JP6322966B2 - Resin composition for sealing and electronic component device - Google Patents

Description

The present invention relates to a sealing resin composition and an electronic component device using the same.

Electronic components such as diodes, transistors, and integrated circuits are distributed on the market or incorporated in electronic devices as electronic component devices sealed with a cured product such as an epoxy resin composition. The epoxy resin composition used for such a sealing material generally comprises a composition such as an epoxy resin, a phenol resin-based curing agent, an inorganic filler, and a coupling agent. In addition, with the recent trend of downsizing, weight reduction, high performance, etc. of electronic devices, the integration of electronic components has progressed, and the performance required for sealing materials (sealing resin compositions) is also high. It has become. Specific performance required for the sealing material includes, for example, adhesion, solder resistance, fluidity, heat resistance, and high-temperature storage characteristics.

Under such circumstances, sealing resin compositions containing a compound having a mercapto group such as a silane coupling agent having a mercapto group and a triazole compound having a mercapto group have been developed (see Patent Document 1 and Patent Document 2). ). By including a compound having a mercapto group, there is an effect that adhesion to an electronic component or the like is increased.

On the other hand, in recent years, inexpensive copper is being used in place of gold as a material for bonding wires and the like used for connecting electronic components and lead frames. However, an electronic component device including a copper wire may not have sufficient high-temperature storage characteristics. There is a demand for further excellent high-temperature storage characteristics for electronic component devices using copper members such as copper wires, and development of a sealing resin composition suitable for sealing such electronic components is desired. ing.

JP 09-165499 A JP 2009-167286 A

The present invention has been made in view of such circumstances, has a sufficient adhesion, and has a high-temperature storage characteristic of the obtained electronic component device, and such a sealing resin composition. An object of the present invention is to provide an electronic component device obtained by using as a sealing material.

The sealing resin composition according to the first aspect of the present invention comprises an epoxy resin (A), a curing agent (B), an inorganic filler (C), and a compound (D) represented by the following formula (1). Contains,
In the following formula (1), ^{R 1} is a secondary or tertiary amino group,
The sealing resin composition further contains a curing accelerator (F), and the curing accelerator (F) is at least selected from the group consisting of a tetra-substituted phosphonium compound and an adduct of a phosphine compound and a quinone compound. One or more phosphorus atom-containing compounds.

In the sealing resin composition according to the first invention, R ¹ is more preferably represented by the following formula (2).

In the sealing resin composition according to the first invention, the content of the compound (D) is preferably 0.01% by mass or more and 1% by mass or less. In addition, content of each component is a ratio with respect to the whole resin composition for sealing (hereinafter the same).

In the sealing resin composition according to the first invention, it is preferable that the composition further contains a coupling agent (E), and the coupling agent (E) contains a silane coupling agent (E1) having a mercapto group.

In the sealing resin composition according to the first invention, the content of the silane coupling agent (E1) having a mercapto group is preferably 0.01% by mass or more and 0.1% by mass or less.

The sealing resin composition according to the first invention is preferably used for sealing an electronic component to which a copper wire is connected.

An electronic component device according to a second invention that meets the above-described object is an electronic component device that includes an electronic component and a sealing material that seals the electronic component, wherein the sealing material is the sealing according to the first invention. It is a cured product of the resin composition for use.

In the electronic component device according to the second invention, it is preferable to have a copper wire connected to the electronic component.

Since the sealing resin composition according to the first invention contains the specific compound (D) having a hydroxybenzoyl group, it is possible to achieve both sufficient adhesion and high-temperature storage characteristics of the obtained electronic component device. Can be achieved.
R ^{1 is represented} by a hydroxy group, an alkoxy group, or a primary, secondary or tertiary amino group, more preferably a hydroxy group or a secondary or tertiary amino group, still more preferably a hydroxy group or the formula (2). Adhesiveness and high-temperature storage characteristics can be further enhanced by using the base.
The said performance can be improved more by making content of a compound (D) into the above-mentioned predetermined range, or using the silane coupling agent (E1) which has a mercapto group preferably in the above-mentioned predetermined range amount.
Furthermore, the adhesiveness in high temperature can be improved by containing the above-mentioned phosphorus atom containing compound as a hardening accelerator (F).
In particular, when the sealing resin composition according to the second invention is used for sealing an electronic component to which a copper wire is connected, adhesion to the copper wire and high-temperature storage characteristics can be effectively enhanced.

The electronic component device according to the second invention uses the sealing resin composition according to the first invention as a sealing material, and has sufficient adhesion between the sealing material and the electronic component, Excellent high-temperature storage characteristics. In particular, when the electronic component device according to the second invention has a copper wire connected to the electronic component, the adhesion to the copper wire and the high-temperature storage characteristics can be sufficiently exhibited.

It is sectional drawing which shows the electronic component apparatus which concerns on the 2nd Embodiment of this invention.

Next, embodiments of the present invention will be described with reference to the accompanying drawings as appropriate.

[Resin composition for sealing]
The sealing resin composition according to the first embodiment of the present invention contains an epoxy resin (A), a curing agent (B), an inorganic filler (C), and a compound (D).

