is an integer of 0 to 10, and i is an integer of 0 to 4.

3. (A) The epoxy resin composition of claim | item 2 in which an epoxy resin contains the epoxy resin further represented by general formula (IV).

（（ＩＶ）式中で、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(In the formula (IV), R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. Represents an integer of 0 to 3.)

4). Item 4. The epoxy resin composition according to item 3, wherein R ^{1 to} R ^{8 of the} epoxy resin represented by the general formula (IV) are all hydrogen atoms.
5. (A) The epoxy resin composition in any one of claim | item 1 -4 in which an epoxy resin contains the epoxy resin represented by general formula (V).

（（Ｖ）式中で、Ｒ^１〜Ｒ^８は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数６〜１０のアリール基、及び炭素数７〜１０のアラルキル基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。

(In formula (V), R ^{1 to} R ⁸ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 to 10 carbon atoms. And all may be the same or different, and n represents an integer of 0 to 3.

6). An electronic component device comprising an element sealed with the epoxy resin composition according to any one of Items 1 to 5.

  The epoxy resin composition according to the present invention is excellent in reliability such as flame retardancy and heat resistance, and if this epoxy resin composition is used to seal electronic parts such as IC and LSI, it has excellent reflow resistance. An electronic component device can be obtained, and its industrial value is great. Furthermore, the epoxy resin composition according to the present invention is excellent in adhesion and reflow resistance to a lead frame obtained by plating copper or a copper alloy, and therefore a lead frame package obtained by plating copper or a copper alloy. It can be set as the sealing material excellent in the use.

  The (A) epoxy resin used in the present invention is generally used in an epoxy resin composition for sealing and is not particularly limited. For example, a phenol novolak type epoxy resin, an orthocresol novolak type epoxy resin, or triphenyl is used. Phenols such as epoxy resins having a methane skeleton, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde Epoxidized novolac resin obtained by condensation or co-condensation with a compound having an aldehyde group such as propionaldehyde, benzaldehyde, salicylaldehyde, etc. under an acidic catalyst. By reaction of polychlorobasic acid such as diglycidyl ether such as substituted, aromatic ring-substituted or unsubstituted bisphenol A, bisphenol F, bisphenol S, biphenol, stilbene type epoxy resin, hydroquinone type epoxy resin, phthalic acid, dimer acid and epichlorohydrin Obtained glycidyl ester type epoxy resin, diaminodiphenylmethane, isocyanuric acid, and other polyamines and epichlorohydrin, glycidylamine type epoxy resin, epoxidized product of dicyclopentadiene and phenols co-condensation resin, epoxy having naphthalene ring Aralkyl-type phenol resins, naphthol / aralkyl resins, etc. synthesized from resins, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Epoxidized aralkyl-type phenol resin, trimethylolpropane-type epoxy resin, terpene-modified epoxy resin Linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid, alicyclic epoxy resin, containing sulfur atoms An epoxy resin etc. are mentioned, These 1 type may be used independently or may be used in combination of 2 or more type.

  Especially, it is preferable to contain the biphenyl aralkyl type epoxy resin shown by the following general formula (III) from a viewpoint of coexistence of a flame retardance and reflow resistance, Furthermore, a flame retardance and reflow resistance, From the viewpoint of compatibility of fluidity, it is preferable to contain two types of biphenyl type epoxy resins represented by (III) and (IV), and the blending weight ratio thereof is (IV) / (III) = 50 / It is preferable that it is 50-5 / 95, 40 / 60-10 / 90 is more preferable, and 30 / 70-15 / 85 is further more preferable. As a compound satisfying such a blending weight ratio, CER-3000L (manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

（（ＩＩＩ）式中で、Ｒ^１〜Ｒ^９は全てが同一でも異なっていてもよく、水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基炭素数６〜１０のアリール基、及び炭素数７〜１０のアラルキル基から選ばれる。ｎは０〜１０の整数を示す。ｉは０〜４の整数を示す。）
炭素数１〜１０のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基が挙げられる。炭素数１〜１０のアルコキシル基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられる。炭素数６〜１０のアリール基としては、例えば、フェニル基、トリル基、キシリル基が挙げられる。炭素数７〜１０のアラルキル基としては、例えば、ベンジル基、フェネチル基が挙げられる。なかでも水素原子又はメチル基が好ましい。

(In formula (III), R ^{1 to} R ⁹ may all be the same or different, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and having 6 to 10 carbon atoms. (It is selected from an aryl group and an aralkyl group having 7 to 10 carbon atoms. N represents an integer of 0 to 10. i represents an integer of 0 to 4.)
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group. Examples of the alkoxyl group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a phenethyl group. Of these, a hydrogen atom or a methyl group is preferable.

