JP6938869B2 - Epoxy resin compositions and semiconductor devices - Google Patents

Description

The present invention relates to epoxy resin compositions and semiconductor devices.

In recent years, in the market trend of miniaturization, weight reduction, and high functionality of electronic devices, semiconductor devices have been highly integrated and thinned year by year, and the surface mounting of semiconductor devices has been promoted. Instead of the lead frame, the semiconductor element is mounted on a substrate such as an organic substrate or a ceramic substrate, the substrate and the semiconductor element are electrically connected by a connecting member, and then the semiconductor element and the connecting member are molded and sealed with a molding material. The shift to area-mounted semiconductor devices that can be obtained by stopping is progressing. Typical examples of the area-mounted semiconductor device include BGA (ball grid array) and CSP (chip scale package) pursuing further miniaturization.

As the encapsulant used in such an area-mounted semiconductor device, it is required to appropriately select a material such as an epoxy resin, a curing agent, and a curing accelerator according to various purposes. Examples of this type of technique include the epoxy resin composition described in Patent Document 1.

According to the same document, it is described that a cured product of an epoxy resin having a small curing shrinkage and a high elastic modulus can be obtained by combining a 6-membered ring lactone. It is described that a 6-membered ring lactone having no hydroxy group is used for such an epoxy resin composition (paragraphs 0057 and 0117 described in Patent Document 1).

Japanese Unexamined Patent Publication No. 2013-32510

However, as a result of examination by the present inventor, it has been found that the epoxy resin composition described in the above document has room for improvement in terms of potential.

The present inventor has focused on improving the potential and conducted various studies on compounds capable of controlling the curing properties of the curing accelerator.
Based on the results of these various studies, the present inventor can increase the potential of an epoxy resin composition using a curing accelerator by using a lactone compound in which a hydroxy group is bonded to a lactone ring. The present invention was completed.

Although the detailed mechanism is not clear, it is considered that the potential can be increased by the hydroxy group bonded to the lactone ring being coordinated or ionic bonded to the curing accelerator.

（上記構造単位（１）中、ｍは１または２の整数、ｎは１〜６の整数を表す。Ｂは１価または２価の有機基を表す。Ｒａは、それぞれ独立して、水素原子、ヒドロキシ基、アルキル基を表す。ｎが２以上のとき、Ｒａは互いに結合して環を形成してもよい。）
According to the present invention
Epoxy resin (A) and
Phenol formaldehyde (B) and
Curing accelerator (C) and
A lactone compound containing the following structural unit (1) having at least one hydroxy group in the lactone ring A, and the like.
The lactone compound has a coumarin structure or a bisque marin structure.
The molar ratio of the content of the lactone compound to the content of the curing accelerator (C) in the epoxy resin composition is 0.1 or more and 4 or less.
The content of the curing accelerator (C) is 0.05% by weight or more and 5% by weight or less with respect to 100% by weight of the entire epoxy resin composition.
Epoxy resin compositions are provided.

(In the structural unit (1), m represents an integer of 1 or 2, n represents an integer of 1 to 6. B represents a monovalent or divalent organic group. Ra represents a hydrogen atom independently. , A hydroxy group and an alkyl group. When n is 2 or more, Ra may be bonded to each other to form a ring.)

Further, according to the present invention.
With semiconductor elements
A semiconductor device including a sealing member for sealing the semiconductor element.
A semiconductor device is provided in which the sealing member is made of a cured product of the epoxy resin composition.

According to the present invention, it is possible to provide an epoxy resin composition having excellent potential and a semiconductor device using the same.

It is sectional drawing which shows an example of the semiconductor device in this embodiment. It is sectional drawing which shows an example of the structure in this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate.

The epoxy resin composition according to the present embodiment contains an epoxy resin (A), a phenol resin (B), a curing accelerator (C), and a lactone compound having at least one hydroxy group on the lactone ring A. It includes.

In the epoxy resin composition of the present embodiment, a lactone compound having a hydroxy group bonded to a lactone ring can be used. Therefore, an epoxy resin composition having excellent potential can be realized. Further, by appropriately controlling the structure of the lactone compound and its content, the balance between potential, fluidity and storability can be improved.

The present inventor has focused on the fact that the epoxy resin compositions so far have room for improvement in terms of potential, and conducted various studies based on this focus. As a result, the present inventor noticed the existence of a compound capable of controlling the curing characteristics of the curing accelerator, and as a result of further study, the curing accelerator was used by using a lactone compound in which a hydroxy group was bonded to the lactone ring. We have found that the potential of the epoxy resin composition can be increased.

The detailed mechanism is not clear, but it is inferred as follows. In the present embodiment, the lactone compound has a hydroxy group bonded to the lactone ring, and therefore has a low pKa (acid dissociation constant). Since the lactone compound becomes an anion and the curing accelerator becomes a cation, the hydroxy group bonded to the lactone ring is coordinated or ionic bonded to the curing accelerator. It is considered that such an interaction can increase the potential of the curing accelerator.

In the present embodiment, the upper limit of pKa of the lactone compound may be, for example, 6 or less, 5.5 or less, 5 or less, or 4.6 or less. This makes it possible to increase the potential of the epoxy resin composition. The lower limit of pKa of the lactone compound is not particularly limited, but may be, for example, 2 or more.

Here, it is known that the pKa of the aromatic hydroxy group is about 9 to 10. For example, the pKa of a 6-membered ring lactone having a hydroxy group bonded to an aromatic ring as shown in the following formula is 9.5. From the results examined by the present inventor of such a lactone compound, it was found that it is difficult to obtain the latent effect as in the present embodiment.

On the other hand, the lactone compound of the present embodiment does not have a hydroxy group bonded to the aromatic ring, but has a hydroxy group bonded to the lactone ring. On the other hand, in the case of a compound having a highly reactive hydroxy group bonded to an aromatic, the reaction of the hydroxy group with the epoxy resin reduces the interaction with the curing accelerator, and a latent effect can be obtained. Can not.

The components of the epoxy resin composition of this embodiment will be described in detail.

[Epoxy resin (A)]
As the epoxy resin (A) of the present embodiment, a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not particularly limited. In the present embodiment, it is particularly preferable to use a non-halogenated epoxy resin as the epoxy resin (A).

Examples of the epoxy resin (A) include biphenyl type epoxy resin; bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin and other bisphenol type epoxy resin; stillben type epoxy resin; phenol novolac. Novolak type epoxy resin such as type epoxy resin and cresol novolac type epoxy resin; polyfunctional epoxy resin such as triphenylmethane type epoxy resin and alkyl-modified triphenylmethane type epoxy resin; phenol aralkyl type epoxy resin having phenylene skeleton, biphenylene skeleton Biphenyl aralkyl type epoxy resin such as phenol aralkyl type epoxy resin having Examples thereof include triazine nuclei-containing epoxy resins such as diglycidyl isocyanurate; and 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.