[Epoxy resin (A)]
The epoxy resin (A) refers to a compound (monomer, oligomer and polymer) having two or more epoxy groups in one molecule, and does not particularly limit the molecular weight and molecular structure. As an epoxy resin (A), for example,
Crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins;
Novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins;
Multifunctional epoxy resins such as triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin;
Phenol aralkyl type epoxy resins such as a phenol aralkyl type epoxy resin having a phenylene skeleton and a phenol aralkyl type epoxy resin having a biphenylene skeleton;
Naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers;
Triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate;
Examples include bridged cyclic hydrocarbon compound-modified phenol type epoxy resins such as dicyclopentadiene-modified phenol type epoxy resins. These may be used alone or in combination of two or more.

As the epoxy resin (A), a phenol aralkyl type epoxy resin represented by the following formula (3) and a biphenyl type epoxy resin represented by the following formula (4) are preferable.

In formula (3), Ar ¹ is a phenylene group (a group consisting of a phenol structure, a structure obtained by removing a hydrogen atom of the number of bonds from phenol) or a naphthylene group (a group consisting of a naphthalene structure, and bonded from naphthalene) The structure excluding the number of hydrogen atoms in the hand). When Ar ¹ is a naphthylene group, the glycidyl ether group may be bonded to either the α-position or the β-position. Ar ² is any one of a phenylene group, a biphenylene group (a group having a biphenylene structure, and a structure in which a hydrogen atom having a number of bonds is removed from biphenyl), and a naphthylene group. R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 10 carbon atoms. g is an integer of 0 to 5 (provided that when Ar ¹ is a phenylene group, it is an integer of 0 to 3). h is an integer of 0 to 8 (provided that when Ar ² is a phenylene group, it is an integer of 0 to 4, and when Ar ² is a biphenylene group, it is an integer of 0 to 6). n ¹ represents the degree of polymerization, the average value is 1-3.

Ar ¹ is preferably a phenylene group. Ar ² is preferably a phenylene group or a biphenylene group. By making Ar ² a phenylene group or a biphenylene group (introducing a phenylene skeleton or a biphenylene skeleton), flame retardancy can be enhanced. In the case where g and h are not 0 in R ³ and R ⁴ , examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as a vinyl group, and an aryl group such as a phenyl group Can be mentioned. g and h are preferably 0.

In the formula (4), a plurality of R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n ² represents the degree of polymerization, the average value is 0-4. Examples of the hydrocarbon group having 1 to 4 carbon atoms include alkyl groups such as a methyl group and an ethyl group, and alkenyl groups such as a vinyl group.

Although it does not specifically limit as content of an epoxy resin (A), As a lower limit, 2 mass% is preferable and 4 mass% is more preferable. Adhesiveness etc. can be exhibited by making content of an epoxy resin (A) more than the said lower limit. As an upper limit of content of an epoxy resin (A), 20 mass% is preferable and 10 mass% is more preferable. By setting the content of the epoxy resin (A) to be equal to or less than the above upper limit value, sufficient low water absorption and low thermal expansion can be exhibited.

[Curing agent (B)]
The curing agent (B) is not particularly limited as long as it is a component capable of curing the epoxy resin (A), and examples thereof include a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent. .

Examples of polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylene diamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylenediamine (MPDA). And polyamine compounds containing aromatic polyamines such as diaminodiphenylsulfone (DDS), dicyandiamide (DICY), organic acid dihydrazide, etc .;
Hexahydrophthalic anhydride (HHPA), alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA), etc. Acid anhydrides including aromatic acid anhydrides; polyphenol compounds such as novolac-type phenolic resins and phenolic polymers;
Polymercaptan compounds such as polysulfide, thioester and thioether;
Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates;
Organic acids such as carboxylic acid-containing polyester resins;
A phenolic resin-based curing agent detailed below;
Etc.

Examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30);
Imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI24);
Lewis acids such as BF ₃ complex are listed.

Examples of the condensation type curing agent include a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; and a resin such as a methylol group-containing melamine resin.

Among these, as the curing agent (B), a phenol resin curing agent is preferable. By using a phenol resin-based curing agent, it is possible to exert a good balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. The phenol resin-based curing agent refers to a compound (monomer, oligomer and polymer) having two or more phenolic hydroxy groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited.

Examples of the phenol resin-based curing agent include novolak type resins such as phenol novolak resin and cresol novolak resin;
Polyfunctional phenolic resins such as triphenolmethane phenolic resin;
Modified phenolic resins such as terpene modified phenolic resin and dicyclopentadiene modified phenolic resin;
Aralkyl type resins such as a phenol aralkyl resin having a phenylene skeleton and / or a biphenylene skeleton, and a naphthol aralkyl resin having a phenylene and / or a biphenylene skeleton;
Examples thereof include bisphenol compounds such as bisphenol A and bisphenol F, and these may be used alone or in combination of two or more.

As a hardening | curing agent (B), the aralkyl type resin represented by following formula (5) is preferable.

In formula (5), Ar ³ is a phenylene group (a group consisting of a phenol structure, a structure in which a hydrogen atom having a number of bonds is removed from phenol) or a naphthylene group (a group consisting of a naphthalene structure, bonded from naphthalene) The structure excluding the number of hydrogen atoms in the hand). When Ar ³ is a naphthylene group, the hydroxy group may be bonded to either the α-position or the β-position. Ar ⁴ is any one of a phenylene group, a biphenylene group (a group consisting of a biphenylene structure, in which a hydrogen atom having a number of bonds is removed from biphenyl), and a naphthylene group. R ⁶ and R ⁷ are each independently a hydrocarbon group having 1 to 10 carbon atoms. i is an integer of 0 to 5 (provided that when Ar ³ is a phenylene group, it is an integer of 0 to 3). j is an integer of 0 to 8 (provided that when Ar ⁴ is a phenylene group, it is an integer of 0 to 4, and when Ar ⁴ is a biphenylene group, it is an integer of 0 to 6). n ³ represents the degree of polymerization, the average value is 1-3.