（（ＩＶ）式中で、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。） The epoxy resin represented by the general formula (III) can be obtained, for example, by reacting a biphenol compound with epichlorohydrin by a known method. Examples of the epoxy resin represented by the general formula (III) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3,3 ′. , 5,5'-tetramethylbiphenyl as the main component, epichlorohydrin is reacted with 4,4'-biphenol or 4,4 '-(3,3', 5,5'-tetramethyl) biphenol The epoxy resin etc. which are obtained by these are mentioned. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable.

(In the formula (IV), R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. Represents an integer of 0 to 3.)

  Examples of the epoxy resin that can be used in combination with the general formula (III) include a bisphenol type epoxy resin, a sulfur atom-containing type epoxy resin, and a stilbene type epoxy resin. Examples of the bisphenol type epoxy resin include an epoxy resin represented by the following general formula (V).

（（Ｖ）式中で、Ｒ^１〜Ｒ^８は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数６〜１０のアリール基、及び炭素数７〜１０のアラルキル基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(In formula (V), R ^{1 to} R ⁸ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 to 10 carbon atoms. And all may be the same or different. N represents an integer of 0 to 3.)

  Examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (VI).

（ここで、Ｒ₁〜Ｒ₈は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０又は１〜３の整数を示す。）

(Here, R _{1 to} R ₈ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. Indicates an integer of 3.)

The sulfur atom-containing epoxy resin represented by the general formula (VI) can be obtained by reacting a thiodiphenol compound with epichlorohydrin by a known method. As R < ₁ > -R < ₈ > in general formula (VI), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, t-butyl group etc., for example. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom, a methyl group, or t-butyl group is preferable. Among the sulfur atom-containing epoxy resins represented by the general formula (VI), R ₁ , R ₄ , R ₅ and R ₈ are hydrogen atoms, and R ₂ , R ₃ , R ₆ and R ₇ are alkyl groups. An epoxy resin is preferable, and an epoxy resin in which R ₁ , R ₄ , R _5, and R ₈ are hydrogen atoms, R ₂ and R ₇ are methyl groups, and R ₃ and R ₆ are t-butyl groups is more preferable. As such a compound, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available.

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

（ここで、Ｒ₁〜Ｒ₈は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０又は１〜３の整数を示す。）

(Here, R _{1 to} R ₈ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. Indicates an integer of 3.)

As R < ₁ > -R < ₈ > in the said general formula (VII), C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, t-butyl group etc., for example. C1-C10 alkenyl groups such as an alkyl group, vinyl group, allyl group, and butenyl group, and the like. Among them, a hydrogen atom, a methyl group, or a t-butyl group is preferable. The stilbene type epoxy resin represented by the general formula (VII) can be obtained by reacting a raw material stilbene phenol with epichlorohydrin by a known method. Examples of the raw material stilbene phenols include 3-t-butyl-4,4′-dihydroxy-3 ′, 5,5′-trimethylstilbene, 3-t-butyl-4,4′-dihydroxy-3. ', 5', 6-trimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-5 , 5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene and the like, among others, 3-t-butyl-4,4'- Dihydroxy-3 ', 5,5'-trimethylstilbene and 4,4'-dihydroxy-3,3', 5,5'-tetramethylstilbene are preferred. These stilbene type phenols may be used alone or in combination of two or more. As such a compound, ESLV-210 (manufactured by Sumitomo Chemical Co., Ltd.) and the like are commercially available.

  The (B) curing agent of the present invention uses a compound represented by general formula (I) and a compound represented by general formula (II).

