KR20160030527A - Process for producing semiconductor devices, and semiconductor device - Google Patents

Abstract

A preparation step of preparing an element mounting board 108 having a plurality of package areas 114 partitioned by a dicing area 112; A molding step of simultaneously molding the semiconductor chip 116 with the epoxy resin composition for sealing and a dicing step of dicing along the dicing area 112 to form the respective semiconductor chips (B) a curing agent, (C) a silicone resin, (D) an inorganic filler, and (E) a curing accelerator. The epoxy resin composition according to claim 1, , Wherein the silicone resin (C) is a methylphenyl-type thermoplastic silicone resin and has a repeating structural unit represented by the following general formulas (a), (b), (c) , A method of manufacturing a semiconductor device.

(Wherein * represents a bond to Si atom in another repeating structural unit or the same repeating structural unit, R ^1a and R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, and they may be the same or different. The content of the phenyl group bonded to the Si atom is 50 mass% or more in one molecule, and the content of the OH group bonded to the Si atom is less than 0.5 mass% in one molecule).

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing a semiconductor device,

The present invention relates to a semiconductor device manufacturing method and a semiconductor device.

2. Description of the Related Art In recent years, in the field of semiconductor packages, small packages such as CSP (Chip Size Package) and BGA have been used in order to meet demands for miniaturization and multi-pin.

Regarding these packaging methods, a MAP (Mold Array Package) method is adopted in which the semiconductor chip is modularized by a batch molding method, and the mounting area and the manufacturing cost can be greatly reduced. The MAP method is a production method in which dozens of chips are arranged in a matrix on a large substrate, and are diced into individual packages after one-side batch encapsulation (see, for example, Patent Documents 1 and 2).

In recent years, electronic components have become highly integrated, high-density mounting, or high-powered. As a result, there is a strong demand for operation and long life of electronic components in a high temperature and high humidity environment. Particularly, BACKGROUND OF THE INVENTION [0002] Electronic components are required to continue to operate satisfactorily even under harsh environments than ordinary electronic components, and sealing resins (molding resins) for electronic components are required to have excellent heat resistance and oil resistance.

In order to improve such characteristics, attempts have been made to improve the properties of the sealing resin of electronic parts using silicone resin. Specific examples include the following.

Patent Document 3 discloses an example of a sealing epoxy resin composition in which a silicone resin containing an aliphatic epoxy group and an adduct of a tertiary phosphine compound and a quinone compound as a curing accelerator are used. Since the aliphatic epoxy group is less reactive, It does not contribute to the cross-linking reaction of the component and deteriorates the water absorption of the sealing material. As a result, although the PKG bending was effective, the solderability was poor.

Patent Document 4 is an example of a sealing epoxy resin composition in which a silicone resin containing an aliphatic epoxy group is combined with a phenol resin of a trisphenol methane type. Since the aliphatic epoxy group is inferior in reactivity, it does not contribute to the crosslinking reaction of the resin component, The water absorption rate of the water-absorbing material is deteriorated. As a result, although the PKG bending was effective, the solderability was poor.

Patent Document 5 describes an epoxy resin composition for sealing which is a combination of a silicone resin containing an aliphatic epoxy group and a bisphenol S epoxy resin. However, since the aliphatic epoxy group is poor in reactivity, it does not contribute to the crosslinking reaction of the resin component, The water absorption of the sealing material is deteriorated. As a result, although the PKG bending was effective, the solderability was poor.

Patent Document 6 discloses an example of a sealing epoxy resin composition comprising a phenyl group and a hydroxyl group or a combination of a silicone resin containing a phenyl group and a propyl group with a phenylaralkyl, biphenyl, biphenyl aralkyl type epoxy resin. If the hydroxyl group is contained in a large amount, the silicone resin becomes high in molecular weight during molding, thereby increasing viscosity, resulting in poor moldability. Further, since the silicone resin contains a long-chain alkyl group such as a propyl group, the flame retardancy of the cured product is significantly lowered.

Patent Document 1: JP-A-8-222654 Patent Document 2: JP-A-2003-060126 Patent Document 3: JP-A-2005-015559 Patent Document 4: JP-A-2005-015561 Patent Document 5: JP-A-2005-015565 Patent Document 6: JP-A-2012-107209 Patent Document 7: JP-A-2012-248774

In the MAP forming process described in Patent Document 1 or the like, when a semiconductor chip is mounted on an element mounting substrate and the semiconductor chip is sealed with a resin material, there is a case where the element mounting substrate is warped due to the difference in thermal expansion coefficient there was.

Particularly in recent years, there is a demand for a thinner semiconductor package. There is a fear that the entire semiconductor package is thinned, and the warpage is liable to surface.

As one approach for solving such warpage, a method of mitigating stress caused by a difference in thermal expansion coefficient between a substrate, a device, and a sealing resin can be considered by using a resin material having excellent flexibility. However, generally, materials with high flexibility tend to be poor in heat resistance.

That is, a resin material capable of achieving the maintenance of characteristics such as heat resistance and the suppression of warpage as a semiconductor device obtained after curing and dicing without causing warping in the MAP forming process has been desired.

