JP6507506B2 - Resin composition for sealing and semiconductor device - Google Patents

Description

  The present invention relates to a sealing resin composition and a semiconductor device.

  Semiconductor devices (electronic components) such as diodes, transistors, and integrated circuits are distributed in the market or incorporated in electronic devices as semiconductor devices molded with a cured product such as an epoxy resin composition. The epoxy resin composition used for such a sealing material generally comprises a composition of an epoxy resin, a phenol resin-based curing agent, an inorganic filler, a coupling agent, and the like. In addition, with the trend of miniaturization, weight reduction, high performance, etc. of electronic devices in recent years, high integration of electronic parts advances, etc., and the performance required for a sealing material (resin composition for sealing) is also high. It has become. Specific performances required of the sealing material include, for example, adhesion, solder resistance, flowability, heat resistance, high temperature storage characteristics and the like.

  Among these, a sealing resin composition containing a compound having a mercapto group, such as a silane coupling agent having a mercapto group, has been developed (see Patent Document 1 and Patent Document 2). By containing a compound having a mercapto group, the adhesion to an electronic component or the like is enhanced.

  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 to connect the semiconductor element and the lead frame, but even more for semiconductor devices using copper members such as copper wires. Such high temperature storage characteristics are required, and development of a sealing resin composition suitable for sealing such a semiconductor element is desired.

JP 2003-268200 A JP 2008-201873 A

  The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a sealing resin composition having sufficient adhesion to metal and also having high temperature storage characteristics of the obtained semiconductor device. .

（式（１ｄ）中、Ｒはジオール部位とトリアジン環部位とを連結する連結基である。）。 ADVANTAGE OF THE INVENTION According to this invention, it is the resin composition for sealing which molds a semiconductor element, Comprising: The resin composition for sealing containing the following components is provided.
(A) Epoxy resin (B) Curing agent (C) Inorganic filler (D) At least one diaminotriazine compound selected from the following formulas (1a) to (1d)

(In formula (1d), R is a linking group linking a diol moiety and a triazine ring moiety.)

（式中、Ｒは一価の有機基である。）

(Wherein R is a monovalent organic group)

Moreover, according to the present invention,
A semiconductor element,
A bonding wire connected to the semiconductor element;
A sealing resin which is formed of a cured product of the above-described sealing resin composition and which seals the semiconductor element and the bonding wire;
A semiconductor device is provided.

  According to the sealing resin composition of the present invention, it is possible to have sufficient adhesion to metals and to improve the high temperature storage characteristics of the obtained semiconductor device.

It is a sectional view showing a semiconductor device concerning this embodiment.

  Hereinafter, embodiments will be described using drawings as appropriate.

[Resin composition for sealing]
The sealing resin composition according to the present embodiment is a sealing resin composition for molding a semiconductor element, and includes the following components.
(A) Epoxy resin (B) Hardener (C) Inorganic filler (D) Diaminotriazine compound represented by the following general formula (1)

（式中、Ｒは一価の有機基である。）

(Wherein R is a monovalent organic group)

  Each component will be described below.

[(A) Epoxy resin]
The (A) epoxy resin is a compound (monomer, oligomer and polymer) having two or more epoxy groups in one molecule, and the molecular weight and the molecular structure are not particularly limited. (A) As epoxy resin, for example, crystalline epoxy resin such as biphenyl type epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin; novolac type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin; Multifunctional epoxy resin such as phenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin; Phenol aralkyl type epoxy resin such as phenol aralkyl type epoxy resin having phenylene skeleton, phenol aralkyl type epoxy resin having biphenylene skeleton; dihydroxynaphthalene Type epoxy resin, naphthol type epoxy resin such as epoxy resin obtained by glycidyl etherification of dimer of dihydroxy naphthalene; triglycidyl isocyanate Cyanurate, triazine nucleus-containing epoxy resins such as monoallyl diglycidyl isocyanurate; 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 the formula (3), Ar ¹ is a phenylene group (a group consisting of a phenol structure and a structure obtained by removing hydrogen atoms of the number of bonds from phenol) or a naphthylene group (a group consisting of a naphthalene structure) 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 consisting of a biphenylene structure and a structure obtained by removing hydrogen atoms of the number of bonds from biphenyl) and a naphthalene 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 Ar ¹ is a phenylene group is an integer of 0 to 3). h is an integer of 0 to 8 (provided that Ar ² is a phenylene group is an integer of 0 to 4 and a biphenylene group is an integer of 0 to 6). n ¹ represents the degree of polymerization, and the average value thereof is 1 to 3.

As Ar ¹ , a phenylene group is preferable. As Ar ² , a phenylene group or a biphenylene group is preferable. The flame retardancy can also be enhanced by setting Ar ² to a phenylene group or a biphenylene group (introducing a phenylene skeleton or a biphenylene skeleton). When g and h are not 0 in R ³ and R ⁴ , examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl and ethyl, alkenyl groups such as vinyl, and aryl groups such as phenyl Can be mentioned. g and h are preferably 0.

In Formula (4), a plurality of R ^{5 's} 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. As a C1-C4 hydrocarbon group, alkenyl groups, such as alkyl groups, such as a methyl group and an ethyl group, a vinyl group, etc. can be mentioned.

  The content of the epoxy resin (A) relative to the total solid content of the encapsulating resin composition is not particularly limited, but the lower limit is preferably 2% by mass or more, and more preferably 4% by mass or more. (A) By making content of an epoxy resin more than the said lower limit, sufficient adhesiveness etc. can be exhibited. As an upper limit of content of an epoxy resin (A), 20 mass% or less is preferable, and 10 mass% or less is more preferable. By making content of an epoxy resin (A) below into the said upper limit, sufficient low water absorption, low thermal expansivity, etc. can be exhibited.