（（Ｉ）式中で、ｎは０〜１０の整数を示す。）

(In the formula (I), n represents an integer of 0 to 10.)

（（ＩＩ）式中で、ｎは０〜１４の整数を示す。）

(In the formula (II), n represents an integer of 0 to 14.)

  SN-170L-SA5 (manufactured by Nippon Steel Chemical Co., Ltd.), which is a 95/5 weight ratio mixture of β-naphthol aralkyl resin of general formula (I) and disulfide type resin of general formula (II) is marketed It is available.

  In the present invention, in addition to the curing agent that is a mixture of the compound represented by the general formula (I) and the compound represented by the general formula (II) as the component (B), it is generally used for an epoxy resin molding material for sealing. The curing agent used can be used in combination as long as the effects of the invention are not lost. For example, phenols such as resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and aldehyde groups such as formaldehyde, benzaldehyde, salicylaldehyde, etc. A novolak-type phenol resin obtained by condensation or co-condensation with a compound having an acidic catalyst, phenol and / or naphthol, and phenol / aralkyl resin synthesized from dimethoxyparaxylene or bis (methoxymethyl) biphenyl, naphthol Diclopentadiene type phenol novola synthesized by copolymerization from aralkyl type phenol resins such as aralkyl resins, phenols and / or naphthols and cyclopentadiene Diclopentadiene-type phenolic resins such as lacquer resins and naphthol novolak resins, and terpene-modified phenolic resins.

  The equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is: Although there is no restriction | limiting in particular, In order to suppress each unreacted part small, it is preferable to set to the range of 0.5-2, and 0.6-1.3 are more preferable. In order to obtain a sealing epoxy resin composition excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

  The sealing epoxy resin composition of the present invention can contain acenaphthylene for the purpose of improving flame retardancy. Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Further, it can be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out only by heat without using a catalyst. At this time, the polymerization temperature is preferably 80 to 160 ° C, more preferably 90 to 150 ° C. 60-150 degreeC is preferable and, as for the softening point of the polymer of the polymer of acenaphthylene obtained or acenaphthylene and another aromatic olefin, 70-130 degreeC is more preferable. When the temperature is lower than 60 ° C., the moldability tends to decrease due to oozing during molding, and when the temperature is higher than 150 ° C., the compatibility with the resin tends to decrease.

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

  As said acenaphthylene, the acenaphthylene premixed with a part or all of (B) hardening | curing agent can also be contained. (B) A premixed mixture of a part or all of the curing agent and one or more of acenaphthylene, a polymer of acenaphthylene, and a polymer of acenaphthylene and another aromatic olefin may be used. As a premixing method, (B) and the acenaphthylene component are each finely pulverized and mixed with a mixer or the like in a solid state, a method in which both components are uniformly dissolved in a solvent that dissolves both components, and then the solvent is removed. B) and / or a method in which both are melt mixed at a temperature equal to or higher than the softening point of the acenaphthylene component, etc., but a melt mixing method in which a uniform mixture is obtained and impurities are less mixed is preferable. The melt mixing is not limited as long as the temperature is equal to or higher than the softening point of (B) and / or the acenaphthylene component, but is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. Moreover, although melt mixing will not have a restriction | limiting in mixing time if both are mixed uniformly, 1 to 20 hours are preferable and 2 to 15 hours are more preferable.

  When the (B) curing agent and acenaphthylene are premixed, the acenaphthylene component may be polymerized or reacted with the (B) curing agent during mixing. In the epoxy resin composition for sealing of the present invention, from the viewpoint of improving flame retardancy due to dispersibility of the acenaphthylene component, the above-mentioned premix (acenaphthylene-modified curing agent) is 90% by weight in the (B) curing agent. It is preferable to be contained above. The amount of acenaphthylene and / or aromatic olefin polymer containing acenaphthylene contained in the acenaphthylene-modified curing agent is preferably 5 to 40% by weight, and more preferably 8 to 25% by weight. If the amount is less than 5% by weight, the flame retardancy tends to decrease, and if it exceeds 40% by weight, the moldability tends to decrease. The content of the acenaphthylene structure contained in the epoxy resin composition of the present invention is preferably 0.1 to 5% by weight and more preferably 0.3 to 3% by weight from the viewpoints of flame retardancy and moldability. If it is less than 0.1% by weight, it tends to be inferior in flame retardancy, and if it is more than 5% by weight, moldability tends to be lowered. As such a compound, trade name SN-170AR10 manufactured by Nippon Steel Chemical Co., Ltd., in which acenaphthylene is added to β-naphthol / aralkyl resin, is commercially available.