Of these, at least of these, from the viewpoint of improving the balance between moisture resistance reliability and moldability, bisphenol type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, phenol aralkyl type epoxy resin, and triphenylmethane type epoxy resin. One may be used. Further, from the viewpoint of suppressing the warp of the semiconductor device, at least one of the phenol aralkyl type epoxy resin and the novolak type epoxy resin may be used. A biphenyl type epoxy resin may be used to improve the fluidity. A biphenyl aralkyl type epoxy resin may be used to control the elastic modulus at high temperature. Among these, a triphenylmethane type epoxy resin or a biphenyl aralkyl type epoxy resin can be used.

（上記一般式（４）および（５）中、Ｒ_１０、Ｒ_１１、およびＲ_１２は炭素数１〜６の炭化水素基又は炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。ａおよびｃは０〜３の整数、ｂは０〜４の整数であり、互いに同じであっても異なっていてもよい。Ｘ_１は、単結合または下記一般式（５Ａ）、（５Ｂ）、または（５Ｃ）のいずれかで表される基を示す。下記一般式（５Ａ）、（５Ｂ）および（５Ｃ）中、Ｒ_１３、Ｒ_１４、Ｒ_１５およびＲ_１６は炭素数１〜６の炭化水素基または炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。ｄは０〜２の整数であり、ｅ、ｆおよびｇは０〜４の整数であり、互いに同じであっても異なっていてもよい。）

The triphenylmethane type epoxy resin contains a structural unit represented by the following general formula (4) and / or the following general formula (5).

(In the above general formulas (4) and (5), R ₁₀ , R ₁₁ , and R ₁₂ are hydrocarbon groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 14 carbon atoms, and are the same as each other. They may be present or different. A and c are integers 0 to 3, b is an integer 0 to 4, and they may be the same or different from each other. X ₁ is a single bond or the following general. Indicates a group represented by any of the formulas (5A), (5B), or (5C). In the following general formulas (5A), (5B) and (5C), R ₁₃ , R ₁₄ , R ₁₅ and R. _{Reference numeral 16} denotes a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different from each other. D is an integer of 0 to 2, and e, f and g are integers from 0 to 4 and may be the same or different from each other.)

（Ｘ_２は、水素原子または下記一般式（６Ｂ）で表される基を示す。）

The biphenyl aralkyl type epoxy resin contains a structural unit represented by the following general formula (6).

(X ₂ represents a hydrogen atom or a group represented by the following general formula (6B).)

The lower limit of the content of the epoxy resin (A) of the present embodiment is, for example, preferably 1% by weight or more, more preferably 3% by weight or more, and 5% by weight, based on 100% by weight of the entire epoxy resin composition. The above is more preferable. The upper limit of the content of the epoxy resin (A) is, for example, preferably 90% by weight or less, more preferably 80% by weight or less, and 70% by weight or less, based on 100% by weight of the entire epoxy resin composition. More preferred. By setting the content of the epoxy resin (A) in the above preferable range, low hygroscopicity can be improved. Further, by setting the content of the epoxy resin (A) to the above-mentioned more preferable range, the solder crack resistance of the obtained semiconductor device can be enhanced. In the present embodiment, the improvement of the solder crack resistance means that cracks and peeling defects occur even when the obtained semiconductor device is exposed to a high temperature in, for example, a solder immersion or solder reflow process. Shows characteristics that make it difficult.

In the present embodiment, the content of the epoxy resin composition with respect to the whole refers to the content of the epoxy resin composition with respect to the whole solid component excluding the solvent when the epoxy resin composition contains a solvent.

The lower limit of the content of the epoxy resin (A), which is a biphenyl aralkyl type epoxy resin or a triphenylmethane type epoxy resin, is preferably 85% by weight or more, preferably 90% by weight, based on the entire epoxy resin (A). % Or more is more preferable, and 95% by weight or more is further preferable. Thereby, the liquidity can be improved. On the other hand, the upper limit of the content of the epoxy resin (A), which is a biphenyl aralkyl type epoxy resin or a triphenylmethane type epoxy resin, is not particularly limited with respect to the entire epoxy resin (A), but is, for example, 100% by weight or less. It may be 99% by weight or less, or 98% by weight or less.

[Phenol resin (B)]
The phenol resin (B) of the present embodiment is a general monomer, oligomer, or polymer having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited.

Examples of the phenol resin (B) include phenol novolac resin, cresol novolac resin and other phenols, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β-naphthol, and the like. A novolak resin obtained by condensing or co-condensing phenols such as dihydroxynaphthalene with formaldehyde or ketones under an acidic catalyst, and a biphenylene skeleton synthesized from the above-mentioned phenols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl. Examples thereof include a phenol aralkyl resin having a phenol aralkyl resin, a phenylaralkyl type phenol resin such as a phenol aralkyl resin having a phenylene skeleton, and a triphenylmethane type phenol resin having a trisphenol methane skeleton. These may be used alone or in combination of two or more. Among these, a triphenylmethane type phenol resin or a biphenyl aralkyl type phenol resin may be used.

（上記一般式（７）および（８）中、Ｒ_１７、Ｒ_１８、およびＲ_１９は炭素数１〜６の炭化水素基又は炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。Ｙ_３は、水酸基を示す。ｈおよびｊは０〜３の整数、ｉは０〜４の整数であり、互いに同じであっても異なっていてもよい。Ｙ_１は、単結合または下記一般式（８Ａ）、（８Ｂ）、または（８Ｃ）のいずれかで表される基を示す。一般式（８Ａ）〜（８Ｃ）中のＲ_２０、Ｒ_２１、Ｒ_２２およびＲ_２３は炭素数１〜６の炭化水素基または炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。ｋは０〜２の整数であり、ｌ、ｍおよびｎは０〜４の整数であり、互いに同じであっても異なっていてもよい。）

The triphenylmethane-type phenol resin contains a structural unit represented by the following general formula (7) and / or the following general formula (8).

(In the above general formulas (7) and (8), R ₁₇ , R ₁₈ , and R ₁₉ are hydrocarbon groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 14 carbon atoms, and are the same as each other. They may be present or different. Y ₃ represents a hydroxyl group. H and j are integers from 0 to 3, i is an integer from 0 to 4, and they may be the same or different from each other. Y ₁ represents a single bond or a group represented by any of the following general formulas (8A), (8B), or (8C). R ₂₀ , R ₂₁ , R in the general formulas (8A) to (8C). ₂₂ and R ₂₃ are hydrocarbon groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 14 carbon atoms, which may be the same or different from each other. K is an integer of 0 to 2. , L, m and n are integers 0-4 and may be the same or different from each other.)