[(B) curing agent]
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. .

  As a polyaddition type curing agent, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA) And polyamine compounds containing dicyandiamide (DICY), organic acid dihydrazide, etc. in addition to aromatic polyamines such as diaminodiphenyl sulfone (DDS); alicyclic compounds such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), etc. Acid anhydride, aromatic acid anhydride such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA), etc .; Anhydrides including aromatic anhydrides; novolac type phenol resin, phenol polymer, etc. Polyphenol compounds; Polymercaptan compounds such as polysulfides, thioesters and thioethers; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; Organic acids such as carboxylic acid-containing polyester resins; Phenol resin-based curing agents described in detail below; etc. Be

As a catalyst type curing agent, for example, 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 (EMI 24); Lewis acids such as BF ₃ complex; and the like.

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

  Among these, as the (B) curing agent, a phenol resin-based curing agent is preferable. By using a phenol resin-based curing agent, flame resistance, moisture resistance, electrical properties, curability, storage stability and the like can be exhibited in a well-balanced manner. The phenolic resin-based curing agent is 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.

  As a phenol resin-based curing agent, for example, novolak type resins such as phenol novolak resin and cresol novolac resin; polyfunctional phenol resins such as triphenolmethane type phenol resin; terpene modified phenolic resin, dicyclopentadiene modified phenolic resin and the like Modified phenolic resins; aralkyl type resins such as phenol aralkyl resins having a phenylene skeleton and / or a biphenylene skeleton, and naphthol aralkyl resins having a phenylene and / or a biphenylene skeleton; bisphenol compounds such as bisphenol A, bisphenol F, etc. One type may be used alone or two or more types may be used in combination.

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

In the formula (5), Ar ³ is a phenylene group (a group consisting of a phenol structure and a structure obtained by removing hydrogen atoms of the number of bonds from phenol) or a naphthylene group (a group consisting of a naphthalene structure) 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 and a structure obtained by removing hydrogen atoms of the number of bonds 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 (however, 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 Ar ⁴ is a phenylene group is an integer of 0 to 4 and a biphenylene group is an integer of 0 to 6). n ³ represents the degree of polymerization, the average value is 1-3.

As Ar ³ , a phenylene group is preferable. As Ar ⁴ , a phenylene group or a biphenylene group is preferable. In addition, flame resistance etc. can also be improved by making Ar ⁴ into a phenylene group or a biphenylene group (introducing a phenylene skeleton or a biphenylene skeleton). 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.

  The content of the curing agent (B) relative to the total solid content of the sealing resin composition is not particularly limited, but the lower limit is preferably 0.5% by mass or more, and more preferably 2% by mass or more. By setting the content of the curing agent (B) to the above lower limit value or the like, sufficient curability, adhesion and the like can be exhibited. As an upper limit of content of a (B) hardening agent, 15 mass% or less is preferable, and 10 mass% or less is more preferable. By setting the content of the curing agent (B) to the upper limit or less, sufficient fluidity and the like can be exhibited.

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

The average particle diameter of the (C) inorganic filler is not particularly limited, but the lower limit thereof is preferably 0.1 μm or more, and more preferably 0.3 μm or more. On the other hand, as an upper limit, 40 micrometers or less are preferable, and 35 micrometers or less are more preferable. Moreover, as a lower limit of the specific surface area of the (C) inorganic filler, 1 m ² / g or more is preferable, and 3 m ² / g or more is more preferable. On the other hand, as an upper limit, 10 m < ² > / g or less is preferable and 7 m < ² > / g or less is more preferable. By using an inorganic filler having an average particle diameter and a specific surface area in such a range, fluidity, low hygroscopicity, and the like can be further improved.

  If necessary, two or more inorganic fillers in the preferred range may be used in combination, for example, using an inorganic filler having an average particle diameter of 0.1 μm to 1 μm and an inorganic filler having an average particle diameter of 10 μm to 40 μm. Is also preferred.

  The content of the inorganic filler (C) relative to the total solid content of the encapsulating resin composition is not particularly limited, but the lower limit is preferably 35% by mass or more, more preferably 70% by mass or more, and 75% by mass The above is particularly preferable. (C) By setting the content of the inorganic filler to the above lower limit value or the like, sufficient low hygroscopicity, low thermal expansion and the like can be exhibited. As an upper limit of content of an (C) inorganic filler, 95 mass% or less is preferable, and 92 mass% or less is more preferable. By setting the content of the (C) inorganic filler to the upper limit value or less, sufficient fluidity and the like can be exhibited.

[(D) diaminotriazine compound]
The (D) diaminotriazine compound is a compound represented by the following formula (1). The (D) diaminotriazine compound may be used alone or in combination of two or more. Since the sealing resin composition of the present embodiment contains a specific compound having two amino groups in the triazine ring structure, sufficient adhesion to metals and high-temperature storage characteristics of the resulting semiconductor device can be obtained. Both can be achieved.
The reason for this is not clear, but the organic group provided at the 6-position in the triazine skeleton improves the compatibility with the epoxy resin in the sealing resin composition, and as a result, the resin composition acts on the metal peripheral portion. It is thought that it becomes easy to flow. Further, it is considered that the two amino groups provided at the 2- and 4-positions in the triazine skeleton and the nitrogen atom at the 3-position improve the adhesion to a lead frame, an organic substrate, a chip or the like.