  (C) A hardening accelerator can be mix | blended with the epoxy resin composition for sealing of this invention as needed. (C) Although a hardening accelerator is generally used for the epoxy resin composition for sealing and is not particularly limited, for example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1 , 5-diaza-bicyclo (4,3,0) nonene, cycloamidine compounds such as 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and these compounds Maleic acid, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone , Quinone compounds such as 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane and phenol resin. A compound having intramolecular polarization, tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof, 2-methylimidazole, 2-phenylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole and derivatives thereof, phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine, and these phosphines Phosphorus compound having intramolecular polarization, tetraphenylphosphoric acid, which is obtained by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, or phenol resin to the compound. And tetraphenylboron salts such as um tetraphenyl borate, triphenylphosphine tetraphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, N-methylmorpholine tetraphenyl borate, and derivatives thereof. May be used alone or in combination of two or more. Among these, from the viewpoints of curability and fluidity, phosphine compounds and adducts of phosphine compounds and quinone compounds are preferred, and tertiary phosphine compounds such as triphenylphosphine and adducts of triphenylphosphine and quinone compounds are more preferred. preferable.

  The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.005 to 2% by weight with respect to the epoxy resin composition for sealing, 0.01 to 0 More preferred is 5% by weight. If it is less than 0.005% by weight, the curability in a short time tends to be inferior, and if it exceeds 2% by weight, the curing rate tends to be too high and it tends to be difficult to obtain a good molded product.

  It is preferable to further blend (D) an inorganic filler in the sealing epoxy resin composition of the present invention. (D) The inorganic filler is blended into the composition for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate , Calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc., or beads spheroidized from these, A glass fiber etc. are mentioned, These may be used independently or may be used in combination of 2 or more type. Among them, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity and mold wear during molding.

  (D) The blending amount of the inorganic filler is preferably 70 to 95% by weight with respect to the sealing epoxy resin composition from the viewpoints of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction and strength improvement, More preferred is 75 to 92% by weight. If the amount is less than 70% by weight, the flame retardancy and reflow resistance tend to decrease, and if it exceeds 95% by weight, the fluidity tends to be insufficient.

  Moreover, it is preferable to add (E) coupling agent to the epoxy resin composition for sealing of this invention, in order to improve the adhesiveness of a resin component and an inorganic filler. For example, known coupling agents such as various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added. . Examples of these include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- ( Minoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, Dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercapto Silane coupling agents such as propylmethyldimethoxysilane, isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N -Aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate Titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl Titanate, tetraisopropylbis (dioctyl phosphite) titanate, etc. Is like titanate coupling agents may be used in combination of two or more even with these alone. Of these, a silane coupling agent having a secondary amino group is preferred from the viewpoint of fluidity and flame retardancy. The silane coupling agent having a secondary amino group is not particularly limited as long as it is a silane compound having a secondary amino group in the molecule. For example, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane Γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ- Anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p- Methoxyphenyl) -γ-aminopropyltrimeth Sisilane, N- (p-methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyl Diethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxy Silane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- (N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyl Triethoxysilane, γ- (N-ethyl) aminopropyltriethoxy Lan, γ- (N-butyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxysilane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropyl Methyldimethoxysilane, γ- (N-butyl) aminopropylmethyldimethoxysilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- ( β-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and the like.

  Among these, from the viewpoint of fluidity, an aminosilane coupling agent represented by the following general formula (VIII) is preferable.