Ar ³ is preferably a phenylene group. Ar ⁴ is preferably a phenylene group or a biphenylene group. Incidentally, the Ar ⁴ by a phenylene group or a biphenylene group (introducing a phenylene skeleton or biphenylene skeleton), it is possible to increase the flame retardancy and the like. When i and j are not 0 in R ⁶ and R ⁷ , examples of the hydrocarbon group having 1 to 10 carbon atoms include those exemplified for R ³ and R ⁴ in the formula (3). i and j are preferably 0.

Although it does not specifically limit as content of a hardening | curing agent (B), As a lower limit, 0.5 mass% is preferable and 2 mass% is more preferable. By setting the content of the curing agent (B) to the lower limit value or more, sufficient curability, adhesion, and the like can be exhibited. As an upper limit of content of a hardening | curing agent (B), 15 mass% is preferable and 10 mass% is more preferable. Sufficient fluidity etc. can be exhibited by making content of a hardening | curing agent (B) below the said upper limit.

[Inorganic filler (C)]
As the inorganic filler (C), known materials used in general sealing resin compositions can be used. Examples of the inorganic filler (C) include silica such as fused spherical silica, fused crushed silica, and crystalline silica, talc, alumina, titanium white, and silicon nitride. Among these, silica is preferable, and fused spherical silica is more preferable. These inorganic fillers (C) may be used alone or in combination of two or more. The shape of the inorganic filler (C) is preferably spherical and has a wide particle size distribution. By using such an inorganic filler, an increase in the melt viscosity of the sealing resin composition can be suppressed, and the content of the inorganic filler (C) can be increased. In order to contain the inorganic filler (C) having a wide particle size distribution, there is a method of using a mixture of a plurality of types of inorganic fillers having different average particle diameters. Moreover, the inorganic filler (C) may be surface-treated with a coupling agent. Furthermore, you may use what processed the inorganic filler (C) previously with the epoxy resin etc. as needed.

Although it does not specifically limit as an average particle diameter of an inorganic filler (C), As a lower limit, 0.1 micrometer is preferable and 0.3 micrometer is more preferable. On the other hand, the upper limit is preferably 40 μm, more preferably 35 μm or less. Moreover, as a lower limit of the specific surface area of an inorganic filler (C), 1 m < ² > / g is preferable and 3 m < ² > / g is more preferable. On the other hand, as an upper limit, 10 m < ² > / g is preferable and 7 m < ² > / g is more preferable. By using an inorganic filler having an average particle diameter or specific surface area in such a range, fluidity, low hygroscopicity, etc. can be improved.

If necessary, for example, an inorganic filler having an average particle size of 0.1 μm or more and 1 μm or less and an average particle size of 1
It is also preferable to use two or more inorganic fillers in the above preferred range in combination, such as using an inorganic filler in the range of 0 μm to 40 μm.

Although it does not specifically limit as content of an inorganic filler (C), As a lower limit, 70 mass% is preferable and 80 mass% is more preferable. By setting the content of the inorganic filler (C) to the lower limit value or more, sufficient low hygroscopicity, low thermal expansion property, and the like can be exhibited. As an upper limit of content of an inorganic filler (C), 95 mass% is preferable and 92 mass% is more preferable. Sufficient fluidity etc. can be exhibited by making content of an inorganic filler (C) below the said upper limit.

[Compound (D)]
The compound (D) is a compound represented by the formula (1). A compound (D) may be used individually by 1 type, or may use 2 or more types together. Since the sealing resin composition of the present invention contains the specific compound (D) having a hydroxybenzoyl group, it is possible to achieve both sufficient adhesion and high-temperature storage characteristics of the obtained electronic component device. it can. The reason for this is not clear, but, for example, when an electron-donating hydroxy group and an electron-withdrawing carbonyl group are connected to a benzene ring, an appropriate polarization state appears, and a compound in such a state ( D) is considered to increase the affinity of the electronic component with the metal. Incidentally, when R ¹ is a polar group, considered affinity enhanced. As a result, the adhesion of the cured product (sealing material) of the encapsulating resin composition to an object to be encapsulated such as an electronic component is increased, and a metal atom diffused from the bonding wire or the like into the cured product is converted into the compound (D). It is conceivable that the deterioration of high-temperature storage characteristics is suppressed. In order to obtain a better polarization state and exhibit such an effect, it is more preferable that the hydroxy group and the carbonyl group are arranged in the ortho position or the para position.

The compound (D) preferably has a structure having no sulfur atom, particularly a mercapto group. A compound having a sulfur atom, particularly a mercapto group, may deteriorate high-temperature storage characteristics. Then, the fall of a high temperature storage characteristic can be suppressed by using the compound (D) which does not have a sulfur atom, especially a mercapto group.

R ^{1 in the} formula (1) is a polar group or a hydrocarbon group. The polar group refers to a group (atomic group) in which polarization is caused by an atom having a high electronegativity such as an oxygen atom, a nitrogen atom, or a halogen atom. Specific polar groups include, for example, a hydroxy group (—OH), an alkoxy group, a primary amino group (—NH ₂ ), a secondary amino group (—NHR, R is an arbitrary substituent), a tertiary amino group ( -NR ₂ , and two R are optional substituents, which may be the same or different, and may be bonded to each other to form a ring structure), a heterocyclic group, other groups, a hydroxy group, a carboxyl group, Examples thereof include a hydrocarbon group having an amino group, a halogen atom or the like as a substituent.