（Ｙ_２は、水素原子または下記一般式（９Ｂ）で表される基を示す。）

The biphenyl aralkyl type phenol resin contains a structural unit represented by the following general formula (9).

(Y ₂ represents a hydrogen atom or a group represented by the following general formula (9B).)

The lower limit of the content of the phenol resin (B) of the present embodiment is, for example, preferably 1% by weight or more, more preferably 2% by weight or more, and 3% by weight, based on 100% by weight of the entire epoxy resin composition. The above is more preferable. The upper limit of the content of the phenol resin (B) is, for example, preferably 60% by weight or less, more preferably 50% by weight or less, and 40% by weight or less, based on 100% by weight of the entire epoxy resin composition. More preferred. By setting the content of the phenol resin (B) in the above preferable range, low hygroscopicity and fluidity can be improved. Further, by setting the content of the phenol resin (B) to the above-mentioned more preferable range, the solder crack resistance of the obtained semiconductor device can be enhanced.

The lower limit of the content of the phenol resin (B), which is a biphenyl aralkyl type phenol resin or a triphenylmethane type phenol resin, is preferably 95% by weight or more, preferably 96% by weight, based on the entire phenol resin (B). % Or more is more preferable, and 97% by weight or more is further preferable. Thereby, the liquidity can be improved. On the other hand, the upper limit of the content of the phenol resin (B), which is a biphenyl aralkyl type phenol resin or a triphenylmethane type phenol resin, is not particularly limited with respect to the entire phenol resin (B), but is, for example, 100% by weight or less. It may be 99% by weight or less, or 98% by weight or less.

[Curing accelerator (C)]
The curing accelerator (C) of the present embodiment may be any as long as it promotes the cross-linking reaction between the epoxy resin (A) and the phenol resin (B), and is used in a general semiconductor encapsulation resin composition. Can be used. The curing accelerator (C) can include, for example, a cationic curing accelerator.

Examples of the curing accelerator (C) of the present embodiment include phosphorus atoms such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. Containing compounds; 1,8-diazabicyclo (5,4,5) undecene-7, benzyldimethylamine, 2-methylimidazole and the like, such as amidine and tertiary amines, and nitrogen atoms such as the quaternary salt of amidine and amine. It can contain one or more selected from the contained compounds. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving curability. Further, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. It is more preferable to include one.

Examples of the organic phosphine that can be used in the epoxy resin composition of the present embodiment include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; Examples thereof include a third phosphine such as triphenylphosphine.

Examples of the tetra-substituted phosphonium compound that can be used in the epoxy resin composition of the present embodiment include compounds represented by the following general formula (10).

（上記一般式（１０）において、Ｐはリン原子を表す。Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は芳香族基またはアルキル基を表す。Ａはヒドロキシ基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシ基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の数、ｚは０〜３の数であり、かつｘ＝ｙである。）

(In the above general formula (10), P represents a phosphorus atom. R ⁴ , R ⁵ , R ⁶ and R ⁷ represent an aromatic group or an alkyl group. A is selected from a hydroxy group, a carboxyl group and a thiol group. Represents an anion of an aromatic organic acid having at least one functional group on the aromatic ring. AH is an aromatic having at least one functional group selected from a hydroxy group, a carboxyl group, and a thiol group on the aromatic ring. Represents an organic acid. X and y are numbers 1 to 3, z is a number 0 to 3, and x = y.)

The compound represented by the general formula (10) can be obtained, for example, as follows, but is not limited thereto. First, tetra-substituted phosphonium halide, aromatic organic acid and base are mixed uniformly with an organic solvent to generate an aromatic organic acid anion in the solution system. Then, water can be added to precipitate the compound represented by the general formula (10). In the compound represented by the general formula (10), R ⁴ , R ⁵ , R ⁶ and R ⁷ bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxy group in the aromatic ring, that is, phenols. Yes, and A is preferably an anion of the phenols. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, and bisphenols such as bisphenol A, bisphenol F, and bisphenol S. Examples thereof include polycyclic phenols such as phenylphenol and biphenol.

Examples of the phosphobetaine compound that can be used in the epoxy resin composition of the present embodiment include compounds represented by the following general formula (11).

（上記一般式（１１）において、Ｐはリン原子を表す。Ｒ^８は炭素数１〜３のアルキル基、Ｒ^９はヒドロキシ基を表す。ｆは０〜５の数であり、ｇは０〜３の数である。）

(In the above general formula (11), P represents a phosphorus atom. R ⁸ represents an alkyl group having 1 to 3 carbon atoms, R ⁹ represents a hydroxy group. F is a number from 0 to 5, and g is 0 to 0. It is a number of 3.

The compound represented by the general formula (11) can be obtained, for example, as follows. First, it is obtained through a step of contacting a tri-aromatic substituted phosphine, which is a tertiary phosphine, with a diazonium salt to replace the tri-aromatic substituted phosphine with the diazonium group of the diazonium salt. However, it is not limited to this.

Examples of the adduct of the phosphine compound and the quinone compound that can be used in the epoxy resin composition of the present embodiment include compounds represented by the following general formula (12).

（上記一般式（１２）において、Ｐはリン原子を表す。Ｒ^１０、Ｒ^１１およびＲ^１２は炭素数１〜１２のアルキル基または炭素数６〜１２のアリール基を表し、互いに同一であっても異なっていてもよい。Ｒ^１３、Ｒ^１４およびＲ^１５は水素原子または炭素数１〜１２の炭化水素基を表し、互いに同一であっても異なっていてもよく、Ｒ^１４とＲ^１５が結合して環状構造となっていてもよい。）

(In the above general formula (12), P represents a phosphorus atom. R ¹⁰ , R ¹¹ and R ¹² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and are identical to each other. ^{R 13} , R ¹⁴ and R ¹⁵ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, which may be the ^{same or different from each other, and R 14} and R ¹⁵ are bonded to each other. It may have a ring structure.)

Examples of the phosphine compound used as an adjunct to the phosphine compound and the quinone compound include triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, tris (benzyl) phosphine and the like. Substituents or those having a substituent such as an alkyl group or an alkoxyl group are preferable, and 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 as an adduct of the phosphine compound and the quinone compound include benzoquinone and anthraquinone, and among them, 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, the adduct can be obtained by contacting and mixing in a solvent in which both organic tertiary phosphine and benzoquinones can be dissolved. As the solvent, ketones such as acetone and methyl ethyl ketone, which have low solubility in adducts, are preferable. However, it is not limited to this.