（式中、Ｒは一価の有機基である。）

(Wherein R is a monovalent organic group)

In addition, if substituent R in Formula (1) is a monovalent organic group, it can be set suitably, as long as the object of the invention is not impaired. Here, "monovalent organic group" indicates that at least one carbon atom is present in the substituent R present at the 6-position of the triazine ring skeleton. That is, the connection between the 6-position carbon of the triazine skeleton and the substituent R is not necessarily limited to the carbon-carbon bond, but is a bond between carbon and other hetero atoms such as nitrogen atom, oxygen atom, sulfur atom, etc. I don't care. 2 or more are preferable and, as for the carbon atom contained in the substituent R, 3 or more are more preferable. The upper limit of the number of carbon atoms in the R substituent is, for example, 30 or less, preferably 20 or less, and more preferably 15 or less.
In addition to the carbon atoms (C) and hydrogen atoms (H), nitrogen atoms (N), oxygen atoms (O), sulfur atoms (S), the substituent R is also silicon atoms (Si), germanium atoms (Ge), etc. Those containing a metalloid atom of the above, a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), and a halogen atom of an iodine atom (I) can also be adopted.
Further, as the substituent R, a linking group such as an ether bond, an ester bond, an amide bond, a urethane bond, a sulfide bond, a thioester bond or the like may be contained in the substituent, and a phenyl group, a naphthyl group, etc. Aromatic substituents including hetero atoms such as pyrrole, pyridine, thiophene, furan, indole and the like; alicyclic substituents such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like; It is also good.

Here, the (D) diaminotriazine compound represented by the general formula (1) has at least one group having an active hydrogen atom selected from an alcoholic hydroxyl group, a phenolic hydroxyl group and a carboxyl group in a substituent R preferable.
When the substituent R contains a group having such an active hydrogen atom in the substituent, the compatibility between the (D) diaminotriazine compound and other components in the sealing resin composition is further improved. it can.
(D) The number of groups having an active hydrogen atom in one molecule of the diaminotriazine compound can be set as appropriate, but it is, for example, 1 or more as the lower limit, and 10 or less as the upper limit, preferably 5 It is below.

The molecular weight of the (D) diaminotriazine compound can be set as appropriate, but the lower limit thereof is, for example, 135 or more, preferably 150 or more, and more preferably 180 or more. The upper limit value of the molecular weight of this compound is, for example, 600 or less, preferably 500 or less, and more preferably 400 or less.
By setting such a range, desired effects can be efficiently exhibited.

  As a (D) diamino triazine compound preferably used in this embodiment, the following compound groups are mentioned, for example.

  The content of the (D) diaminotriazine compound relative to the total solid content of the encapsulating resin composition is not particularly limited, but the lower limit thereof is preferably 0.01% by mass or more, more preferably 0.03% by mass or more . By setting the content of the (D) diaminotriazine compound to the above lower limit value or the like, sufficient high temperature storage characteristics and the like can be exhibited. As an upper limit of content of a (D) diamino triazine compound, 1.0 mass% or less is preferable, 0.5 mass% or less is more preferable, 0.2 mass% or less is especially preferable. By setting the content of the (D) diaminotriazine compound to the upper limit value or less, sufficient fluidity and the like can be exhibited.

[(E) coupling agent]
The sealing resin composition may further contain (E) a coupling agent. (E) A coupling agent is a component which connects the (A) epoxy resin etc. which are resin components, and the (C) inorganic filler. (E) As a coupling agent, silane coupling agents, such as an epoxysilane, an aminosilane, a mercaptosilane (silane coupling agent which has a mercapto group) (E1), can be mentioned. These (E) coupling agents may be used alone or in combination of two or more.

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

  Examples of the aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane (sometimes called anilinosilane), and the like.

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

  Among these (E) coupling agents, 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, but according to the sealing resin composition of the present embodiment, it contains a specific triazine compound Therefore, the high temperature storage characteristics and the high adhesion to metals can be more compatible than in the case of using the mercaptosilane.

  The content of the (E) coupling agent relative to the total solid content of the resin composition is not particularly limited, but the lower limit is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. As an upper limit, 1 mass% or less is preferable, and 0.5 mass% or less is more preferable. By setting the content of the (E) coupling agent to the above range, the function of the (E) coupling agent can be effectively expressed.

  When the (D) diaminotriazine compound and mercaptosilane (E1) are used in combination, the lower limit value of the content of the mercaptosilane is preferably 0.01% by mass or more, and more preferably 0.02% by mass or more . By making content of a mercaptosilane (E1) more than the said lower limit, adhesiveness etc. can be improved effectively. As an upper limit of content of mercaptosilane (E1), 0.1 mass% or less is preferable, and 0.07 mass% or less is more preferable. By setting the content of mercaptosilane (E1) to the above upper limit value or less, it is possible to achieve both more excellent high temperature storage characteristics and high adhesion to metal.

[(F) curing accelerator]
The sealing resin composition of the present embodiment may further contain (F) a curing accelerator. The curing accelerator (F) is a component having a function of accelerating the reaction of (A) epoxy resin and (B) curing agent, and commonly used curing accelerators are used.

(F) As a curing accelerator, a phosphorus atom-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, an adduct of a phosphonium compound and a silane compound; -Mentioning an amidine such as diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole and the like, a tertiary amine, and further a nitrogen atom-containing compound such as the amidine and the quaternary salt of the amine. These can be used alone or in combination of two or more.
Among these, phosphorus atom-containing compounds are preferable from the viewpoints of curability, adhesion and the like. Furthermore, from the viewpoints of solder resistance, flowability, etc., an adduct of a phosphobetaine compound or a phosphine compound and a quinone compound is particularly preferable, and tetra-substituted from the viewpoint that the contamination of the mold in continuous molding is mild. Particularly preferred are phosphorus atom-containing compounds such as phosphonium compounds and adducts of phosphonium compounds and silane compounds.