Examples of the alkoxy group represented by R ¹ include a methoxy group, an ethoxy group, a propoxy group, a phenoxy group, and benzyloxy. Examples of the substituent (R) that the secondary or tertiary amino group has include a hydrocarbon group, a heterocyclic group, and other hydrocarbon groups having the above-described substituent. Examples of the hydrocarbon group represented by R ¹ or R include hydrocarbon groups having 1 to 20 carbon atoms, and specifically include alkyl groups such as methyl groups and ethyl groups, vinyl groups, and allyl groups. And aryl groups such as phenyl group, naphthyl group, and tolyl group. Examples of the heterocyclic group represented by R ¹ or R include aromatic heterocyclic groups such as a furyl group, a pyridyl group, a thienyl group, and a triazole group, other oxanyl groups, and piperidinyl groups. Examples of the halogen atom include a chlorine atom and a fluorine atom.

R ¹ is preferably a polar group, and is preferably a hydroxy group, an alkoxy group, or a primary, secondary, or tertiary amino group. When R ¹ is such an electron donating group, it is considered that a better polarization state is expressed. Among the alkoxy groups, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group is more preferable. R ¹ is more preferably a hydroxy group or a primary, secondary or tertiary amino group, more preferably a primary, secondary or tertiary amino group, still more preferably a secondary or tertiary amino group, and a secondary amino group. The group is particularly preferred. The secondary or tertiary amino group preferably has a polar group as a substituent. As the polar group possessed by the secondary or tertiary amino group, a heterocyclic group is preferred. As the heterocyclic group, a nitrogen atom-containing heterocyclic group or an aromatic heterocyclic group is more preferable, a nitrogen atom-containing aromatic heterocyclic group is more preferable, and a triazole group is particularly preferable. The triazole group refers to a monovalent group obtained by removing one hydrogen atom from triazole. This triazole may be 1,2,3-triazole or 1,2,4-triazole, 4-Triazole is preferred. R ¹ is particularly preferably a group represented by the above formula (2) (a group in which R is a 2H-1,2,4-triazol-5-yl group in the general formula —NHR of a secondary amino group). .
Among the compounds (D), R ¹ is a hydroxy group or a group represented by the above formula (2) (in the general formula —NHR of a secondary amino group, R is 2H-1,2,4-triazole-5- When it is a group that is an yl group, it is particularly excellent in high-temperature storage characteristics and adhesion.

For example, when a compound in which R ¹ is represented by the formula (2) is used as the compound (D), two types of compounds that generate such a compound by reaction may be mixed and used. Examples of such two kinds of compounds include a combination of hydroxybenzoic acid and aminotriazole.

Although it does not specifically limit as content of a compound (D), As a lower limit, 0.01 mass% is preferable, 0.02 mass% is more preferable, 0.03 mass% is further more preferable. As an upper limit of content of a compound (D), 1 mass% is preferable, 0.5 mass% is more preferable, and 0.3 mass% is further more preferable. By setting the content of the compound (D) within the above range, sufficient adhesion and high-temperature storage characteristics can be exhibited without greatly affecting other characteristics.

[Coupling agent (E)]
The sealing resin composition may further contain a coupling agent (E). A coupling agent (E) is a component which connects the epoxy resin (A) etc. which are resin components, and an inorganic filler (C). Examples of the coupling agent (E) include silane coupling agents such as epoxy silane, aminosilane, and mercaptosilane (a silane coupling agent having a mercapto group) (E1). These coupling agents (E) may be used individually by 1 type, or may use 2 or more types together.

Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and the like.

Examples of aminosilanes include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane (sometimes referred to as anilinosilane), and the like.

Examples of mercaptosilane (E1) include γ-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane. In addition, the mercaptosilane includes compounds that exhibit the same function by thermal decomposition, such as bis (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) disulfide.

Among these coupling agents (E), it is preferable to use epoxysilane, anilinosilane, mercaptosilane (E1), or a combination thereof. Anilinosilane is effective in improving fluidity, and mercaptosilane (E1) can enhance adhesion. On the other hand, as described above, a compound having a mercapto group may not have sufficient high-temperature storage characteristics. However, according to the encapsulating resin composition of the present invention, since the compound (D) is contained, mercaptosilane ( If E1) and the compound (D) of the present invention are used in combination, excellent high-temperature storage characteristics and adhesion can be achieved.

Although it does not specifically limit as content of a coupling agent (E), As a lower limit, 0.01 mass% is preferable and 0.05 mass% is more preferable. As an upper limit, 1 mass% is preferable and 0.5 mass% is more preferable. By making content of a coupling agent (E) into the said range, the function of a coupling agent (E) can be expressed effectively.

Moreover, when using together a compound (D) and mercaptosilane (E1), as a lower limit of content of this mercaptosilane, 0.01 mass% is preferable and 0.02 mass% is more preferable. By setting the content of mercaptosilane (E1) to the lower limit value or more, the adhesion can be effectively increased. As an upper limit of content of mercaptosilane (E1), 0.1 mass% is preferable and 0.07 mass% is more preferable. By setting the content of mercaptosilane (E1) to the upper limit value or less, the high-temperature storage characteristics can be further improved.