As the compound represented by the general formula (12), a compound in which R ¹⁰ , R ¹¹ and R ¹² bonded to a phosphorus atom are phenyl groups and R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms, that is, 1 , 4-A compound to which benzoquinone and triphenylphosphine are added is preferable because it reduces the thermal elasticity of the cured product of the sealing resin composition.

Examples of the adduct of the phosphonium compound and the silane compound that can be used in the semi-epoxy resin composition of the present embodiment include compounds represented by the following general formula (13).

（上記一般式（１３）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ^１６、Ｒ^１７、Ｒ^１８およびＲ^１９は、それぞれ、芳香環または複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｒ^２０は、Ｙ^２およびＹ^３と結合する有機基である。式中Ｒ^２１は、Ｙ^４およびＹ^５と結合する有機基である。Ｙ^２およびＹ^３は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内のＹ^２およびＹ^３が珪素原子と結合してキレート構造を形成するものである。Ｙ^４およびＹ^５はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内のＹ^４およびＹ^５が珪素原子と結合してキレート構造を形成するものである。Ｒ^２０、およびＲ^２１は互いに同一であっても異なっていてもよく、Ｙ^２、Ｙ^３、Ｙ^４およびＹ^５は互いに同一であっても異なっていてもよい。Ｚ^１は芳香環または複素環を有する有機基、あるいは脂肪族基である。）

(In the above general formula (13), P represents a phosphorus atom and Si represents a silicon atom. R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are organic groups or fats having an aromatic ring or a heterocycle, respectively. Represents a group group and may be the same or different from each other. In the formula, R ²⁰ is an organic group that binds to ^{Y 2} and Y ^{3. In the formula, R 21} binds to Y ⁴ and Y ^5. Organic groups Y ² and Y ³ represent groups formed by a proton donating group releasing a proton, and Y ^{2 and Y 3} in the same molecule combine with a silicon atom to form a chelate structure. Y ⁴ and Y ⁵ represent a group formed by a proton donating group releasing a proton, and Y ^{4 and Y 5} in the same molecule combine with a silicon atom to form a chelate structure. R ²⁰ , And R ²¹ may be the same or different from each other ^{, and Y 2} , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. Z ¹ has an aromatic or heterocyclic ring. It is an organic group or an aliphatic group.)

In the general formula (13), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include, for example, a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group and a methyl group. , Ethyl group, n-butyl group, n-octyl group, cyclohexyl group and the like. Among these, alkyl group such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group and hydroxynaphthyl group, alkoxy group and the like. , An aromatic group having a substituent such as a hydroxyl group or an unsubstituted aromatic group is more preferable.

Further, in the general formula (13), R ²⁰ is an organic group bonded to ^{Y 2} and Y ^3. Similarly, R ²¹ is an organic group that binds to ^{Y 4} and Y ^5. Y ² and Y ³ are groups formed by a proton-donating group releasing a proton, and Y ² and Y ³ in the same molecule combine with a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by a proton donating group releasing a proton, and Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure. The groups R ²⁰ and R ²¹ may be the same or different from each other, and Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. ^{In such a group represented by −Y 2-} R ²⁰ −Y ³ − and Y ⁴ −R ²¹ −Y ⁵ − in the general formula (13), the proton donor releases two protons. As the proton donor, an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule is preferable, and further, a carboxyl group or a hydroxyl group is added to an adjacent carbon constituting an aromatic ring. An aromatic compound having at least two is preferable, and an aromatic compound having at least two hydroxyl groups on adjacent carbons constituting the aromatic ring is more preferable, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxy. Naphthalene, 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 Examples thereof include alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin, and among these, catechol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable.

^{Further, Z 1} in the general formula (13) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. An aliphatic hydrocarbon group such as a hexyl group and an octyl group, an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a naphthyl group and a biphenyl group, a glycidyloxy group such as a glycidyloxypropyl group, a mercaptopropyl group and an aminopropyl group. , Reactive substituents such as mercapto group, alkyl group having amino group and vinyl group, etc. Among these, methyl group, ethyl group, phenyl group, naphthyl group and biphenyl group are used from the viewpoint of thermal stability. , More preferred.

As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then at room temperature. The sodium methoxide-methanol solution is added dropwise with stirring. Further, when a solution prepared in advance in which a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide is dissolved in methanol is added dropwise to the solution under 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, the method for producing an adduct of a phosphonium compound and a silane compound is not limited to this.

The lower limit of the content of the curing accelerator (C) of the present embodiment is preferably, for example, 0.05% by weight or more, more preferably 0.08% by weight or more, based on 100% by weight of the entire epoxy resin composition. It is preferable, and 0.1% by weight or more is more preferable. The upper limit of the content of the curing accelerator (C) is, for example, preferably 10% by weight or less, more preferably 7.5% by weight or less, and 5% by weight, based on 100% by weight of the entire epoxy resin composition. % Or less is more preferable. Appropriate curing can be performed by setting the content of the curing accelerator (C) to the above lower limit value or more. Further, by setting the content of the curing accelerator (C) to the above upper limit value or less, the storability and fluidity can be improved.

[Lactone compound]
The lactone compound of the present embodiment contains a lactone compound containing the following structural unit (1), which has at least one hydroxy group on the lactone ring A.

（上記構造単位（１）中、ｍは１または２の整数、ｎは１〜６の整数を表す。Ｂは１価または２価の有機基を表す。Ｒａは、それぞれ独立して、水素原子、ヒドロキシ基、アルキル基を表す。ｎが２以上のとき、Ｒａは互いに結合して環を形成してもよい。Ｒａは、無置換でも置換基を有していてもよい。）

(In the structural unit (1), m represents an integer of 1 or 2, n represents an integer of 1 to 6. B represents a monovalent or divalent organic group. Ra represents a hydrogen atom independently. , A hydroxy group and an alkyl group. When n is 2 or more, Ra may be bonded to each other to form a ring. Ra may be unsubstituted or have a substituent.)

The lactone ring A may have, for example, a 5- to 7-membered heterocyclic compound, and more preferably a 6-membered heterocyclic compound. In this case, the heteroatom of the heterocyclic compound is an oxygen atom.

In the 6-membered ring lactone ring A, the benzene skeleton, the naphthalene skeleton, or the pyridine skeleton may be condensed with the 6-membered ring lactone ring A (lactone skeleton) by condensing adjacent carbon atoms.

The lactone compound of this embodiment may have a coumarin structure or a bisque marin structure.