(Organic phosphine)
Examples of organic phosphines include: primary phosphines such as ethyl phosphine and phenyl phosphine; secondary phosphines such as dimethyl phosphine and diphenyl phosphine; tertiary phosphines such as trimethyl phosphine, triethyl phosphine, tributyl phosphine and triphenyl phosphine it can.

(Tetra substituted phosphonium compound)
As a tetra substituted phosphonium compound, the compound etc. which are represented by following formula (6) can be mentioned, for example.

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 a number of 1 to 3, z is a number of 0 to 3 and x = y.

  The compound represented by Formula (6) is obtained, for example, as follows, but is not limited thereto. First, a tetrasubstituted phosphonium halide, an aromatic organic acid and a base are mixed with an organic solvent and uniformly mixed, and an aromatic organic acid anion is generated in the solution system. Water can then be added to precipitate the compound of formula (6).

In the compound represented by the formula (6), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ bonded to a phosphorus atom are phenyl groups, and AH is a compound having a hydroxy group in an aromatic ring, that is, phenols, and [a] ^- it is preferred that the anion of the phenol. The phenols include monocyclic phenols such as phenol, cresol, resorcinol and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene and anthraquinol, bisphenols such as bisphenol A, bisphenol F and bisphenol S, phenyl Polycyclic phenols, such as phenol and biphenol, etc. can be mentioned.

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

In formula (7), P is a phosphorus atom. R ¹² is an alkyl group having 1 to 3 carbon atoms. R ¹³ is a hydroxy group. k is an integer of 0 to 5; m is an integer of 0 to 3;

  The compound represented by Formula (7) is obtained as follows, for example. It is obtained through the process of contacting the triaromatic substituted phosphine, which is a tertiary phosphine, with a diazonium salt, and replacing the triaromatic substituted phosphine with the diazonium group possessed by the diazonium salt. However, it is not limited to this.

(Adduct of phosphine compound and quinone compound)
As an adduct of a phosphine compound and a quinone compound, the compound etc. which are represented by following formula (8) can be mentioned, for example.

In formula (8), P is a phosphorus atom. R <^14> , R <^15> and R < ¹⁶ > are respectively independently a C1-C12 alkyl group or a C6-C12 aryl group. R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent 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.

  As a phosphine compound used for the adduct of a phosphine compound and a quinone compound, for example, no aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, tris (benzyl) phosphine etc. Those in which a substituent or a substituent such as an alkyl group or an alkoxyl group is present are preferable. Examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. Triphenyl phosphine is preferred from the viewpoint of availability.

  As a quinone compound used for the adduct of a phosphine compound and a quinone compound, benzoquinone, anthraquinones etc. are mentioned, for example, Among these, p-benzoquinone is preferable from the point of storage stability.

  As a method for producing an adduct of a phosphine compound and a quinone compound, for example, an adduct may be obtained by contacting and mixing these in a solvent in which both organic tertiary phosphine and benzoquinones can be dissolved. it can. As the solvent, ketones such as acetone and methyl ethyl ketone having a low solubility in the adduct are preferable. However, it is not limited to this.

In the compound represented by the formula (8), a compound wherein R ¹⁴ , R ¹⁵ and R ¹⁶ bonded to a phosphorus atom is a phenyl group, and R ¹⁷ , R ¹⁸ and R ¹⁹ are a hydrogen atom, ie, 1,4 The compound in which-benzoquinone and triphenyl phosphine are added is preferable at the point to which the thermal elasticity modulus of the hardened | cured material of a resin composition is reduced.

(Adduct of phosphonium compound and silane compound)
As an adduct of a phosphonium compound and a silane compound, the compound etc. which are represented by following formula (9) can be mentioned, for example.

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 in which a proton donating group releases a proton, 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 each represent a group in which a proton donating group releases a proton, 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 as or different from each other, and Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same as or different from each other. Z ¹ is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.

As R ²⁰ , R ²¹ , R ²² and R ²³ , for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl Groups, n-octyl group, cyclohexyl group and the like can be mentioned. Among these, alkyl groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group and hydroxynaphthyl group, and aromatic groups or unsubstituted aromatic groups having a substituent such as alkoxy group and hydroxy group are preferable. .

The group represented by -Y ² -R ²⁴ -Y ^3- and Y ⁴ -R ²⁵ -Y ^5- in the formula (9) is a group in which a proton donor releases two protons. It is 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 preferable, and hydroxy groups respectively connected to adjacent carbons constituting one aromatic ring More preferred are aromatic compounds having at least two. As such a proton donor, for example, 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.

The organic group having an aromatic ring or heterocycle represented by Z ¹ in Formula (9) or an aliphatic group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, etc. Aliphatic hydrocarbon group, aromatic hydrocarbon group such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxy group such as glycidyl oxypropyl group, mercaptopropyl group and aminopropyl group, mercapto group and amino group Reactive substituents, such as an alkyl group and a vinyl group, etc. are mentioned. Among these, a methyl group, an ethyl group, a phenyl group, a naphthyl group and a biphenyl group are preferable in terms of heat stability and the like.

  Examples of the method for producing the adduct of the phosphonium compound and the silane compound include the following methods. First, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol for dissolution, and then a sodium methoxide-methanol solution is dropped under stirring at room temperature. Furthermore, 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 precipitated. 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 which tetra-substituted phosphonium compounds (for example, formulas The compound represented by (6) or an adduct of a phosphine compound and a quinone compound (for example, a compound represented by the formula (8)) is preferable, and an adduct of a phosphine compound and a quinone compound is more preferable.