[Curing accelerator (F)]
The sealing resin composition may further contain a curing accelerator (F). Curing accelerator (F)
Is a component having a function of promoting the reaction between the epoxy resin (A) and the curing agent (B), and a generally used curing accelerator is used.

Examples of the curing accelerator (F) include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds;
Amidines and tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine and 2-methylimidazole, and nitrogen atom-containing compounds such as the quaternary salts of the amidine and amine These can be used, and one or more of these can be used in combination. Of these, phosphorus atom-containing compounds are preferred from the viewpoints of curability and adhesion. Furthermore, from the viewpoint of solder resistance, fluidity, etc., an adduct of a phosphobetaine compound, a phosphine compound and a quinone compound is particularly preferable. From the point of slight contamination of the mold in continuous molding, tetra substitution Particularly preferred are phosphorus atom-containing compounds such as phosphonium compounds and adducts of phosphonium compounds and silane compounds.

(Organic phosphine)
Examples of the organic phosphine include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine. it can.

(Tetra-substituted phosphonium compound)
Examples of the tetra-substituted phosphonium compound include a compound represented by the following formula (6).

In formula (6), P is a phosphorus atom. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are an aromatic group or an alkyl group. [A] ^- is the anion of a hydroxy group, having at least one aromatic organic acid or a functional group selected from carboxyl group and a thiol group on the aromatic ring. AH is an aromatic organic acid having at least one functional group selected from a hydroxy group, a carboxy group, and a thiol group in an aromatic ring. x and y are numbers 1 to 3, z is a number 0 to 3, and x = y.

Although the compound represented by Formula (6) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Subsequently, when water is added, the compound represented by Formula (6) can be precipitated.

In the compound represented by the formula (6), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxy group in an aromatic ring, that is, phenols. [A] ⁻ is preferably an anion of the phenol. Phenols include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, bisphenols such as bisphenol A, bisphenol F, and bisphenol S, and phenyl Examples thereof include polycyclic phenols such as phenol and biphenol.

(Phosphobetaine compound)
As a phosphobetaine compound, the compound etc. which are represented by following formula (7) can be mentioned, for example.

Wherein ^{(7), R 12} is an alkyl group having 1 to 3 carbon atoms. R ¹³ is a hydroxy group. k is an integer of 0-5. m is an integer of 0-3.

The compound represented by Formula (7) is obtained as follows, for example. A triaromatic substituted phosphine that is a third phosphine and a diazonium salt are brought into contact with each other, and the triaromatic substituted phosphine and the diazonium group of the diazonium salt are substituted. However, the present invention is not limited to this.

(Adduct of phosphine compound and quinone compound)
Examples of the adduct of a phosphine compound and a quinone compound include a compound represented by the following formula (8).

In formula (8), P is a phosphorus atom. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁸ and R ¹⁹ may be bonded to form a cyclic structure.

Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent or a substituent such as an alkyl group or an alkoxyl group are preferred. Examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

Examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include benzoquinone and anthraquinones. Among these, p-benzoquinone is preferable from the viewpoint of storage stability.

As a method for producing an adduct of a phosphine compound and a quinone compound, for example, an adduct can be obtained by contacting and mixing them in a solvent capable of dissolving both organic tertiary phosphine and benzoquinones. it can. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, it is not limited to this.

In the compound represented by the formula (8), R ¹⁴ , R ¹⁵ and R ¹⁶ bonded to the phosphorus atom are phenyl groups, and R ¹⁷ , R ¹⁸ and R ¹⁹ are hydrogen atoms, that is, 1, 4 -The compound which added benzoquinone and triphenylphosphine is preferable at the point etc. which reduce the elastic modulus at the time of the hardened | cured material of a resin composition.

(Adduct of phosphonium compound and silane compound)
Examples of the adduct of a phosphonium compound and a silane compound include a compound represented by the following formula (9).

In formula (9), P is a phosphorus atom and Si is a silicon atom. R ²⁰ , R ²¹ , R ²² and R ²³ are each independently an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. R ²⁴ is an organic group bonded to the groups Y ² and Y ³ . R ²⁵ is an organic group bonded to the groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by releasing a proton from a proton donating group, and groups Y ² and Y ³ in the same molecule are bonded to a silicon atom to form a chelate structure. Y ⁴ and Y ⁵ represent a group formed by releasing a proton from a proton donating group, and groups Y ⁴ and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure. R ²⁴ and R ²⁵ may be the same or different, and Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. Z ¹ is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.

Examples of R ²⁰ , R ²¹ , R ²² and R ²³ include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group, a methyl group, an ethyl group, and n-butyl. Group, n-octyl group, cyclohexyl group and the like. Among these, alkyl groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group and hydroxynaphthyl group, aromatic groups having substituents such as alkoxy groups and hydroxy groups, or unsubstituted aromatic groups are preferable. .

The groups represented by —Y ² —R ²⁴ —Y ³ — and Y ⁴ —R ²⁵ —Y ⁵ — in the formula (9) are composed of groups in which the proton donor releases two protons. It is what is done. The proton donor is preferably an organic acid having at least two carboxy groups or hydroxy groups in the molecule. Furthermore, an aromatic compound having at least two carboxy groups or hydroxy groups respectively connected to adjacent carbons constituting one aromatic ring is preferred, and hydroxy groups respectively connected to adjacent carbons constituting one aromatic ring. An aromatic compound having at least two is more preferable. Examples of such proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, 1 -Hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin and the like. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.