The lactone compound having a coumarin structure can include a structure represented by the following general formula (I).

_{R 1 to} R ₈ in the general formula (I) may be the same or different. R _{1 to} R ₈ have a hydrogen atom, a hydroxyl group, and a carbon atom number of 1 to 20, preferably 1 to 12, more preferably 1 to 6, and have a linear or branched alkyl group or a carbon atom number of 6. Represents an aryl group, an alkalil group or an aralkyl group, which is ~ 20. However, at least 1 or more of _{R 1 to} R _{4 are hydroxyl groups. In the present embodiment, R 4} may have a hydroxyl group in the general formula (I).

The lactone compound having a bisque marine structure is not particularly limited, but may be, for example, a structure in which the two coumarin structures are linked by a predetermined cross-linking group (via B in the structural formula (1)).

The lactone compound having such a bisque marine structure can include a structure represented by the following general formula (II).

（ＩＩ）

(II)

R in the general formula (II) is selected from the following chemical formulas.

In the present embodiment, the lactone compound having a bisque marine structure can enhance the potential effect of the epoxy resin composition more than the lactone compound having a coumarin structure. The detailed mechanism is not clear, but it can be considered as follows. That is, the dicoumarol skeleton in which two coumarin skeletons are connected has a structure in which physical movement is restricted. Therefore, the coordination bond between the anion and the cation can be further stabilized. At this time, it is considered that the coordination bond or ionic bond (interaction) by the dicumol skeleton to the cation of the curing accelerator becomes stronger and the cation can be further stabilized. Therefore, by using the lactone compound having a bisque marine structure, it is possible to obtain the same or higher effect even with a small amount of addition than in the case of the lactone compound having a coumarin structure.

In the present embodiment, the lower limit of the molar ratio of the content of the lactone compound to the content of the curing accelerator (C) in the epoxy resin composition may be, for example, 0.1 or more, preferably 0.2 or more. It is more preferably 0.3 or more. This makes it possible to increase the potential and fluidity of the epoxy resin composition. Further, the storability of the epoxy resin composition can be improved. The upper limit of the molar ratio of the content of the lactone compound to the content of the curing accelerator (C) in the epoxy resin composition is not particularly limited, but may be, for example, 4 or less, preferably 3 or less. Yes, more preferably 2 or less. This makes it possible to improve the balance between the potential of the epoxy resin composition and the curing properties.

In the present embodiment, the lower limit of the content of the lactone compound may be, for example, 0.01% by weight or more, preferably 0.02% by weight or more, more preferably 0.02% by weight or more, based on the entire epoxy resin composition. It is 0.025% by weight or more. This makes it possible to increase the potential and fluidity of the epoxy resin composition. Further, the storability of the epoxy resin composition can be improved. The upper limit of the content of the lactone compound is not particularly limited with respect to the entire epoxy resin composition, but may be, for example, 1% by weight or less, preferably 0.75% by weight or less, and more preferably 0.75% by weight or less. It is 0.5% by weight or less. This makes it possible to improve the balance between the potential of the epoxy resin composition and the curing properties.

[Inorganic filler (D)]
The epoxy resin composition of the present embodiment can further contain an inorganic filler (D).

In the present embodiment, the inorganic filler (D) is not particularly limited, but for example, molten crushed silica, molten silica, crystalline silica, secondary aggregated silica, alumina, titanium white, aluminum hydroxide, talc, clay, and glass. Examples include fibers. One or a combination of two or more of these can be used. Among these, the inorganic filler (D) is particularly preferably molten silica. Since the molten silica has poor reactivity with the curing accelerator (C), it prevents the curing reaction of the epoxy resin composition from being hindered even when it is blended in a large amount in the epoxy resin composition of the present embodiment. be able to. Further, by using molten silica as the inorganic filler (D), the reinforcing effect of the obtained semiconductor device is further improved.

The shape of the inorganic filler (D) may be, for example, granular, lumpy, scaly, or the like, and among them, granular (particularly spherical) is preferable.

The lower limit of the average particle size of the inorganic filler (D) of the present embodiment is, for example, preferably 1 μm or more, and more preferably 3 μm or more. The upper limit of the average particle size of the inorganic filler (D) is, for example, preferably 100 μm or less, and more preferably 50 μm or less. By setting the average particle size of the inorganic filler (D) within the above range, the filling property can be improved and the increase in the melt viscosity of the epoxy resin composition can be suppressed.

The lower limit of the content of the inorganic filler (D) of the present embodiment is preferably, for example, 40% by weight or more, more preferably 50% by weight or more, and 60% by weight, based on 100% by weight of the entire epoxy resin composition. % Or more is more preferable. The upper limit of the content of the inorganic filler (D) is, for example, preferably 97.5% by weight or less, more preferably 97% by weight or less, and 95% by weight, based on 100% by weight of the entire epoxy resin composition. % Or less is more preferable. By setting the content of the inorganic filler (D) to the above lower limit value or more, it is possible to suppress the warp of the package molded by using the epoxy resin composition of the present embodiment, and also to suppress the amount of moisture absorption and the strength. Can be reduced. Further, by setting the content of the inorganic filler (D) to the above upper limit value or less, the fluidity of the epoxy resin composition of the present embodiment can be enhanced and the moldability can be improved.

The epoxy resin composition of the present embodiment may contain other additives, if necessary, in addition to the compounds (A) to (D) and the lactone compound. Examples of other additives include coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, flame retardants such as brominated epoxy resin, antimony oxide, and phosphorus compounds, silicone oil, and silicone. Low stress components such as rubber, natural waxes, synthetic waxes, higher fatty acids or metal salts thereof, mold release agents such as paraffin, and various additives such as antioxidants can be used. You may use one kind or two or more kinds of these.

In the method for producing the epoxy resin composition of the present embodiment, for example, in addition to the compounds (A) to (D) and the lactone compound described above, if necessary, other additives and the like are added at room temperature using a mixer. It is obtained by mixing, heating and kneading using a hot roll, a heating kneader, etc., cooling, and pulverizing.

The epoxy resin composition of the present embodiment can be used, for example, as a sealing resin composition used for sealing electronic components such as semiconductor elements.

The semiconductor device of the present embodiment can include a semiconductor element and a sealing member for sealing the semiconductor element. Such a sealing member is composed of a cured product of the epoxy resin composition of the present embodiment. The semiconductor device of the present embodiment can be obtained by, for example, using a molding method such as a transfer mold, a compression mold, or an injection mold to cure and mold the epoxy resin composition and seal an electronic component such as a semiconductor element. ..