A problem to be solved by the present invention is to provide a thermoplastic resin composition which is excellent in low melt viscosity and high fluidity at the time of molding and has a balance of heat resistance, And a method for manufacturing the semiconductor device.

This object is achieved by the present invention described in the following [1] to [9].

[1] a preparation step of preparing an element mounting board having a plurality of package areas partitioned by a dicing region;

Mounting a semiconductor chip on each of the package areas of the element mounting board;

A molding step of simultaneously molding the semiconductor chip with an epoxy resin composition for sealing,

A dicing step is performed along the dicing region to separate the semiconductor chips into individual pieces

/ RTI >

The above-mentioned epoxy resin composition for sealing,

(A) an epoxy resin,

(B) a curing agent,

(C) a silicone resin,

(D) an inorganic filler,

(E) Curing accelerator

/ RTI >

Wherein the silicone resin (C) is a methylphenyl-type thermoplastic silicone resin and has a repeating structural unit represented by the following general formulas (a), (b), (c) and (d) ≪ / RTI >

[Chemical Formula 1]

(Wherein * represents a bond to Si atom in another repeating structural unit or the same repeating structural unit, R ^1a and R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, and they may be the same or different. The content of the phenyl group bonded to the Si atom is 50 mass% or more in one molecule, and the content of the OH group bonded to the Si atom is less than 0.5 mass% in one molecule).

[2] The method for producing a semiconductor device according to [1], wherein the silicone resin (C) further comprises a repeating structural unit represented by the following formulas (e) and (f).

(2)

(Wherein * represents a bond to a Si atom in another repeating structural unit or the same repeating structural unit, and R ^1e represents a methyl group or a phenyl group.) The content of the hydrogen atom bonded to the Si atom is less than 0.5 mass% in one molecule. )

[3] The method for producing a semiconductor device according to [1] or [2], wherein the softening point of the silicone resin (C) is 60 占 폚 or more and 100 占 폚 or less and the number average molecular weight is 1,000 or more and 10,000 or less.

[4] The method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the content of the silicone resin (C) in the total epoxy resin composition for sealing is not less than 0.1 mass% and not more than 5 mass%.

[5] The epoxy resin composition according to [1], wherein the epoxy resin (A) is at least one selected from biphenyl type epoxy resin, phenol aralkyl type epoxy resin, trisphenol methane type epoxy resin, bisphenol type epoxy resin, (pseudo) anthracene type epoxy resin, A method of manufacturing a semiconductor device according to any one of [1] to [4].

[6] The method for producing a semiconductor device according to any one of [1] to [5], wherein the curing agent (B) is a phenol-based curing agent.

[7] The method for manufacturing a semiconductor device according to [6], wherein the phenolic curing agent comprises at least one of a phenol aralkyl resin or a phenol resin having a trisphenol methane skeleton.

[8] The method for manufacturing a semiconductor device according to any one of [1] to [7], wherein the curing accelerator (E) is at least one selected from the compounds represented by the following general formulas (1) to (3).

(3)

R ² , R ³ , R ⁴ and R ⁵ represent an aromatic group or an alkyl group, A represents a group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group; AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring, x represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, y is a number from 1 to 3, z is a number from 0 to 3, and x = y.

[Chemical Formula 4]

(Wherein R ⁶ is an alkyl group having 1 to 3 carbon atoms and R ⁷ is a hydroxyl group, a is a number of 0 to 5, and b is a number of 0 to 4.)

[Chemical Formula 5]

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an organic group having an aromatic ring or a heterocyclic ring (hereinafter referred to as an organic group having an aromatic ring or a heterocyclic ring) , Or an aliphatic group, and may be the same or different from each other. In the formula, R ¹² is an organic group which is bonded to the groups Y ² and Y ^{3. In the} formulas, R ¹³ represents an organic group which is 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 bind to silicon atoms to form a chelate structure Y ⁴ and Y ⁵ are proton Y ² and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure, R ¹² and R ¹³ may be the same or different, and Y ² , Y ^3, Y ^4, and Y ⁵ are the same or different from each other to be It is. Z ¹ is an organic group, or an aliphatic group having an aromatic ring or a heterocyclic ring.)

[9] A semiconductor device obtained by the manufacturing method according to any one of [1] to [8].

In the method for manufacturing a semiconductor device of the present invention, an epoxy resin composition containing a specific silicone resin is used. The epoxy resin composition is excellent in low-melt viscosity and high fluidity at the time of molding, so that the production efficiency at the time of semiconductor production can be improved. Further, by providing the cured product obtained from the epoxy resin composition as a sealing material for sealing the semiconductor element, it is possible to provide a semiconductor device excellent in balance of heat resistance, anti-warping property, solder crack resistance, temperature cycle resistance and moisture resistance reliability .

Conventional silicone resins tend to cause low Tg, high thermal expansion rate, low thermal resistance, and low reliability of a semiconductor device. However, in the conventional silicone resin, a low Tg, a high thermal expansion coefficient, By using a specific silicone resin, these trade-offs do not occur and an excellent balance result can be obtained.