Examples of the organic group having an aromatic ring or heterocyclic ring represented by Z ¹ in formula (9) or an aliphatic group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. Aliphatic hydrocarbon group, aromatic hydrocarbon group such as phenyl group, benzyl group, naphthyl group, biphenyl group, glycidyloxy group such as glycidyloxypropyl group, mercaptopropyl group, aminopropyl group, mercapto group, amino group Examples thereof include reactive substituents such as alkyl groups and vinyl groups. Among these, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of thermal stability.

Examples of the method for producing an adduct of a phosphonium compound and a silane compound include the following methods. First, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added and dissolved in a flask containing methanol, and then a sodium methoxide-methanol solution is added dropwise with stirring at room temperature. Further, when a methanol solution of tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide prepared in advance is added dropwise with stirring at room temperature, crystals are deposited. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

Examples of the curing accelerator (F) include compounds represented by the above formulas (6) to (9). Among these, a tetra-substituted phosphonium compound (for example, a formula) The compound represented by (6)) or an adduct of a phosphine compound and a quinone compound (for example, a compound represented by formula (8)) is preferred, and an adduct of a phosphine compound and a quinone compound is more preferred.

Although it does not specifically limit as content of a hardening accelerator (F), As a lower limit, 0.1 mass% is preferable and 0.2 mass% is more preferable. Sufficient curability etc. can be obtained by making content of a hardening accelerator (F) more than the said lower limit. As an upper limit of content of a hardening accelerator (F), 1 mass% is preferable and 0.5 mass% is more preferable. Sufficient fluidity | liquidity etc. can be obtained by making content of a hardening accelerator (F) below into the said upper limit.

[Other ingredients]
The sealing resin composition may further contain other components as necessary. Examples of other components include a colorant, an ion scavenger, a release agent, a low stress component, and a flame retardant.
Examples of the colorant include carbon black and bengara.
Examples of the ion scavenger include hydrotalcite. An ion scavenger may be used as a neutralizing agent.
Examples of the mold release agent include natural waxes such as carnauba wax, synthetic waxes, higher fatty acids such as zinc stearate, metal salts thereof, paraffin, and the like.
Examples of the low stress component include silicone oil and silicone rubber.
Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene.

When using a sulfur atom-containing compound other than mercaptosilane in the sealing resin composition of the present invention, the content of the sulfur atom-containing compound other than mercaptosilane is preferably 0.3% by mass as an upper limit value. 0.1 mass% is more preferable. Thus, by reducing the content of the sulfur atom-containing compound, high-temperature storage characteristics and the like can be improved. On the other hand, the lower limit of the content of the sulfur atom-containing compound other than mercaptosilane may be 0% by mass, but 0.01% by mass is preferable from the viewpoint of securing a certain degree of adhesion.

The sealing resin composition of the present invention can be prepared, for example, by the following method. First, the above-described components are uniformly mixed at room temperature using a mixer or the like, and then melt-kneaded using a kneader such as a heating roll, a kneader, or an extruder as necessary. Subsequently, if necessary, the obtained kneaded product is cooled and pulverized, and adjusted to a desired degree of dispersion, fluidity, and the like to obtain a sealing resin composition. The sealing resin composition of the present invention can be used as a powder composition, as well as a varnish using an organic solvent or a liquid composition using a liquid epoxy resin. When a solvent is included, the content of each component is converted to solid content.

[Electronic component equipment]
As shown in FIG. 1, an electronic component device 10 according to a second embodiment of the present invention includes an electronic component 11 and a sealing material 12 that seals the electronic component 11. Specifically, the electronic component 11 is fixed on the die pad 13 via a die bond material cured body 14. The electronic component device 10 includes a lead frame 16 connected from an electrode pad (not shown) of the electronic component 11 via a bonding wire 15.

The electronic component (element) 11 to be sealed refers to, for example, a component (element) that performs output in response to power input. Specifically, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, A solid-state image sensor, other semiconductor elements, etc. can be mentioned. The sealing material 12 is a cured product of the sealing resin composition according to the first embodiment. The bonding wire 15 can be a gold wire, a copper wire, or the like. As a material of the lead frame 16, copper, copper alloy, 42 alloy, or the like can be used.

Examples of the electronic component device 10 include a dual in-line package (DIP), a chip carrier with a plastic lead (PLCC), a quad flat package (QFP), and a low profile quad flat package ( LQFP), Small Outline Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package ( TCP), ball grid array (BGA), chip size package (CSP), and the like, but are not limited thereto.

For example, the electronic component device 10 fixes the electronic component 11 on the die pad 13 using a die bond material, connects the lead frame 16 with the bonding wire 15, and then seals these structures (sealed objects). It is manufactured by sealing using a resin composition. For this sealing, for example, after an object to be sealed composed of the electronic component 11 or the like is placed in the mold cavity, the sealing resin composition is molded and cured by a molding method such as transfer molding, compression molding, or injection molding. Can be performed. In the electronic component device 10 in which the electronic component 11 is sealed, if necessary, after curing the sealing resin composition at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours, Installed in electronic devices.

The electronic component device 10 uses the sealing resin composition according to the first embodiment as the sealing material 12, and the space between the sealing material 12 and the electronic component 11, the bonding wire 15, the lead frame 16, and the like. Adhesiveness is sufficient, and excellent high-temperature storage characteristics. In particular, even when a copper wire is used for the bonding wire 15 or the like, sufficient high-temperature storage characteristics and the like can be exhibited.