The semiconductor device of the present embodiment is not particularly limited, and is, for example, SIP (Single Inline Package), HSIP (SIP with Heatsink), ZIP (Zig-zag Inline Package), DIP (Dual Inline Package), SDIP (SDIP). Inline Package, SOP (Small Outline Package), SSOP (Shrink Small Outline Package), TSOP (Thin Small Outline Package), SOJ (Small Outline Quad) Pitch), TQFP (Thin Quad Flat Package), QFJ (PLCC) (Quad Flat J-led Package), BGA (Ball Grid Array) and the like.

Next, the semiconductor device 100 will be described with reference to FIG.
FIG. 1 is a cross-sectional view showing an example of the semiconductor device 100.

The semiconductor device 100 is a semiconductor including a substrate 10, a semiconductor element 20 mounted on one surface of the substrate 10, and a sealing resin layer 30 for sealing the one surface of the substrate 10 and the semiconductor element 20. It is a package. That is, the semiconductor device 100 is a single-sided sealing type semiconductor package in which the other side of the substrate 10 opposite to the above one side is not sealed by the sealing resin layer 30. The sealing resin layer 30 is composed of a cured product of the epoxy resin composition of the present embodiment. As a result, the coefficient of linear expansion of the sealing resin layer 30 at the time of heat can be increased, so that the difference in the coefficient of linear expansion of the sealing resin layer 30 and the substrate 10 at the time of heat can be reduced. Therefore, it is possible to suppress the warpage of the entire semiconductor device 100 when it is used in a high temperature environment.

In the present embodiment, the upper surface of the semiconductor element 20 may be covered with the sealing resin layer 30 (FIG. 1) or may be exposed from the sealing resin layer 30 (not shown).

In the example shown in FIG. 1, an organic substrate is used as the substrate 10. For example, a plurality of solder balls 12 are provided on the back surface of the substrate 10 opposite to the front surface (mounting surface) on which the semiconductor element 20 is mounted. Further, the semiconductor element 20 is flip-chip mounted on the substrate 10, for example. The semiconductor element 20 is electrically connected to the substrate 10 via, for example, a plurality of bumps 22. As a modification, the semiconductor element 20 may be electrically connected to the substrate 10 via a bonding wire.

In this example shown in FIG. 1, the gap between the semiconductor element 20 and the substrate 10 is filled with, for example, an underfill 32. As the underfill 32, for example, a film-like or liquid underfill material can be used. The underfill 32 and the sealing resin layer 30 may be made of different materials, but may be made of the same material. The epoxy resin composition of the present embodiment can be used as a mold underfill material. Therefore, the underfill 32 and the sealing resin layer 30 can be made of the same material and can be formed in the same process. Specifically, the sealing step of sealing the semiconductor element 20 with the epoxy resin composition and the filling step of filling the gap between the substrate 10 and the semiconductor element 20 with the epoxy resin composition are the same steps (collective). Can be carried out at.

In the present embodiment, the thickness of the sealing resin layer 30 is, for example, the thickness of the sealing resin layer 30 from the mounting surface of the substrate 10 (one surface opposite to the surface on which the solder balls 12 for external connection are formed). It may be the shortest distance to the top surface. The thickness of the sealing resin layer 30 refers to the thickness of the sealing resin layer 30 based on the above one surface in the normal direction of one surface on which the semiconductor element 20 of the substrate 10 is mounted. In this case, the upper limit of the thickness of the sealing resin layer 30 may be, for example, 0.4 mm or less, 0.3 mm or less, or 0.2 mm or less. On the other hand, the lower limit of the thickness of the sealing resin layer 30 is not particularly limited, but may be, for example, 0 mm or more (exposed type) or 0.01 mm or more.
Further, the upper limit of the thickness of the substrate 10 may be, for example, 0.8 mm or less, or 0.4 mm or less. On the other hand, the lower limit of the thickness of the substrate 10 is not particularly limited, but may be, for example, 0.1 mm or more.
According to this embodiment, it is possible to reduce the thickness of the semiconductor package in this way. Further, even in a thin semiconductor package, warpage of the semiconductor device 100 can be suppressed by forming the sealing resin layer 30 using the epoxy resin composition according to the present embodiment. Further, in the present embodiment, for example, the thickness of the sealing resin layer 30 can be set to be equal to or less than the thickness of the substrate 10. As a result, the semiconductor device 100 can be made thinner more efficiently.

Next, the structure 102 will be described.
FIG. 2 is a cross-sectional view showing an example of the structure 102. The structure 102 is a molded product formed by MAP molding. Therefore, by individualizing the structure 102 for each semiconductor element 20, a plurality of semiconductor packages can be obtained.

The structure 102 includes a substrate 10, a plurality of semiconductor elements 20, and a sealing resin layer 30. The plurality of semiconductor elements 20 are arranged on one surface of the substrate 10. FIG. 2 illustrates a case where each semiconductor element 20 is flip-chip mounted on a substrate 10. In this case, each semiconductor element 20 is electrically connected to the substrate 10 via a plurality of bumps 22. On the other hand, each semiconductor element 20 may be electrically connected to the substrate 10 via a bonding wire. As the substrate 10 and the semiconductor element 20, the same ones as those exemplified in the semiconductor device 100 can be used.

In the example shown in FIG. 2, the gap between each semiconductor element 20 and the substrate 10 is filled with, for example, an underfill 32. As the underfill 32, for example, a film-like or liquid underfill material can be used. On the other hand, the above-mentioned epoxy resin composition can also be used as a mold underfill material. In this case, sealing of the semiconductor element 20 and filling of the gap between the substrate 10 and the semiconductor element 20 are performed collectively.

The sealing resin layer 30 seals the plurality of semiconductor elements 20 and the above-mentioned one surface of the substrate 10. In this case, the other surface of the substrate 10 opposite to the above one surface is not sealed by the sealing resin layer 30. Further, the sealing resin layer 30 is composed of a cured product of the epoxy resin composition described above. As a result, it is possible to suppress the warp of the structure 102 and the semiconductor package obtained by separating the structure 102 into individual pieces. The sealing resin layer 30 is formed by, for example, sealing and molding an epoxy resin composition using a known method such as a transfer molding method or a compression molding method. Further, in the present embodiment, the upper surface of each semiconductor element 20 may be sealed by the sealing resin layer 30 as shown in FIG. 2, or may be exposed from the sealing resin layer 30.

In the present embodiment, the case where the epoxy resin composition of the present invention is used as a sealing material for a semiconductor device has been described, but the use of the epoxy resin composition of the present invention is not limited to this. Further, for example, the epoxy resin composition of the present invention can be used for packages that require wire bonding.