The foregoing and other objects, features, and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments thereof with reference to the accompanying drawings.
1 is a process sectional view showing a manufacturing procedure of a semiconductor device in the first embodiment.
2 is a process top view showing a manufacturing procedure of the semiconductor device in the first embodiment.
3 is a process sectional view showing a manufacturing procedure of the semiconductor device in the first embodiment.
4 is a longitudinal sectional view showing an example of an electronic component module according to the second embodiment.

Hereinafter, a method of manufacturing a semiconductor device and a semiconductor device of the present invention will be described in detail based on a preferred embodiment.

≪ First Embodiment >

The manufacturing method of the semiconductor device 100 of the present embodiment is referred to as a so-called "MAP method" and includes the following steps. First, an element mounting board 108 having a plurality of package areas 114 partitioned by a dicing region 112 is prepared (hereinafter referred to as preparation step). Subsequently, the semiconductor chip 116 is mounted on each of the package areas 114 of the element mounting board 108 (hereinafter referred to as mounting step). Subsequently, the semiconductor chip 116 is simultaneously molded with the epoxy resin composition for sealing (hereinafter referred to as a molding process). Dicing is performed along the dicing region 112 to separate each of the molded semiconductor chips 116 (hereinafter, referred to as an individualizing step).

The epoxy resin composition for sealing according to the present embodiment comprises (A) an epoxy resin, (B) a curing agent, (C) a silicone resin, (D) an inorganic filler, and (E) a curing accelerator, Methylphenyl type thermoplastic silicone resin having a repeating structural unit represented by the following general formulas (a), (b), (c) and (d).

[Chemical Formula 6]

(Wherein * represents a bond to Si atom in another repeating structural unit or the same repeating structural unit, R ^1a and R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, and they may be the same or different. The content of the phenyl group bonded to the Si atom is 50 mass% or more in one molecule, and the content of the OH group bonded to the Si atom is less than 0.5 mass% in one molecule).

Hereinafter, each step will be described in detail.

(Preparation process)

In this preparation step, the element mounting substrate 108 is prepared. The substrate on which the element is mounted can be appropriately set so long as the object of the invention is not impaired, for example, an organic substrate is exemplified.

(Mounting process)

Next, the mounting process of the present embodiment will be described.

2 is a process top view of the mounting process. 1 (a) is a cross-sectional view along the line A-A 'in Fig. 2.

As shown in Fig. 2, a plurality of semiconductor chips 116 are arranged on the element mounting surface 110 of the element mounting board 108. As shown in Fig. On the element mounting surface 110, a package area 114 defined by a dicing region 112 is formed. The package areas 114 are arranged at predetermined intervals. One semiconductor chip 116 may be formed in one package area 114, or a plurality of semiconductor chips 116 may be formed. In this embodiment, an example in which one semiconductor chip 116 is disposed in one package area 114 will be described. The outer edge of the semiconductor chip 116 corresponds to the outer edge of the package area 114.

The distance between the central package areas 114 closest to the center position is L1 and the distance between the center package area 114 and the outer package area 114 disposed outside the center package area 114 is L2 do. L2 may be equal to L1 or greater than L1. By setting L2 = L1, the semiconductor chips 116 can be arranged at high density. Further, by making L2 > L1, the difference between the coefficient of linear expansion of the element mounting surface 110 and the coefficient of linear expansion on the opposite surface side outside the element mounting board 108 can be reduced. This makes it possible to reduce warpage of the outside of the element mounting board 108 in particular.

1A, the element mounting board 108 and the semiconductor chip 116 are electrically connected through, for example, a solder bump 118 and a wiring layer (not shown). In addition, the electrode of the element mounting board 108 and the semiconductor chip 116 may be connected by a bonding wire.

Connection between the element mounting board 108 and the semiconductor chip 116 is performed, for example, as follows.

First, the semiconductor chip 116 is fixed to the element mounting board 108 with an adhesive, and then the elements are heat-pressed. In the present embodiment, the adhesive may be a liquid or a sheet. The adhesive may have a flux activator.

The semiconductor chip 116 and the element mounting board 108 are soldered to each other by heating the laminate composed of the semiconductor chip 116 and the element mounting board 108 to a temperature equal to or higher than the melting point of the solder bump 118. [ Thereby, the semiconductor chip 116 and the element mounting board 108 are connected to each other.

The semiconductor chip 116 is not particularly limited, but preferably has a chip size package structure, for example.

(Molding process)

Next, the molding process of the present embodiment will be described.

As shown in Fig. 1 (b), the semiconductor chip 116 on the element mounting board 108 is simultaneously molded with a sealing material. The entirety of the semiconductor chip 116 is covered with the molding resin layer 120. As a result, a semiconductor package is formed. In the semiconductor package, the gaps between the semiconductor chips 116 are buried in the molding resin layer 120.

In the molding process, the molding resin layer 120 is formed on the element mounting board 108 on which the semiconductor chip 116 is mounted by using a sealing epoxy resin composition containing a specific silicone resin.

Hereinafter, the epoxy resin composition for sealing will be described.

≪ Epoxy resin composition for sealing >

In the epoxy resin composition for sealing according to the present embodiment,

(A) an epoxy resin,

(B) a curing agent,

(C) a silicone resin,

(D) an inorganic filler,

(E) Curing accelerator

Lt; / RTI >

The silicone resin (C) is a methylphenyl-type thermoplastic silicone resin, and has a repeating structural unit represented by the following general formulas (a), (b), (c) and (d).