  Although it does not specifically limit as content in the whole solid part of the resin composition for sealing of (F) hardening accelerator, As a lower limit, 0.1 mass% or more is preferable, 0.2 mass% or more is more preferable . (F) By setting the content of the curing accelerator to the above lower limit value or the like, sufficient curability and the like can be obtained. As an upper limit of content of a (F) hardening accelerator, 1 mass% or less is preferable, and 0.5 mass% or less is more preferable. (F) By setting the content of the curing accelerator to the upper limit value or less, sufficient flowability and the like can be obtained.

[Other ingredients]
The sealing resin composition may further contain other components as necessary. As another component, a coloring agent, an ion trapping agent, a mold release agent, a low stress component, a flame retardant etc. can be mentioned.
Examples of colorants include carbon black and bengala.
As an ion trapping agent, hydrotalcite etc. can be mentioned. Ion scavengers may also be used as neutralizing agents.
Examples of mold release agents include natural waxes such as carnauba wax, synthetic waxes, higher fatty acids such as zinc stearate and metal salts thereof, and paraffins.
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, phosphazene and the like.

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

[Semiconductor device]
Next, a semiconductor device to which the sealing resin composition according to the present embodiment is applied will be described.
FIG. 1 is a cross-sectional view showing a semiconductor device 100 according to the present embodiment.
The semiconductor device 100 of the present embodiment includes the semiconductor element 20, the bonding wire 40 connected to the semiconductor element 20, and the sealing resin 50, and the sealing resin 50 is used for the above-described sealing. It consists of a cured product of the resin composition.
More specifically, the semiconductor element 20 is fixed on the base 30 through the die attach material 10, and the semiconductor device 100 is connected to the electrode pad 22 provided on the semiconductor element 20 through the bonding wire 40. And the outer lead 34 connected.

The semiconductor element 20 to be sealed is, for example, a component (element) to which output is performed with respect to input of power, and specifically, an integrated circuit, a large scale integrated circuit, a transistor, a thyristor, a diode, a solid development element And other elements can be mentioned.
The bonding wire 40 can be set in consideration of the semiconductor element 20 and the like to be used, but for example, a copper bonding wire can be used.

  The form of the semiconductor device 100 is, for example, dual in-line package (DIP), plastic leaded chip carrier (PLCC), quad flat package (QFP), 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), etc., but is not limited thereto.

  In the semiconductor device 100, for example, after fixing the semiconductor element 20 on the die pad 32 (substrate 30) using the die attach material 10 and connecting the die pad 32 (base material 30) which is a lead frame with the bonding wire 40, The structure (object to be sealed) is sealed by using the sealing resin composition. In this sealing, for example, after an object to be sealed including the semiconductor element 20 and the like is placed in a mold cavity, the sealing resin composition is molded and cured by a molding method such as transfer molding, compression molding or injection molding. It can be done by The semiconductor device 100 in which the semiconductor element 20 is sealed cures the sealing resin composition at a temperature of about 80 ° C. to about 200 ° C. for about 10 minutes to 10 hours, if necessary, and It is mounted on equipment etc.

  The semiconductor device 100 uses the above-described sealing resin composition as the sealing resin 50, and the adhesion between the sealing resin 50 and the semiconductor element 20, the bonding wire 40, the electrode pad 22 and the like is sufficient. Also excellent in high temperature storage characteristics. In particular, even when a copper wire is used as the bonding wire 40, sufficient high temperature storage characteristics and the like can be exhibited.

（式中、Ｒは一価の有機基である。）。
２． 半導体素子と、前記半導体素子に接続される、銅ボンディングワイヤと、を封止するために用いられる、１．に記載の封止用樹脂組成物。
３． 前記一般式（１）で示されるジアミノトリアジン化合物が、Ｒ置換基内にアルコール性水酸基、フェノール性水酸基及びカルボキシル基から選ばれる活性水素原子を有する基１つ以上を有する、１．または２．に記載の封止用樹脂組成物。
４． 前記硬化剤がフェノール樹脂系硬化剤である、１．ないし３．のいずれかに記載の封止用樹脂組成物。
５． 前記封止用樹脂組成物全体に対する前記無機充填材の含有量が、３５質量％以上９５質量％以下である、１．ないし４．のいずれかに記載の封止用樹脂組成物。
６． 半導体素子と、
前記半導体素子に接続されるボンディングワイヤと、
１．ないし５．のいずれかに記載の封止用樹脂組成物の硬化物により構成され、かつ前記半導体素子と前記ボンディングワイヤを封止する封止樹脂と、
を備える半導体装置。 As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to the said embodiment, The structure can also be changed in the range which does not change the summary of this invention.
Hereinafter, an example of a reference form is added.
1. It is a resin composition for sealing which molds a semiconductor element, Comprising: The resin composition for sealing containing the following components.
(A) Epoxy resin
(B) Hardening agent
(C) Inorganic filler
(D) Diaminotriazine compound represented by the following general formula (1)

(Wherein, R is a monovalent organic group).
2. Used for sealing a semiconductor element and a copper bonding wire connected to the semiconductor element The resin composition for sealing as described in-.
3. The diaminotriazine compound represented by the general formula (1) has one or more groups having an active hydrogen atom selected from an alcoholic hydroxyl group, a phenolic hydroxyl group and a carboxyl group in an R substituent. Or 2. The resin composition for sealing as described in-.
4. The curing agent is a phenol resin curing agent, Or 3. The sealing resin composition according to any one of the above.
5. Content of the said inorganic filler with respect to the said whole resin composition for sealing is 35 mass% or more and 95 mass% or less. Or 4. The sealing resin composition according to any one of the above.
6. A semiconductor element,
A bonding wire connected to the semiconductor element;
1. To 5. And a sealing resin that is formed of a cured product of the sealing resin composition according to any one of the above, and seals the semiconductor element and the bonding wire.
Semiconductor device provided with

  Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the description of these examples.