The present invention is not limited to the above-described embodiment, and the configuration thereof can be changed without changing the gist of the present invention.
Hereinafter, examples of the reference form will be added.
1. A sealing resin composition containing an epoxy resin (A), a curing agent (B), an inorganic filler (C), and a compound (D) represented by the following formula (1).
(In Formula (1), R ¹ is a polar group or a hydrocarbon group.)
2.1. The sealing resin composition described in the above, wherein R ¹ is a hydroxy group, an alkoxy group, or a primary, secondary, or tertiary amino group.
3.2. The sealing resin composition described in the above, wherein R ¹ is a secondary or tertiary amino group.
4.3. The encapsulating resin composition described above, wherein R ¹ is represented by the following formula (2).
5.1. ~ 4. The sealing resin composition according to any one of the above, wherein the content of the compound (D) is 0.01% by mass or more and 1% by mass or less.
6.1. ~ 5. The sealing resin composition according to any one of the above, further comprising a coupling agent (E), wherein the coupling agent (E) includes a silane coupling agent (E1) having a mercapto group. A resin composition for sealing.
7.6. The sealing resin composition described in the above, wherein the content of the silane coupling agent (E1) having a mercapto group is 0.01% by mass or more and 0.1% by mass or less. object.
8.1. ~ 7. The sealing resin composition according to any one of the above, further comprising a curing accelerator (F), wherein the curing accelerator (F) is a tetra-substituted phosphonium compound, and an adduct of a phosphine compound and a quinone compound. A sealing resin composition, which is at least one phosphorus atom-containing compound selected from the group consisting of:
9.1. ~ 8. The sealing resin composition according to any one of the above, wherein the sealing resin composition is used for sealing an electronic component to which a copper wire is connected.
10. In an electronic component device having an electronic component and a sealing material for sealing the electronic component,
The sealing material is 1. ~ 8. An electronic component device, which is a cured product of the sealing resin composition according to any one of the above.
11.10. The electronic component device according to claim 1, further comprising a copper wire connected to the electronic component.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to description of these Examples at all.

The components used in Example 1 , Reference Examples 1-2, Examples 4-5, Reference Example 3, Examples 7-8 , and Comparative Examples 1-2 are shown below.

Curing agent (B)
-Phenol resin curing agent 1: Phenol aralkyl resin having a biphenylene skeleton (trade name GPH-65 manufactured by Nippon Kayaku Co., Ltd.)
・ Phenolic resin curing agent 2: Phenol novolac resin (trade name PR-HF-3, manufactured by Sumitomo Bakelite Co., Ltd.)

Inorganic filler (C)
Inorganic filler 1: spherical fused silica with an average particle size of 30 μm and specific surface area of 1.7 m ² / g Inorganic filler 2: spherical fused silica with an average particle size of 0.5 μm and specific surface area of 5.9 m ² / g

Compound (D)
Compound 1: N- (2H-1,2,4-triazol-5-yl) salicylamide represented by the following formula (10) (CDA-1 manufactured by Adeka)

-Compound 2: 2-hydroxybenzoic acid-Compound 3: methyl 4-hydroxybenzoate

Compound (d)
Compound 4: 3-amino-5-mercapto-1,2,4-triazole represented by the following formula (11)

Coupling agent (E)
Coupling agent 1: N-phenyl-γ-aminopropyltrimethoxysilane Coupling agent 2: γ-mercaptopropyltrimethoxysilane

Curing accelerator (F)
Curing accelerator 1: Triphenylphosphine-1,4-benzoquinone adduct represented by the following formula (12) synthesized by the following method

(Synthesis of curing accelerator 1)
A separable flask equipped with a condenser and a stirrer was charged with 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 ml of acetone, and reacted at room temperature with stirring. The precipitated crystals were washed with acetone, filtered and dried to obtain dark green crystal curing accelerator 1.
Curing accelerator 2: Tetra-substituted phosphonium compound represented by the following formula (13) synthesized by the following method

(Synthesis of curing accelerator 2)
2,3-dihydroxynaphthalene in a separable flask equipped with a condenser and a stirrer;
81 g (0.080 mol), 16.77 g (0.040 mol) of tetraphenylphosphonium bromide and 100 ml of methanol were charged and stirred to dissolve uniformly. When a sodium hydroxide solution prepared by previously dissolving 1.60 g (0.04 ml) of sodium hydroxide in 10 ml of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain a curing accelerator 2.

Other components / coloring agent: carbon black / ion scavenger: hydrotalcite (DHT-4H manufactured by Kyowa Chemical Co., Ltd.)
・ Release agent: Carnauba wax (Nikko Carnaba manufactured by Nikko Fine Products)

[Example 1]
Epoxy resin 1 (8.7 parts by mass), phenol resin-based curing agent 1 (6.4 parts by mass), inorganic filler 1 (73.72 parts by mass), inorganic filler 2 (10 parts by mass), compound 1 ( 0.03 parts by mass), coupling agent 1 (0.2 parts by mass), curing accelerator 1 (0.25 parts by mass), colorant (0.4 parts by mass), ion scavenger (0.1 parts by mass) ) And a release agent (0.2 parts by mass) at room temperature using a mixer, and then roll-kneaded at 70 to 100 ° C. Subsequently, after cooling, it was pulverized to obtain a sealing resin composition of Example 1.