(7)

(Wherein * represents a bond to Si atom in another repeating structural unit or the same repeating structural unit, R ^1a and R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, and they may be the same or different. The content of the phenyl group bonded to the Si atom is 50 mass% or more in one molecule, and the content of the OH group bonded to the Si atom is less than 0.5 mass% in one molecule).

Hereinafter, each component contained in the epoxy resin composition for sealing in this embodiment will be described in order.

[Epoxy resin]

Examples of the epoxy resin (A) in the present embodiment include phenol aralkyl type epoxy resins (phenol aralkyl type epoxy resins having a biphenylene skeleton, phenol aralkyl type epoxy resins having a phenylene skeleton and the like), biphenyl type epoxy resins, An anthracene epoxy resin of bisphenol type epoxy resin (bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc.), and anthracene type epoxy resin, and these may be used singly or in combination of two or more kinds May be used.

The content of the epoxy resin (A) used in the epoxy resin composition for sealing of the present embodiment is not particularly limited, but is preferably 3 mass% or more and 20 mass% or less, more preferably 5 mass% or less, Or more and 15 mass% or less, and most preferably 6 mass% or more and 10 mass% or less.

When the content of the entire epoxy resin (A) is set to the lower limit value or more, the fluidity at the time of melting of the epoxy resin composition for sealing is improved. By setting the upper limit to the above value, the solderability of the molded article can be improved.

≪ Phenol aralkyl type epoxy resin having biphenylene skeleton >

Examples of the phenol aralkyl type epoxy resin having a biphenylene skeleton in the present embodiment include resins having a structure represented by the following general formula (4).

[Chemical Formula 8]

(Wherein R ¹⁴ and R ¹⁵ are each a hydrogen atom or an organic group having 1 to 4 carbon atoms and may be the same or different), c is a number of 0 to 3, and d is a number of 0 to 4. n is an average value Which is a number from 1 to 5.)

R ¹⁴ and R ¹⁵ in the general formula (4) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or an isobutyl group, a methoxy group, An alkoxy group having 1 to 4 carbon atoms such as a butoxy group and the like, among which a hydrogen atom or a methyl group is preferable. As the phenol aralkyl type epoxy resin having a biphenylene skeleton in the present embodiment, an epoxy resin containing n = 1 as a main component is more preferable. For example, NC-3000L (trade name, manufactured by Nippon Kayaku Co., Ltd.) Are commercially available. When the phenol aralkyl type epoxy resin having a biphenylene skeleton is used, since the distance between the crosslinking points becomes long, the elastic modulus of the cured product can be reduced and the soldering resistance is improved.

<Biphenyl-type epoxy resin>

Examples of the biphenyl type epoxy resin in the present embodiment include those containing a resin having a structure represented by the following general formula (5).

[Chemical Formula 9]

(Wherein R ¹⁶ to R ²³ are each a hydrogen atom or an organic group having 1 to 4 carbon atoms, which may be the same or different)

R ¹⁶ to R ²³ in the general formula (5) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group or an isobutyl group, a methoxy group, An alkoxy group having 1 to 4 carbon atoms such as a butoxy group and the like, among which a hydrogen atom or a methyl group is preferable. Examples of the biphenyl type epoxy resin in the present invention include 4,4'-bis (2,3-epoxypropoxy) biphenyl or 4,4'-bis (2,3-epoxypropoxy) , Epoxy resin mainly composed of 5,5'-tetramethylbiphenyl, epichlorohydrin and 4,4'-biphenol or 4,4 '- (3,3', 5,5'-tetramethyl) And epoxy resins obtained by reacting phenol. Among them, epoxy resins having 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl as a main component Epoxy resins are more preferable, and for example, YX-4000K and YX-4000H (all trade names, manufactured by Mitsubishi Kagaku Co., Ltd.) are commercially available. When the biphenyl-type epoxy resin is used, adhesiveness to the circuit board and the lead frame is improved, and soldering resistance is improved.

&Lt; Phenol aralkyl type epoxy resin having phenylene skeleton &gt;

Examples of the phenol aralkyl type epoxy resin having a phenylene skeleton in the present embodiment include resins having a structure represented by the following general formula (6).

[Chemical formula 10]

(Wherein, R ^24, R ²⁵ is a hydrogen atom or an organic group having from 1 to 4 carbon atoms, may be the same or different may be one another. E is a number of 0 ~ 3, f is a number of 0 ~ 4. N is the average value Which is a number from 1 to 5.)

R ²⁴ and R ²⁵ in the general formula (6) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group or an isobutyl group, a methoxy group, An alkoxy group having 1 to 4 carbon atoms such as a butoxy group and the like, among which a hydrogen atom or a methyl group is preferable. As the phenol aralkyl type epoxy resin having phenylene skeleton in the present embodiment, an epoxy resin containing n = 1 as a main component is more preferable, and for example, NC-2000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) Is available as a commercial product. When the phenol aralkyl type epoxy resin having a phenylene skeleton is used, since the distance between the crosslinking points is enlarged, the elastic modulus of the cured product can be reduced and the soldering resistance is improved.