（上記構造単位（１）中、ｍは１または２の整数、ｎは１〜６の整数を表す。Ｂは１価または２価の有機基を表す。Ｒａは、それぞれ独立して、水素原子、ヒドロキシ基、アルキル基を表す。ｎが２以上のとき、Ｒａは互いに結合して環を形成してもよい。）
２． １．に記載のエポキシ樹脂組成物であって、
前記ラクトン化合物の酸解離定数（ｐＫａ）が、６以下である、エポキシ樹脂組成物。
３． １．または２．に記載のエポキシ樹脂組成物であって、
前記ラクトン環Ａが６員環である、エポキシ樹脂組成物。
４． １．から３．のいずれか１つに記載のエポキシ樹脂組成物であって、
前記ラクトン化合物が、クマリン構造またはビスクマリン構造を有する、エポキシ樹脂組成物。
５． １．から４．のいずれか１つに記載のエポキシ樹脂組成物であって、
前記硬化促進剤（Ｃ）が、カチオン硬化促進剤を含む、エポキシ樹脂組成物。
６． １．から５．のいずれか１つに記載のエポキシ樹脂組成物であって、
当該エポキシ樹脂組成物中の前記硬化促進剤（Ｃ）の含有量に対する前記ラクトン化合物の含有量のモル比は、０．１以上４以下である、エポキシ樹脂組成物。
７． １．から６．のいずれか１つに記載のエポキシ樹脂組成物であって、
前記ラクトン化合物の含有量は、当該エポキシ樹脂組成物全体に対して、０．０１重量％以上１重量％以下である、エポキシ樹脂組成物。
８． １．から７．のいずれか１つに記載のエポキシ樹脂組成物であって、
無機充填材をさらに含む、エポキシ樹脂組成物。
９． １．から８．のいずれか１つに記載のエポキシ樹脂組成物であって、
半導体素子の封止に用いる、エポキシ樹脂組成物。
１０． 半導体素子と、
前記半導体素子を封止する封止部材と、を備える半導体装置であって、
前記封止部材が、１．から９．のいずれか１つに記載のエポキシ樹脂組成物の硬化物で構成される、半導体装置。
Although the embodiments of the present invention have been described above with reference to the drawings, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the reference form will be added.
1. 1. Epoxy resin (A) and
Phenol formaldehyde (B) and
Curing accelerator (C) and
An epoxy resin composition comprising a lactone compound having the following structural unit (1) and having at least one hydroxy group in the lactone ring A.

(In the structural unit (1), m represents an integer of 1 or 2, n represents an integer of 1 to 6. B represents a monovalent or divalent organic group. Ra represents a hydrogen atom independently. , A hydroxy group and an alkyl group. When n is 2 or more, Ra may be bonded to each other to form a ring.)
2. 1. 1. The epoxy resin composition according to
An epoxy resin composition in which the acid dissociation constant (pKa) of the lactone compound is 6 or less.
3. 3. 1. 1. Or 2. The epoxy resin composition according to
An epoxy resin composition in which the lactone ring A is a 6-membered ring.
4. 1. 1. From 3. The epoxy resin composition according to any one of the above.
An epoxy resin composition in which the lactone compound has a coumarin structure or a bisque marine structure.
5. 1. 1. From 4. The epoxy resin composition according to any one of the above.
An epoxy resin composition in which the curing accelerator (C) contains a cationic curing accelerator.
6. 1. 1. From 5. The epoxy resin composition according to any one of the above.
An epoxy resin composition in which the molar ratio of the content of the lactone compound to the content of the curing accelerator (C) in the epoxy resin composition is 0.1 or more and 4 or less.
7. 1. 1. From 6. The epoxy resin composition according to any one of the above.
The epoxy resin composition has a content of the lactone compound of 0.01% by weight or more and 1% by weight or less with respect to the entire epoxy resin composition.
8. 1. 1. From 7. The epoxy resin composition according to any one of the above.
An epoxy resin composition further comprising an inorganic filler.
9. 1. 1. From 8. The epoxy resin composition according to any one of the above.
An epoxy resin composition used for encapsulating semiconductor devices.
10. With semiconductor elements
A semiconductor device including a sealing member for sealing the semiconductor element.
The sealing member is 1. From 9. A semiconductor device composed of a cured product of the epoxy resin composition according to any one of the above.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.

The components used in each Example and each Comparative Example are shown below.
(Preparation of epoxy resin composition)
First, in Examples 1 to 13 and Comparative Example 1, the raw materials blended according to Table 1 were mixed in a mortar at room temperature, and then melt-mixed on a hot plate at 120 ° C. for 3 minutes. After cooling, it was pulverized again at room temperature using a mortar to obtain an epoxy resin composition.
Further, in Example 14, Example 15, and Comparative Example 2, each raw material blended according to Table 2 was mixed at room temperature using a mixer, and then roll-kneaded at 70 to 100 ° C. After cooling, it was pulverized to obtain an epoxy resin composition.
Details of each component in Tables 1 and 2 are as follows. The unit in Tables 1 and 2 is% by weight.

Epoxy resin (A)
Epoxy resin 1: Phenolic aralkyl type epoxy resin having a biphenylene skeleton (NC-3000 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 276 g / eq, softening point 57 ° C.)

Phenol formaldehyde (B)
Phenol resin 1: Phenol aralkyl resin having a biphenylene skeleton (GPH-65 manufactured by Nippon Kayaku Co., Ltd., hydroxyl group equivalent 196 g / eq, softening point 65 ° C.)

Hardening accelerator (C)
Curing Accelerator 1: A compound obtained by the following synthetic method to which 1,4-benzoquinone and triphenylphosphine are added [Method for synthesizing Curing Accelerator 1]
6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 ml of acetone were charged into a separable flask equipped with a cooling tube and a stirrer, and the mixture was reacted at room temperature under stirring. The precipitated crystals were washed with acetone, filtered and dried to obtain a dark green crystal curing accelerator 1.