About the component used by Examples 1-19 and Comparative Examples 1-3, it shows below.
(A) Epoxy resin / Epoxy resin 1: Biphenyl type epoxy resin (Mitsubishi Chemical Co., Ltd. trade name YX4000K)
Epoxy resin 2: Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. trade name NC-3000)
Epoxy resin 3: Phenolic aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. trade name NC-2000)

(B) Curing agent / phenol resin curing agent 1: Phenolic aralkyl resin having a biphenylene skeleton having a hydroxyl equivalent of 198 g / eq and a softening point of 64.5 ° C. (manufactured by Nippon Kayaku Co., Ltd., trade name “GPH-65” ). In the following general formula (10), R ⁴⁷ has a structure of 4,4′-dimethylenebiphenyl.
-Phenolic resin-based curing agent 2: A phenolic resin having a trisphenolmethane skeleton having a hydroxyl equivalent of 97 g / eq and a softening point of 110 ° C (manufactured by Meiwa Kasei Co., Ltd., trade name "MEH-7500"). In the following general formula (10), it has a structure in which R ⁴⁷ is hydroxyphenylmethylene.

-Phenolic resin-based curing agent 3: Phenolic novolac resin (trade name PR-HF-3 manufactured by Sumitomo Bakelite Co., Ltd.)

(C) Inorganic filler / inorganic filler 1: Spherical fused silica / inorganic filler ² having an average particle diameter of 30 μm and a specific surface area of 1.7 m ² / g 2: an average particle diameter of 0.5 μm, a specific surface area of 5.9 m ² / g Spherical fused silica

(D) Diaminotriazine Compound Compound 1: Diaminotriazine Compound Represented by the Following Formula (1a) (2,4-Diamino-6- (4,5-dihydroxypentyl) -1,3,5-triazine)

（化合物１の合成）
冷却管及び撹拌装置付きのセパラブルフラスコに２，４−ジアミノ−６−ビニル−ｓ−トリアジン１３．７ｇ（０．１ｍｏｌ）、酢酸パラジウム０．２２４ｇ（０．００１ｍｏｌ）、トリフェニルホスフィン０．５２ｇ（０．００２ｍｏｌ）を仕込み、フラスコ内部をアルゴン置換した。さらにフラスコ内に３−クロロ‐１，２−プロパンジオール１１ｇ（０．１ｍｏｌ）、トリエチルアミン２０．２ｇ（０．２ｍｏｌ）、テトラヒドロフラン２００ｍｌを仕込み、６０℃で２４時間加熱した。反応用液を濃縮後、酢酸エチル２００ｍｌに溶解し、水洗した。反応物の酢酸エチル溶液をフラスコに移し、パラジウム炭素１ｇを添加した。反応系内を水素で置換し、水素を充てんした風船からフラスコ内部へ水素を供給しながら１２時間撹拌した。反応用液をろ過濃縮し、ヘキサン／酢酸エチル混合溶媒で再結晶した。析出した結晶をろ過、減圧乾燥することで、化合物１を得た。

(Synthesis of Compound 1)
In a separable flask equipped with a condenser and a stirrer, 13.7 g (0.1 mol) of 2,4-diamino-6-vinyl-s-triazine, 0.224 g (0.001 mol) of palladium acetate, 0.52 g of triphenylphosphine (0.002 mol) was charged, and the inside of the flask was purged with argon. Further, 11 g (0.1 mol) of 3-chloro-1,2-propanediol, 20.2 g (0.2 mol) of triethylamine and 200 ml of tetrahydrofuran were charged in a flask and heated at 60 ° C. for 24 hours. The reaction solution was concentrated, dissolved in 200 ml of ethyl acetate, and washed with water. The ethyl acetate solution of the reaction was transferred to a flask and 1 g of palladium on carbon was added. The inside of the reaction system was replaced with hydrogen and stirred for 12 hours while supplying hydrogen to the inside of the flask from a balloon filled with hydrogen. The reaction solution was filtered and concentrated, and recrystallized with a hexane / ethyl acetate mixed solvent. The precipitated crystals were filtered and dried under reduced pressure to obtain compound 1.

（化合物２の合成）
撹拌装置付きのセパラブルフラスコに２，４，６−トリアミノ−１，３，５−トリアジン１２．６ｇ（０．１ｍｏｌ）、ＤＬ−グリセリン酸１０．６ｇ（０．１ｍｏｌ）、４−（４，６−ジメトキシ−１，３，５−トリアジン−２−イル）−４−メチルモルホリニウムクロリド２７．６ｇ（０．１ｍｏｌ）、Ｎ−メチルモルホリン１０．１ｇ（０．１ｍｏｌ）、テトラヒドロフラン２００ｍｌを仕込み、１２時間撹拌した。白色沈殿を濾去し、反応溶液を濃縮した。ヘキサン／酢酸エチル混合溶媒で再結晶した。析出した結晶をろ過、減圧乾燥することで、化合物２を得た。 Compound 2: Diaminotriazine compound (N- (3,5-diamino-2,4,6-triazinyl) -2,3-dihydroxypropanamide) represented by the following formula (1b)

(Synthesis of Compound 2)
In a separable flask equipped with a stirrer, 12.6 g (0.1 mol) of 2,4,6-triamino-1,3,5-triazine, 10.6 g (0.1 mol) of DL-glyceric acid, 4- (4, 27.6 g (0.1 mol) of 6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, 10.1 g (0.1 mol) of N-methylmorpholine, and 200 ml of tetrahydrofuran Stir for 12 hours. The white precipitate was filtered off and the reaction solution was concentrated. Recrystallization was performed with a hexane / ethyl acetate mixed solvent. The precipitated crystals were filtered and dried under reduced pressure to obtain compound 2.