（ここで、Ｒ¹は水素原子、炭素数１〜６のアルキル基及び炭素数１〜２のアルコキシ基から選ばれ、Ｒ²は炭素数１〜６のアルキル基及びフェニル基から選ばれ、Ｒ³はメチル基又はエチル基を示し、ｎは１〜６の整数を示し、ｍは１〜３の整数を示す。）

(Wherein R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group; ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to ^3. )

  Examples of the aminosilane coupling agent represented by the general formula (VIII) include γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, and γ-anilinopropylmethyl. Diethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropyltrimethoxysilane, N- (p -Methoxyphenyl) -γ -Aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldiethoxysilane, N- (p-methoxyphenyl) -Γ-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldimethoxysilane, and the like. Particularly preferred is γ-anilinopropyltrimethoxysilane.

  The blending amount of the silane coupling agent having a secondary amino group is preferably 30% by weight or more, more preferably 50% by weight or more based on the total amount of the coupling agent in order to exhibit its performance. (E) The total amount of coupling agent is preferably 0.05 to 5% by mass, more preferably 0.1 to 2.5% by mass, based on the epoxy resin composition for sealing. . If it is less than 0.05% by mass, the adhesion to the frame tends to be lowered, and if it exceeds 5% by mass, the moldability of the package tends to be lowered.

  A conventionally known non-halogen, non-antimony (F) flame retardant can be blended in the sealing epoxy resin composition of the present invention as required. For example, a phosphorus compound represented by the following general formula (IX), a phosphorus compound coated with an inorganic substance such as red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc oxide and / or a thermosetting resin such as a phenol resin, melamine, etc. , Melamine derivatives, melamine modified phenolic resins, compounds having a triazine ring, cyanuric acid derivatives, nitrogen-containing compounds such as isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, magnesium hydroxide, etc. One of these may be used alone, or two or more may be used in combination.

（ここで、Ｒ^１、Ｒ^２及びＲ^３は炭素数１〜１０の置換又は非置換のアルキル基、アリール基、アラルキル基及び水素原子を示し、すべて同一でも異なってもよい。ただしすべてが水素原子である場合を除く。）

(Here, R ¹ , R ² and R ³ represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group and a hydrogen atom, which may all be the same or different. Except when it is an atom.)

Among the phosphorus compounds represented by the general formula (IX), R ^{1 to} R ³ are preferably substituted or unsubstituted aryl groups, particularly preferably phenyl groups, from the viewpoint of hydrolysis resistance.

  (F) As for the compounding quantity of a flame retardant, it is preferable that the quantity of a phosphorus atom is 0.01 to 0.2 weight% with respect to the epoxy resin composition for sealing. More preferably, it is 0.02 to 0.1 weight%, More preferably, it is 0.03 to 0.08 weight%. If it is less than 0.01% by weight, the flame retardancy is lowered, and if it exceeds 0.2% by weight, the moldability and moisture resistance are lowered.

In addition, an anion exchanger can be added to the epoxy resin composition for encapsulating electronic components of the present invention from the viewpoint of improving the moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcites, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth, etc. These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (X) is preferable.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (X)
(0 <X ≦ 0.5, m is a positive number)

  Furthermore, in the sealing epoxy resin composition of the present invention, as other additives, higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, release agents such as polyethylene oxide, carbon black, etc. If necessary, a color relieving agent, a silicone oil, a stress relaxation agent such as rubber powder, and the like can be blended.

  The epoxy resin composition for sealing of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, a raw material having a predetermined blending amount is mixed with a mixer or the like. A method of cooling and pulverizing after mixing sufficiently, melt-kneading with a mixing roll, an extruder or the like can be mentioned. It is easy to use if it is tableted with dimensions and weight that match the molding conditions.