[ Reference Examples 1-2, Examples 4-5, Reference Example 3, Examples 7-8 , Comparative Examples 1-2]
Reference Example 1-2, Example 4-5, Reference Example 3, Example 7-8 , except having used the usage-amount (compounding quantity) of each component as shown in Table 1 like Example 1. The sealing resin compositions of Comparative Examples 1 and 2 were obtained.

Manufacturing of semiconductor device (electronic component device) TEG (Test Element Group) chip (3.5mm x 3.5mm) 352 pin BGA (substrate is 0.56mm thick, bismaleimide / triazine resin / glass cloth substrate, package The size was mounted on 30 mm × 30 mm, thickness 1.17 mm). Subsequently, wire bonding was performed on the electrode pad with a wire pitch of 80 μm using a copper wire (copper purity 99.99 mass%, diameter 25 μm).
Using the low-pressure transfer molding machine (“Y series” manufactured by TOWA), the obtained structure was subjected to each of the obtained conditions under conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 2 minutes. Sealing molding was performed using the sealing resin compositions of Examples , Reference Examples, and Comparative Examples to prepare 352-pin BGA packages. Thereafter, the obtained BGA package was post-cured at 175 ° C. for 4 hours to obtain a semiconductor device (electronic component device).

[Evaluation]
The sealing resin compositions and semiconductor devices of the obtained Examples , Reference Examples and Comparative Examples were evaluated by the following methods. The evaluation results are shown in Table 1.

[Adhesion]
The adhesion to each metal (Ag, Cu, PPF (pre-plating frame), Ni) was evaluated by the following method. The obtained sealing resin composition was integrally molded on the substrate made of each metal under the conditions of 175 ° C., 6.9 MPa, and 2 minutes, and post-cured at 175 ° C. for 4 hours. Thereafter, the shear adhesive strength with each substrate was measured at 260 ° C.

[High temperature storage characteristics]
The obtained semiconductor device was subjected to HTSL (high temperature storage test) by the following method. Each semiconductor device was stored under conditions of a temperature of 200 ° C. and 1000 hours. About the semiconductor device after storage, the electrical resistance value between the wire and the electrode pad was measured. A semiconductor device whose average value shows an electrical resistance value of less than 110% with respect to the average value of the initial resistance value is ◎, a semiconductor device whose electrical resistance value is 110% or more and 120% or less is good, and is larger than 120%. Those showing electrical resistance values were marked with x.

As shown in Table 1, it can be seen that each of the sealing resin compositions of Examples has sufficient adhesion, and the obtained electronic component device (semiconductor device) has excellent high-temperature storage characteristics. Specifically, Comparative Example 1 containing no compound (D) has relatively low adhesion and high-temperature storage characteristics, does not have the structure of Formula (1), and has a mercapto group (4) Comparative Example 2 containing -amino-5-mercapto-1,2,4-triazole) has improved adhesion to Comparative Example 1, but has not improved high-temperature storage characteristics. On the other hand, Example 1 which contains a compound (D) , Reference Examples 1-2, Examples 4-5, Reference Example 3, and Examples 7-8 have adhesiveness equivalent to or higher than Comparative Example 2. However, the high-temperature storage characteristics are increasing. In particular, when the compounds 1 and 2 having an alkoxy group or an amino group are used as the compound (D), adhesion and high-temperature storage characteristics are further enhanced (Example 1, Reference Example 1, Examples 4 to 5, Reference Example 3). Examples 7 to 8 ) When the compound 1 having an amino group is used, it can be seen that the adhesion and high-temperature storage characteristics are further enhanced (Examples 1, 4, 5, 7, and 8). In addition, when a compound (D) and a mercaptosilane (coupling agent 2) as a coupling agent (D) are used in combination, a compound having a mercapto group (coupling agent 2) is contained. It can be seen that the high-temperature storage characteristics are maintained while further improving the adhesion (Example 5 , Reference Example 3, Example 7 ).

10: Electronic component device, 11: Electronic component, 12: Sealing material, 13: Die pad, 14: Die bond material cured body, 15: Bonding wire, 16: Lead frame

Claims (8)

Containing epoxy compound (A), curing agent (B), inorganic filler (C) and compound (D) represented by the following formula (1),
In the following formula (1), ^{R 1} is a secondary or tertiary amino group,
The sealing resin composition further contains a curing accelerator (F), and the curing accelerator (F) is at least selected from the group consisting of a tetra-substituted phosphonium compound and an adduct of a phosphine compound and a quinone compound. A sealing resin composition, which is one or more phosphorus atom-containing compounds.
The sealing resin composition according to claim 1 , wherein R ¹ is represented by the following formula (2).
The sealing resin composition according to claim 1 or 2 , wherein the content of the compound (D) is 0.01% by mass or more and 1% by mass or less. The sealing resin composition according to any one of claims 1 to 3 , further comprising a coupling agent (E), wherein the coupling agent (E) has a mercapto group (E1). The sealing resin composition characterized by including this. 5. The sealing resin composition according to claim 4 , wherein the content of the silane coupling agent (E1) having a mercapto group is 0.01% by mass or more and 0.1% by mass or less. Resin composition. The resin composition for sealing according to any one of claims 1 to 5, wherein the resin composition for sealing is used for sealing an electronic component to which a copper wire is connected. In an electronic component device having an electronic component and a sealing material for sealing the electronic component,
The said sealing material is a hardened | cured material of the resin composition for sealing of any one of Claims 1-6 , The electronic component apparatus characterized by the above-mentioned. 8. The electronic component device according to claim 7 , further comprising a copper wire connected to the electronic component.