（化合物３の合成）
冷却管及び撹拌装置付きのセパラブルフラスコに４−ブロモカテコール１８．９ｇ（０．１ｍｏｌ）、２，４−ジアミノ−６−ビニル−ｓ−トリアジン１３．７ｇ（０．１ｍｏｌ）、酢酸パラジウム０．２２４ｇ（０．００１ｍｏｌ）、トリフェニルホスフィン０．５２ｇ（０．００２ｍｏｌ）を仕込み、フラスコ内部をアルゴン置換した。さらにフラスコ内にトリエチルアミン２０．２ｇ（０．２ｍｏｌ）、テトラヒドロフラン２００ｍｌを仕込み、６０℃で２４時間加熱した。反応用液を濃縮後、酢酸エチル２００ｍｌに溶解し、水洗した。反応物の酢酸エチル溶液をフラスコに移し、パラジウム炭素１ｇを添加した。反応系内を水素で置換し、水素を充てんした風船からフラスコ内部へ水素を供給しながら１２時間撹拌した。反応用液をろ過濃縮し、ヘキサン／酢酸エチル混合溶媒で再結晶し、析出した結晶をろ過、減圧乾燥することで、化合物３を得た。 Compound 3: Diaminotriazine compound represented by the following formula (1c) (2,4-diamino-6- [2- (3,4-dihydroxyphenyl) ethyl] -1,3,5-triazine)

(Synthesis of Compound 3)
In a separable flask equipped with a condenser and a stirrer, 18.9 g (0.1 mol) of 4-bromocatechol, 13.7 g (0.1 mol) of 2,4-diamino-6-vinyl-s-triazine, 0.1. 224 g (0.001 mol) and 0.52 g (0.002 mol) of triphenylphosphine were charged, and the inside of the flask was purged with argon. Further, 20.2 g (0.2 mol) of triethylamine and 200 ml of tetrahydrofuran were charged into the flask and heated at 60 ° C. for 24 hours. The reaction solution was concentrated, dissolved in 200 ml of ethyl acetate, and washed with water. The ethyl acetate solution of the reaction was transferred to a flask and 1 g of palladium on carbon was added. The inside of the reaction system was replaced with hydrogen and stirred for 12 hours while supplying hydrogen to the inside of the flask from a balloon filled with hydrogen. The reaction solution was concentrated by filtration, recrystallized with a mixed solvent of hexane / ethyl acetate, and the precipitated crystals were filtered and dried under reduced pressure to obtain compound 3.

Compound 4: Diaminotriazine compound represented by the following formula (1 d) (product name VD-3 (in the formula, R is a linking group linking a diol moiety and a triazine ring moiety) manufactured by Shikoku Kasei Co., Ltd.)

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

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

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

(Synthesis of curing accelerator 1)
In a separable flask equipped with a condenser and a stirrer, 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 ml of acetone were charged and reacted at room temperature with stirring. The precipitated crystals were washed with acetone, filtered, and dried to obtain a dark green crystalline hardening accelerator 1.

Curing accelerator 2: a tetra-substituted phosphonium compound represented by the following formula (13) synthesized by the following method

(Synthesis of curing accelerator 2)
In a separable flask equipped with a condenser and a stirrer, 15.00 g (0.060 mol) of bis (4-hydroxyphenyl) sulfone, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide and 100 ml of methanol are charged and stirred uniformly. It was dissolved. 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 to precipitate crystals. The precipitated crystals were filtered, washed with water and vacuum dried to obtain a hardening accelerator 2.

（硬化促進剤３の合成）
冷却管及び攪拌装置付きのセパラブルフラスコに２,３−ジヒドロキシナフタレン１２．８１ｇ（０．０８０ｍｏｌ）、テトラフェニルホスホニウムブロミド１６．７７ｇ（０．０４０ｍｏｌ）及びメタノール１００ｍｌを仕込み攪拌し、均一に溶解させた。予め水酸化ナトリウム１．６０ｇ（０．０４ｍｌ）を１０ｍｌのメタノールに溶解した水酸化ナトリウム溶液をフラスコ内に徐々に滴下すると結晶が析出した。析出した結晶をろ過、水洗、真空乾燥し、硬化促進剤３を得た。
・硬化促進剤４：以下の方法にて合成した、下記式（１５）で表されるテトラ置換ホスホニウム化合物

（硬化促進剤４の合成）
冷却管及び攪拌装置付きのセパラブルフラスコに２,３−ジヒドロキシナフタレン１２．８１ｇ（０．０８０ｍｏｌ）、トリメトキシフェニルシラン７．９２ｇ（０．０４ｍｏｌ）、テトラフェニルホスホニウムブロミド１６．７７ｇ（０．０４０ｍｏｌ）及びメタノール１００ｍｌを仕込み攪拌し、均一に溶解させた。予め水酸化ナトリウム１．６０ｇ（０．０４ｍｌ）を１０ｍｌのメタノールに溶解した水酸化ナトリウム溶液をフラスコ内に徐々に滴下すると結晶が析出した。析出した結晶をろ過、水洗、真空乾燥し、硬化促進剤４を得た。
・硬化促進剤５：トリフェニルホスフィン Curing accelerator 3: a tetra-substituted phosphonium compound represented by the following formula (14) synthesized by the following method

(Synthesis of curing accelerator 3)
In a separable flask equipped with a condenser and a stirrer, 12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide and 100 ml of methanol are charged and uniformly dissolved. The 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 to precipitate crystals. The precipitated crystals were filtered, washed with water and vacuum dried to obtain a hardening accelerator 3.
Curing accelerator 4: a tetra-substituted phosphonium compound represented by the following formula (15) synthesized by the following method

(Synthesis of curing accelerator 4)
In a separable flask equipped with a condenser and a stirrer, 12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 7.92 g (0.04 mol) of trimethoxyphenylsilane, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide. ) And 100 ml of methanol were charged and uniformly dissolved. 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 to precipitate crystals. The precipitated crystals were filtered, washed with water and vacuum dried to obtain a hardening accelerator 4.
-Hardening accelerator 5: triphenyl phosphine

Other ingredients and coloring agents: carbon black and ion capturing agent: hydrotalcite (DHT-4H manufactured by Kyowa Chemical Co., Ltd.)
Releasing agent: Carnauba wax (Nikko Carnauba manufactured by Nikko Fine Products Co., Ltd.)