  As an electronic component device provided with an element sealed with the epoxy resin composition for sealing obtained in the present invention, for example, a semiconductor device can be mentioned. Specifically, an element such as a semiconductor chip is fixed on a lead frame (island, tab), the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding or bump, and then the sealing of the present invention. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Oline), which are sealed by transfer molding using an epoxy resin composition. Resin-sealed ICs such as J-lead package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), and the like TCP (Tape Carrier Package) in which a semiconductor chip lead-bonded to a carrier is sealed with the sealing epoxy resin composition of the present invention, wiring formed on a wiring board or glass, wire bonding, flip chip bonding, solder, etc. The semiconductor chips connected in the above are formed on a semiconductor device, a wiring board or glass mounted with bare chips such as COB (Chip On Board) and COG (Chip On Glass) sealed with the sealing epoxy resin composition of the present invention. The semiconductor chip, transistor, diode, thyristor and other active elements connected to the wiring by wire bonding, flip chip bonding, solder, etc. and / or passive elements such as capacitors, resistors, coils, etc., and the sealing epoxy resin of the present invention Sealed with composition A semiconductor chip is mounted on an interposer substrate on which terminals for connecting an hybrid IC, MCM (Multi Chip Module) motherboard are formed, and the semiconductor chip and wiring formed on the interposer substrate are connected by bumps or wire bonding, and then the sealing of the present invention is performed. Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), etc., in which the semiconductor chip mounting side is sealed with an epoxy resin composition for stopping. In addition, even if these semiconductor devices are stacked type packages in which two or more elements are stacked on a mounting substrate, the epoxy resin composition for sealing two or more elements at a time It may be a batch mold type package sealed with. Moreover, the epoxy resin composition for sealing of the present invention can also be used effectively for printed circuit boards.

  As a method for sealing an element using the epoxy resin composition for sealing of the present invention, a low-pressure transfer molding method is most common, but an injection molding method, a compression molding method, or the like may be used.

Examples 1-4, Comparative Examples 1-6
As the epoxy resin of component (A), a biphenyl aralkyl type epoxy resin (epoxy resin 1, Nippon Kayaku Co., Ltd.) having an epoxy equivalent of 282, a softening point of 60 ° C., and R ^{1 to} R ⁸ of the general formula (III) is a hydrogen atom (Trade name NC-3000), epoxy equivalent 242, softening point 95 ° C., and R ^{1 to} R ⁸ of the general formula (IV) are hydrogen atoms and R ^{1 of the} general formula (III) ~ R ⁸ is a hydrogen atom biphenyl aralkyl type epoxy resin 20/80 weight ratio mixture (epoxy resin 2, Nippon Kayaku Co., Ltd. trade name CER-3000L), epoxy equivalent 196, melting point 106 ° C. Biphenyl type epoxy resin in which R ¹ R ³ R ⁶ R ^{8 in the} general formula (IV) is a methyl group and R ² R ⁴ R ⁵ R ⁷ is a hydrogen atom (Epoxy Resin 3, Japan Epoxy Resin Co., Ltd. trade name Epicoat YX-4000H), epoxy equivalent of 188, melting point of 77 ° C., R ¹ R ³ R ⁶ R ⁸ of the above general formula (V) is a methyl group and R ² R ⁴ R ⁵ R ⁷ is a hydrogen atom Bisphenol F type epoxy resin (epoxy resin 4, trade name YSLV-80XY, manufactured by Nippon Steel Chemical Co., Ltd.), (B) as a curing agent, a hydroxyl group equivalent of 183, a softening point of 70 ° C. and the above general formula (I ) Β-naphthol-aralkyl resin and disulfide resin of the above general formula (II) in a weight ratio of 95/5 (curing agent 1, trade name SN-170L-SA5 manufactured by Nippon Steel Chemical Co., Ltd.), hydroxyl group Equivalent 172, phenol aralkyl resin having a softening point of 70 ° C. (curing agent 2, trade name Mirex XLC-3L manufactured by Mitsui Chemicals, Inc.), hydroxyl group equivalent of 200, biphenyl having a softening point of 73 ° C. Aralkyl resin (curing agent 3, trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.), adduct of triphenylphosphine and 1,4-benzoquinone as a curing accelerator for component (C), inorganic filler for component (D) Spherical fused silica having an average particle size of 18 μm and a specific surface area of 3.8 m ² / g, and γ-glycidoxypropyltrimethoxysilane (coupling agent, product name A manufactured by Nihon Unicar Co., Ltd.) as the coupling agent of component (E) -187), polyethylene wax as a release agent, and carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Corporation) as a colorant were prepared. These are each compounded in parts by weight shown in Table 1, and roll kneading is performed under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. Produced.