<Trisphenol methane-type epoxy resin>

As the trisphenol methane-type epoxy resin in the present embodiment, those containing a resin having a structure represented by the following general formula (7) can be cited.

(11)

N is an average value of 1 to 10, g is a number of 0 to 3, and h is an integer of 0 to 3. In the formula, R ²⁶ represents a hydrogen atom or an organic group having 1 to 4 carbon atoms, 4.)

R ²⁶ in the general formula (7) represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or an isobutyl group, a methoxy group, An alkoxy group having 1 to 4 carbon atoms such as a methoxy group, and the like. Among them, a hydrogen atom or a methyl group is preferable. As the trisphenol methane-type epoxy resin in the present embodiment, an epoxy resin containing n = 1 as a main component is more preferable, and for example, Tactix 742 (trade name, manufactured by Huntsman Advanced Materials Co., Ltd.), 1032 H60 (trade name, manufactured by Mitsubishi Kagaku K.K.), EPPN-501 and EPPN-502 (trade names, manufactured by Nippon Kayaku Co., Ltd.) are commercially available. When this trisphenol methane-type epoxy resin is used, the Tg can be improved by increasing the cross-linking density, and the soldering resistance is improved.

<Bisphenol A type epoxy resin>

As the bisphenol A type epoxy resin in the present embodiment, those containing a resin having a structure represented by the following general formula (8) can be mentioned.

[Chemical Formula 12]

(Wherein R ²⁷ is a hydrogen atom or an organic group having 1 to 4 carbon atoms, and may be the same or different), i is a number of 0 to 4, and n is an average value of 0 to 5.

R ²⁷ in the general formula (8) represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or an isobutyl group, a methoxy group, An alkoxy group having 1 to 4 carbon atoms such as a methoxy group, and the like. Among them, a hydrogen atom or a methyl group is preferable. As the bisphenol A type epoxy resin in the present embodiment, an epoxy resin containing n = 0 as a main component is more preferable. For example, Epicot YL6810 (trade name, manufactured by Mitsubishi Chemical Corp.) Do. When this bisphenol A type epoxy resin is used, since the distance between the crosslinking points is increased, the elastic modulus of the cured product can be reduced and the soldering resistance is improved.

<Anthracene type epoxy resin>

Examples of the anthracene epoxy resin in the present embodiment include those containing a resin having a structure represented by the following general formula (9).

[Chemical Formula 13]

(In the formula, R ²⁸ is a hydrogen atom or an organic group having 1 to 4 carbon atoms, and may be the same or different.) J is a number of 0 to 8, and n is an average value of 0 to 5.

R ²⁸ in the general formula (9) represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or an isobutyl group, a methoxy group, An alkoxy group having 1 to 4 carbon atoms such as a methoxy group, and the like. Among them, a hydrogen atom or a methyl group is preferable. As the anthracene epoxy resin represented by the general formula (9), an epoxy resin containing n = 0 as a main component is more preferable. For example, YX8800 (trade name, manufactured by Mitsubishi Kagaku), YL7310 (Mitsubishi Kagaku Co., (Trade name, manufactured by Nippon Steel Chemical Co., Ltd.) are commercially available. When the anthracene epoxy resin is used, since the distance between the crosslinking points becomes long, the elastic modulus of the cured product can be reduced, and soldering resistance is improved.

[Curing agent]

The (B) curing agent in the present embodiment is not particularly limited as long as it is generally used in the epoxy resin composition for sealing, and examples thereof include phenol type curing agents, amine type curing agents, acid anhydride type curing agents and mercaptan type curing agents . Among these, a phenol-based curing agent is preferable in view of balance among flame retardance, moisture resistance, electrical properties, curability, storage stability and the like.

<Phenolic curing agent>

The phenol-based curing agent is not particularly limited as long as it is generally used in the epoxy resin composition for sealing, and examples thereof include phenol novolac resins, cresol novolac resins, phenols such as phenol, cresol, resorcin, catechol, bisphenol A, F, phenols such as phenylphenol and aminophenol and / or resins obtained by condensation or co-condensation of naphthols such as? -Naphthol,? -Naphthol and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde in the presence of an acidic catalyst, phenols And / or a phenol aralkyl resin having a biphenylene skeleton synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, a phenol aralkyl resin having a phenylene skeleton, a trisphenol methane skeleton And the like, and they may be used alone or in combination of two or more.

<Amine type curing agent>

Examples of the amine-based curing agent include aliphatic polyamines such as diethylene triamine (DETA), triethylene tetramine (TETA) and meta xylene diamine (MXDA), diaminodiphenylmethane (DDM), m- (DICY), an organic acid dihydrazide, and the like, in addition to aromatic polyamines such as diisocyanate (MPDA) and diaminodiphenylsulfone (DDS). These may be used alone or in combination of two Or a combination of two or more species may be used.

<Acid anhydride type curing agent>

Examples of the acid anhydride-based curing agent include aliphatic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) and maleic anhydride, anhydrous trimellitic acid (TMA) and anhydrous pyromellitic acid And aromatic acid anhydrides such as benzophenone tetracarboxylic acid (BTDA) and phthalic anhydride, and these may be used alone or in combination of two or more.