Example 1
Epoxy resin 1 (5.80 parts by mass), phenolic resin-based curing agent 1 (5.50 parts by mass), inorganic filler 1 (77.50 parts by mass), inorganic filler 2 (10.00 parts by mass), compounds 1 (0.05 parts by mass), coupling agent 2 (0.20 parts by mass), curing accelerator 1 (0.25 parts by mass), colorant (0.40 parts by mass), ion scavenger (0.10) Parts by mass) and the releasing agent (0.20 parts by mass) were mixed at normal temperature using a mixer, and then roll-kneaded at 70 to 100 ° C. Then, after cooling, the resultant was pulverized to obtain a sealing resin composition of Example 1.

[Examples 2 to 19, Comparative Examples 1 to 3]
The sealing resin compositions of Examples 2 to 19 and Comparative Examples 1 to 3 were obtained in the same manner as Example 1 except that the amounts used (blended amounts) of the respective components were as shown in Table 1. .

Manufacturing of semiconductor devices (electronic component devices) 352-pin BGA with TEG (Test Element Group) chip (3.5 mm x 3.5 mm) (substrate is 0.56 mm thick, bismaleimide triazine resin / glass cloth substrate, package The size was mounted on 30 mm × 30 mm, thickness 1.17 mm). Next, wire bonding was performed to the electrode pad at a wire pitch of 80 μm using a copper wire (copper purity 99.99% by mass, diameter 25 μm).
Each of the obtained structures was obtained using a low pressure transfer molding machine ("Y series" manufactured by TOWA) under conditions of a mold temperature of 175 ° C, an injection pressure of 6.9 MPa, and a curing time of 2 minutes. It seal-molded using the resin composition for sealing of an Example and a comparative example, and produced the 352 pin BGA package. 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 respective Examples and Comparative Examples obtained were evaluated by the following methods. The evaluation results are shown in Table 1.

[Adhesiveness]
The adhesion to each metal (Ag, Cu, PPF (pre-plating frame), Ni) was evaluated by the following method. The obtained resin composition for sealing was integrally molded under the conditions of 175 ° C. and 6.9 MPa for 2 minutes and post-cured at 175 ° C. for 4 hours on the substrate made of each metal. Thereafter, the shear adhesion to each substrate was measured under the condition of 260 ° C.
In addition, evaluation of adhesiveness is performed by the relative value which made Comparative example 1 "1.0".

[High temperature storage characteristics]
The obtained semiconductor device was subjected to HTSL (high temperature storage test) according to the following method. Each semiconductor device was stored under conditions of a temperature of 200 ° C. for 1000 hours. The electrical resistance value between the wire and the electrode pad was measured for the semiconductor device after storage. The average value of each semiconductor device shows an electrical resistance value of less than 110% with respect to the average value of the initial resistance value ◎, and the one showing an electrical resistance value of 110% or more and 120% or less ○ greater than 120% The thing which shows an electrical resistance value was made into x.

As shown in Table 1, it can be seen that the sealing resin compositions of the examples have sufficient adhesion and the high-temperature storage characteristics of the obtained electronic component device (semiconductor device) are also excellent. On the other hand, in Comparative Example 1-3 in which the diaminotriazine compound was not contained, it was difficult to achieve both the adhesion and the high-temperature storage characteristics.
Specifically, in Comparative Example 1 in which 3-amino-5-mercapto-1,2,4-triazole was used instead of the diaminotriazine compound, the result of inferior high-temperature storage property was obtained. Moreover, in the comparative example 2-3, although the high temperature storage property was comparatively excellent, it resulted in it being inferior to the adhesiveness with respect to a metal.

100 Semiconductor Device 10 Die Attach Material 20 Semiconductor Element 22 Electrode Pad 30 Base Material 32 Die Pad 34 Outer Lead 40 Bonding Wire 50 Sealing Resin

Claims (5)

It is a resin composition for sealing which molds a semiconductor element, Comprising: The resin composition for sealing containing the following components.
(A) Epoxy resin (B) Curing agent (C) Inorganic filler (D) At least one diaminotriazine compound selected from the following formulas (1a) to (1d)

(In formula (1d), R is a linking group linking a diol moiety and a triazine ring moiety.)   The sealing resin composition according to claim 1, which is used to seal a semiconductor element and a copper bonding wire connected to the semiconductor element. Wherein the curing agent is a phenolic resin-based curing agent, according to claim 1 or encapsulating resin composition according to 2. The sealing resin composition according to any one of claims 1 to 3 , wherein a content of the inorganic filler with respect to the entire sealing resin composition is 35% by mass or more and 95% by mass or less. A semiconductor element,
A bonding wire connected to the semiconductor element;
A sealing resin comprising a cured product of the sealing resin composition according to any one of claims 1 to 4 , and sealing the semiconductor element and the bonding wire.
Semiconductor device provided with

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