  The produced epoxy resin compositions for sealing of Examples and Comparative Examples were evaluated by the following tests. The results are shown in Table 1. The epoxy resin composition for sealing was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 180 ° C. for 5 hours.

(1) Spiral flow (fluidity index)
The sealing epoxy resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was determined.

(2) UL-94 Flammability Using a mold for molding a test piece having a thickness of 1/16 inch, the sealing epoxy resin composition is molded under the above conditions and post-cured, and the UL-94 test method is used. A combustion test was performed according to the above, and evaluation was performed with five test pieces to determine combustibility.

(3) Reflow resistance A lead frame in which the copper alloy is not plated, and a lead frame in which the copper alloy is previously plated with nickel-palladium-gold (Ni-Pd-Au), etc., are used. An 80-pin flat package having an outer dimension of 20 mm × 14 mm × 2 mm mounted with a × 0.4 mm silicone chip is formed by molding and post-curing using the epoxy resin composition for sealing at 85 ° C., 85 The sample was humidified for 168 hours under the condition of% RH and reflow treatment was performed at 260 ° C. for 10 seconds, the presence or absence of cracks was observed, and the number of cracked packages relative to the number of test packages (n = 5) was evaluated. In addition, using an ultrasonic flaw detector, the separation of the interface between the back surface of the island and the inner lead part and the epoxy resin composition for sealing was observed, and the evaluation was made based on the number of peeling occurrence packages with respect to the number of test packages (n = 5). did.

The epoxy resin compositions according to Comparative Examples 1 to 6 that do not contain the combination of the curing agents of the general formulas (I) and (II) have good reflow resistance when a package including a lead frame that is not subjected to plating treatment is sealed. However, it is inferior in cracking and peeling in reflow resistance evaluation when a package including a lead frame subjected to plating is sealed. Moreover, the epoxy resin composition by the comparative examples 1 and 2 is inferior also in a flame retardance.
On the other hand, according to the epoxy resin compositions of Examples 1 to 4 containing the curing agents represented by the general formulas (I) and (II), the resistance when the package including the lead frame subjected to the plating treatment is sealed is shown. Cracks and peeling in reflowability evaluation are good, and flame retardancy is good. In particular, the epoxy resin composition of Example 1 containing an epoxy resin of general formula (III) and the epoxy resin composition of Example 2 containing epoxy resins of general formulas (III) and (IV) in a weight ratio of 20/80 Is excellent in cracking and peeling in reflow resistance evaluation when a package including a lead frame subjected to plating is sealed.

    As shown in the examples, the epoxy resin composition for sealing according to the present invention can achieve flame retardancy with non-halogen and non-antimony, and seals electronic components such as ICs and LSIs including lead frames plated using the epoxy resin composition. If stopped, a good product having good moldability such as fluidity and curability and excellent cracking and peeling in reflow resistance evaluation can be obtained, and its industrial value is great.

Claims (6)

(A) An epoxy resin and (B) a curing agent, wherein the (B) curing agent includes a curing agent represented by the general formula (I) and a curing agent represented by the general formula (II). Epoxy resin composition for frame package sealing.

(In the formula (I), n represents an integer of 0 to 10.)

(In the formula (II), n represents an integer of 0 to 14.) The epoxy resin composition according to claim 1, wherein the (A) epoxy resin contains an epoxy resin represented by the general formula (III).

(In formula (III), R ^{1 to} R ⁹ may all be the same or different, and are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. And n represents an integer of 0 to 10. i represents an integer of 0 to 4.) The epoxy resin composition according to claim 2, wherein the (A) epoxy resin further contains an epoxy resin represented by the general formula (IV).

(In the formula (IV), R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. Represents an integer of 0 to 3.) The epoxy resin composition according to claim 3, wherein R ^{1 to} R ^{8 of the} epoxy resin represented by the general formula (IV) are all hydrogen atoms. The epoxy resin composition according to any one of claims 1 to 4, wherein the (A) epoxy resin contains an epoxy resin represented by the general formula (V).

(In formula (V), R ^{1 to} R ⁸ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 to 10 carbon atoms. And all may be the same or different. N represents an integer of 0 to 3.)   An electronic component device comprising an element sealed with the epoxy resin composition according to claim 1.