<Mercaptan-based curing agent>

Examples of the mercaptan-based curing agent include trimethylolpropanol (3-mercaptobutylate) and trimethylolethane terephthalate (3-mercaptobutylate). These may be used alone or in combination of two or more May be used.

<Other Curing Agent>

Examples of other curing agents include isocyanate compounds such as isocyanate prepolymer and blocked isocyanate, and organic acids such as carboxylic acid-containing polyester resin. These may be used alone or in combination of two or more May be used.

Two or more kinds of curing agents of different systems may be used in combination.

When the (B) curing agent is a phenol-based curing agent, there is no particular restriction on the ratio of the equivalent ratio of the epoxy resin (A) to the curing agent (B), that is, the ratio of the number of moles of epoxy groups in the epoxy resin / number of moles of phenolic hydroxyl groups in the phenolic curing agent In order to obtain an epoxy resin composition excellent in floatability and transparency, the range is preferably 0.5 or more and 2 or less, more preferably 0.6 or more and 1.5 or less, most preferably 0.8 or more and 1.2 or less.

[Silicone Resin]

The (C) silicone resin in the present embodiment is a methylphenyl-type thermoplastic silicone resin and is a resin having a repeating structural unit represented by the following general formulas (a), (b), (c) to be.

[Chemical Formula 14]

(Wherein * represents a bond to Si atom in another repeating structural unit or the same repeating structural unit, R ^1a and R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, and they may be the same or different. The content of the phenyl group bonded to the Si atom is 50 mass% or more in one molecule, and the content of the OH group bonded to the Si atom is less than 0.5 mass% in one molecule).

When the phenyl group is contained in an amount of 50 mass% or more in one molecule, compatibility with the epoxy resin or the phenol-based curing agent is enhanced, the flame resistance is increased, and the absorbency of the resin-cured product can be reduced.

The content of the OH group bonded to the Si atom and the hydrogen atom bonded to the Si atom represented by the repeating structure of the following general formulas (e) and (f) in the silicone resin (C) . When the amount is 0.5% by mass or more, the molecular weight of the silicone resin is increased during the molding of the epoxy resin composition for sealing, whereby the melt viscosity of the epoxy resin composition for sealing is increased and the fluidity is lowered. May occur.

[Chemical Formula 15]

(Wherein * represents a bond to a Si atom in another repeating structural unit or the same repeating structural unit, and R ^1e represents a methyl group or a phenyl group.) The content of the hydrogen atom bonded to the Si atom is less than 0.5 mass% in one molecule. )

The softening point of the silicone resin (C) is preferably 60 占 폚 or higher and 100 占 폚 or lower. If the softening point is less than 60 캜, the glass transition temperature is lowered, and the flexural fluctuation of the electronic component at the time of operation (high temperature) and at the time of stopping (room temperature) becomes large. When the softening point is higher than 100 캜, the compatibility with the resin component deteriorates, so that the deflection control ability is not sufficiently exhibited and the surface of the electronic component is also contaminated.

The number average molecular weight of the silicone resin (C) is preferably 1000 or more and 10000 or less. If the number average molecular weight is less than 1000, the volatile components increase, and voids tend to be generated in the electronic component. When the number average molecular weight is more than 10,000, the compatibility with the resin component deteriorates, so that the deflection control ability is not sufficiently exhibited and the surface of the electronic component is also contaminated.

(C) the silicone resin is selected from the group consisting of dichlorodimethylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, trichloromethylsilane, trichlorophenylsilane, chlorotrimethylsilane, chlorotriphenylsilane With a compounding ratio in accordance with the aimed branch structure, phenyl group content and molecular weight, hydrolyzing the resulting silanol group, and dehydrating condensation and purification of the produced silanol group. (Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 233FLAKE (trade name, manufactured by Toray Dow Corning Co., Ltd.), 249FLAKE (trade name, manufactured by Toray Dow Corning Co., Ltd.) However, in order to use it in the epoxy resin composition for sealing, it is preferable to be purified and used by washing or the like for dechlorination.

These (C) silicone resins may be used alone or in combination of two or more.

The content of the silicone resin (C) in the total epoxy resin composition for encapsulation is preferably not less than 0.1% by mass and not more than 5% by mass, more preferably not less than 0.5% by mass and not more than 2% , Preferably 1% by mass or less. By setting the content within the above range, good moldability, good bending property and peeling resistance of the semiconductor device can be obtained. If it is less than 0.1% by mass, the effect contained is hard to be obtained, and the glass transition temperature of the cured product is lowered, the thermal expansion coefficient is increased, and the warpage is increased. If it exceeds 5% by mass, the dispersion state in the epoxy resin deteriorates, resulting in an increase in melt viscosity and a decrease in fluidity, resulting in defective adhesion, poor charging, and wire deflection.

[Inorganic filler]

As the inorganic filler (D) in the present embodiment, an inorganic filler generally used in the art can be used. Specifically, examples thereof include fused silica, spherical silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. These inorganic fillers may be used singly or in combination. Suitably, molten spherical silica is used.