ラクトン化合物２：下記式で表される４−ヒドロキシクマリン（東京化成(株)製、Ｈ０２３５、）

Lactone compound Lactone compound 1: Dicoumarol represented by the following formula (manufactured by Tokyo Kasei Co., Ltd., M0216)

Lactone compound 2: 4-Hydroxycoumarin represented by the following formula (manufactured by Tokyo Kasei Co., Ltd., H0235,)

Inorganic filler (D)
Inorganic filler 1: Fused spherical silica (average particle size: 31 μm, specific surface area: 1.6 m ² / g, manufactured by Denka Co., Ltd., FB-508S)

(Additive)
Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
Colorant 1: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600)
Release agent 1: Glycerin montanic acid ester (melting point 80 ° C., manufactured by Clariant, Recolve WE4)
Ion scavenger 1: Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H)
Low stress agent 1: Epoxy / polyether-modified siloxane (manufactured by Toray Dow Corning Co., Ltd., FZ-3730))
Low stress agent 2: Carboxyl group-terminated butadiene / acrylonitrile copolymer (manufactured by PTI Japan Co., Ltd., CTBN1008-SP)

Each evaluation of the epoxy resin composition was carried out for each Example and each Comparative Example as follows.
(Curast @ 175 ° C)
Using a curast meter (manufactured by A & D Co., Ltd., curast meter WP type), the curast torque of the epoxy resin composition is measured over time at a mold temperature of 175 ° C., and 4 minutes after the start of measurement. The measured curast torque value was taken as the saturation torque value. As the tablet, 4.3 g of the epoxy resin composition was placed in a mold having a diameter of 25 mm, and the tablet was locked for 5 t for 1 minute. Further, the epoxy resin composition was tested for a sample immediately after tablet preparation and a sample after storage in a constant temperature bath at 40 ° C. for 24 hours and 72 hours. The rise time of curast was observed from the time when about 60% of the reaction functional groups reacted.

(DSC)
Using a differential scanning calorimeter (DSC-6100 manufactured by Seiko Instruments Inc.), the temperature rise rate was measured at 10 ° C./min at a temperature range of 30 ° C. to 300 ° C. for 10 mg of the epoxy resin composition. bottom.

(Minimum melt viscosity)
The minimum melt viscosity was measured using (1) a viscometer or (2) rectangular flow path pressure measurement.
(1) Viscometer: The minimum melt viscosity was measured for a tablet-shaped epoxy resin composition using a cone plate type viscometer (manufactured by Toa Kogyo Co., Ltd., serial number CV-1S). As the tablet-shaped epoxy resin composition, 100 mg of the epoxy resin composition was placed in a 25 mmφ mold and locked for 3 tons for 1 minute. Further, the epoxy resin composition was tested for a sample immediately after tablet preparation, a sample after storage at 40 ° C. for 24 hours, and a sample after storage at 40 ° C. for 72 hours.
The melt viscosity by the viscometer shows the measurement result 8 s after the start of the measurement. As a procedure, the measurement is started immediately after the sample (tablet-shaped epoxy resin composition) is placed on a hot plate at 175 ° C. Immediately after the placement is 0 s, the measured value is the value 8 s after that.
(2) Rectangular flow path pressure measurement: The minimum melt viscosity is measured using a low-pressure transfer molding machine (manufactured by NEC Co., Ltd., 40t manual press) under the conditions of a ^{mold temperature of 175 ° C. and an injection speed of 177 cm 3 / sec.} The epoxy resin composition is injected into a rectangular flow path having a width of 13 mm and a length of 175 cm, and the change with time of pressure is measured by a pressure sensor embedded 25 mm from the upstream tip of the flow path, and the epoxy resin composition is prepared. The minimum pressure during flow was measured. Further, the obtained epoxy resin composition was tested for a sample immediately after tablet preparation, a sample after storage at 40 ° C. for 24 hours, and a sample after storage at 40 ° C. for 72 hours.

(Spiral flow)
In the epoxy resin compositions of Examples 14 and 15 and Comparative Example 2, a low-pressure transfer molding machine (KTS-15 manufactured by Kotaki Seiki Co., Ltd.) was used to measure a spiral flow according to ANSI / ASTM D 3123-72. The epoxy resin composition obtained above was injected into a mold under the conditions of a mold temperature of 175 ° C., an injection amount of 6.9 MPa, and a holding time of 15 minutes, and the flow length was measured.

(Bending strength, flexural modulus)
In the epoxy resin compositions of Examples 14 and 15 and Comparative Example 2, according to JIS K 6911, using a transfer molding machine, the mold temperature was 175 ° C., the injection pressure was 6.9 MPa, the curing time was 15 minutes, and 80 mm × 10 mm. A test piece of an epoxy resin having a thickness of × 4 mm (thickness) was molded, and the bending strength and flexural modulus were measured at 25 ° C. and 260 ° C.

From Examples 1 to 13, it was found that the epoxy resin composition of the present invention has excellent potential. Further, from Examples 14 and 15, it was found that a semiconductor encapsulant having excellent potential can be obtained by using the epoxy resin composition of the present invention.
Although the present invention has been described in more detail based on the above examples, these are examples of the present invention, and various configurations other than the above can be adopted.

100 Semiconductor device 102 Structure 10 Substrate 12 Solder ball 20 Semiconductor element 22 Bump 30 Encapsulating resin layer 32 Underfill

Claims (8)

Epoxy resin (A) and
Phenol formaldehyde (B) and
Curing accelerator (C) and
A lactone compound containing the following structural unit (1) having at least one hydroxy group in the lactone ring A, and the like.
The lactone compound has a coumarin structure or a bisque marin structure.
The molar ratio of the content of the lactone compound to the content of the curing accelerator (C) in the epoxy resin composition is 0.1 or more and 4 or less.
The content of the curing accelerator (C) is 0.05% by weight or more and 5% by weight or less with respect to 100% by weight of the entire epoxy resin composition.
Epoxy resin composition.

(In the structural unit (1), m represents an integer of 1 or 2, n represents an integer of 1 to 6. B represents a monovalent or divalent organic group. Ra represents a hydrogen atom independently. , A hydroxy group and an alkyl group. When n is 2 or more, Ra may be bonded to each other to form a ring.) The epoxy resin composition according to claim 1.
An epoxy resin composition in which the acid dissociation constant (pKa) of the lactone compound is 6 or less. The epoxy resin composition according to claim 1 or 2.
An epoxy resin composition in which the lactone ring A is a 6-membered ring. The epoxy resin composition according to any one of claims 1 to 3.
An epoxy resin composition in which the curing accelerator (C) contains a cationic curing accelerator. The epoxy resin composition according to any one of claims 1 to 4.
The epoxy resin composition has a content of the lactone compound of 0.01% by weight or more and 1% by weight or less with respect to the entire epoxy resin composition. The epoxy resin composition according to any one of claims 1 to 5.
An epoxy resin composition further comprising an inorganic filler. The epoxy resin composition according to any one of claims 1 to 6.
An epoxy resin composition used for encapsulating semiconductor devices. With semiconductor elements
A semiconductor device including a sealing member for sealing the semiconductor element.
A semiconductor device in which the sealing member is made of a cured product of the epoxy resin composition according to any one of claims 1 to 7.

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