The average particle diameter of the inorganic filler (D) is preferably 0.01 占 퐉 or more and 150 占 퐉 or less from the viewpoint of the packing property. The average particle diameter can be measured using a laser diffraction scattering particle size distribution meter.

The content of the inorganic filler in the whole epoxy resin composition for sealing (D) is preferably 75% by mass or more and 93% by mass or less, more preferably 80% by mass or more and 91% by mass or less, Mass% or more and 90 mass% or less. Within the above-mentioned range, the semiconductor device is sufficiently in close contact with the semiconductor device under high temperature, and the warpage is small, so that no large stress is applied to the device, so that peeling resistance can be obtained. If the content is less than the lower limit value, good solder crack resistance can not be obtained, the weight reduction rate at high temperature rises, the linear expansion coefficient increases, the warpage increases, and the peeling resistance decreases. If the content exceeds the upper limit, the flowability and moldability of the epoxy resin composition for sealing are lowered.

It is also preferable to include the inorganic filler (D1) having an average particle diameter of not less than 7 μm and not more than 50 μm and the inorganic filler (D2) having an average particle diameter of not more than 1 μm simultaneously. (D2) is preferably 60% by mass or more and 85% by mass or less, more preferably 65% by mass or more and 83% by mass or less in total epoxy resin composition for sealing, and the content of (D2) Is preferably not less than 1% by mass and not more than 25% by mass, more preferably not less than 3% by mass and not more than 20% by mass in the epoxy resin composition for use in the epoxy resin composition. When the thickness is in the above range, the semiconductor device is sufficiently in close contact with the semiconductor device under high temperature, and no significant stress is applied to the device, so that the anti-bending property and the peeling resistance can be obtained.

When an inorganic flame retardant such as metal hydroxide such as aluminum hydroxide or magnesium hydroxide or zinc borate, zinc molybdatezanate or antimony trioxide described below is used, the total amount of the inorganic flame retardant and the inorganic filler is within the above range .

[Curing accelerator]

The (E) curing accelerator has a function of accelerating the reaction between the epoxy groups of the epoxy resin and the reaction between the epoxy resin and the curing agent, and a commonly used curing accelerator is used.

Specific examples of the (E) curing accelerator include organic phosphorus compounds such as organic phosphine, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds ; Amidine and tertiary amines exemplified by 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole, etc., And nitrogen atom-containing compounds such as nitrate, nitrate, and nitrate. One or more of these may be used in combination. Among them, a phosphorus atom-containing compound is preferable from the viewpoint of curability, and a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound is particularly preferable from the viewpoints of solder resistance and fluidity, Particularly, phosphorus atom-containing compounds such as tetra-substituted phosphonium compounds, adducts of phosphonium compounds and silane compounds are particularly preferable in terms of contamination.

Examples of the organic phosphine which can be used in the epoxy resin composition for sealing include primary phosphines such as ethylphosphine and phenylphosphine; A second phosphine such as dimethylphosphine or diphenylphosphine; And tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.

Examples of tetra-substituted phosphonium compounds that can be used in the epoxy resin composition for sealing include compounds represented by the following general formula (1).

[Chemical Formula 16]

R ² , R ³ , R ⁴ and R ⁵ represent an aromatic group or an alkyl group, A represents a group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group; AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring, x represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, y is a number from 1 to 3, z is a number from 0 to 3, and x = y.

The compound represented by the general formula (1) is obtained, for example, in the following manner, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed with an organic solvent and uniformly mixed to generate an aromatic organic acid anion in the solution system. Subsequently, by adding water, the compound represented by the general formula (1) can be precipitated. In the compound represented by the general formula (1), R ² , R ³ , R ⁴ and R ⁵ bonded to the phosphorus atom are phenyl groups and AH is a compound having a hydroxyl group in the aromatic ring, that is, Is preferably an anion of the phenol. The phenols in the present embodiment include monocyclic phenols such as phenol, cresol, resorcin and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene and anthraquinone, bisphenol A, bisphenol F, bisphenol S, etc. And bisphenols, phenyl phenols, biphenols, and other polycyclic phenols.

Examples of the phosphobetaine compound include compounds represented by the following general formula (2).

[Chemical Formula 17]

(Wherein R ⁶ is an alkyl group having 1 to 3 carbon atoms and R ⁷ is a hydroxyl group, a is a number of 0 to 5, and b is a number of 0 to 4.)

The compound represented by the general formula (2) is obtained, for example, as follows. First, a triazoaryl-substituted phosphine, which is a third phosphine, is brought into contact with a diazonium salt to obtain a diazonium-substituted phosphine and a diazonium salt. However, the present invention is not limited thereto.

Examples of the adduct of a phosphine compound and a quinone compound include compounds represented by the following general formula (10).

[Chemical Formula 18]

R ²⁹ , R ³⁰ and R ³¹ each represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms and may be the same or different from each other, R ³² , R ³³ and R ^{34 each} represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different, and R ³³ and R ³⁴ may combine to form a cyclic structure.

Examples of the phosphine compound used in the addition of the phosphine compound and the quinone compound include triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, tris Substituents such as an unsubstituted or alkyl group or alkoxyl group are preferably present in an aromatic ring such as a phosphine group, and examples of the substituent group such as an alkyl group and an alkoxyl group include those having a carbon number of 1 to 6. From the viewpoint of availability, triphenylphosphine is preferable.

Examples of the quinone compound used in the addition of the phosphine compound and the quinone compound include benzoquinone and anthraquinone. Of these, p-benzoquinone is preferable from the viewpoint of storage stability.

As a production method of the adduct of the phosphine compound and the quinone compound, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both the organic tertiary phosphine and the benzoquinone. As the solvent, ketones such as acetone, methyl ethyl ketone and the like may preferably have low solubility in the adduct. However, the present invention is not limited thereto.

In the compound represented by the general formula (10), compounds wherein R ²⁹ , R ³⁰ and R ³¹ bonded to the phosphorus atom are phenyl groups and R ³² , R ³³ and R ³⁴ are hydrogen atoms, that is, 1,4-benzoquinone A compound obtained by adding a norbornene and triphenylphosphine is preferable in that the modulus of elasticity of the cured product of the epoxy resin composition for sealing is reduced.

Examples of adducts of the phosphonium compound and the silane compound include compounds represented by the following general formula (3).

[Chemical Formula 19]

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an organic group having an aromatic ring or a heterocyclic ring (hereinafter referred to as an organic group having an aromatic ring or a heterocyclic ring) , Or an aliphatic group, and may be the same or different from each other. In the formula, R ¹² is an organic group which is bonded to the groups Y ² and Y ^{3. In the} formulas, R ¹³ represents an organic group which is 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 bind to silicon atoms to form a chelate structure Y ⁴ and Y ⁵ are proton Y ² and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure, R ¹² and R ¹³ may be the same or different, and Y ² , Y ^3, Y ^4, and Y ⁵ are the same or different from each other to be It is. Z ¹ is an organic group, or an aliphatic group having an aromatic ring or a heterocyclic ring.)

Examples of R ⁸ , R ⁹ , R ¹⁰ and R ^{11 in the} general formula (3) include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, Of these, an alkyl group such as a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group and a hydroxynaphthyl group, an alkoxy group, a hydroxyl group Or an unsubstituted aromatic group is more preferable.

In the general formula (3), R ¹² is an organic group bonded to Y ² and Y ³ . Similarly, R ¹³ is an organic group which is bonded to the groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups in which the proton donating group releases protons, and groups Y ² and Y ^{3 in the} same molecule bind to silicon atoms to form a chelate structure. Likewise, Y ⁴ and Y ⁵ are groups in which the proton donating group releases protons, and groups Y ⁴ and Y ⁵ in the same molecule bind to silicon atoms to form a chelate structure. The groups R ¹² and R ¹³ may be the same or different, and the groups Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different. The group represented by -Y ² -R ¹² -Y ³ - and Y ⁴ -R ¹³ -Y ⁵ - in the general formula (3) is a group in which the proton donor is composed of a group formed by releasing two protons, Is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule and further preferably an aromatic compound having at least two carboxyl groups or hydroxyl groups at adjacent carbon atoms constituting aromatic rings, More preferred are aromatic compounds having at least two hydroxyl groups at adjacent carbon atoms, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2 ' 2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycidyl It may include Lin et al., Of these, catechol, 1,2-dihydroxy naphthalene, 2,3-dihydroxy naphthalene is more preferable.

Z ¹ in the general formula (3) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic group, and specific examples thereof include aliphatic carbons such as a methyl group, an ethyl group, a propyl group, a butyl group, A hydrogen 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, an alkyl group having a mercapto group, A vinyl group, and the like. Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group and a biphenyl group are more preferable in terms of thermal stability.

As a method for producing adducts of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane or a proton donor such as 2,3-dihydroxynaphthalene is added and dissolved in a flask containing methanol, Then, sodium methoxide-methanol solution is added dropwise at room temperature with stirring. Next, a solution prepared by dissolving tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide prepared in advance in methanol therein is added dropwise with stirring at room temperature to precipitate crystals. 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 present invention is not limited thereto.

The silicone resin such as the component (C) may increase the melt viscosity of the epoxy resin composition for sealing to deteriorate the moldability. However, as the curing accelerator, the compound represented by the above general formulas (1) to (3) It is easy to ensure good fluidity at the time of molding. In particular, adducts of a phosphine compound and a quinone compound, and adducts of a phosphonium compound and a silane compound are particularly preferable from the viewpoint of being sufficiently adhered to a semiconductor device under high temperature. The reason for this is not clear, but it is preferable to use an epoxy resin represented by the general formulas (4) to (9) in the present invention, an aromatic resin having a plurality of hydroxyl groups contained in the structure derived from the phenolic curing agent, It is considered that not only excellent fluidity, adhesion property, and flexural behavior but also good humidity resistance reliability characteristics are exhibited by exhibiting a unique behavior at the interface of the semiconductor element at high temperature.

The content of the (E) curing accelerator is preferably 0.1% by mass or more and 1% by mass or less, more preferably 0.11% by mass or more and 0.7% by mass or less in the entire epoxy resin composition for sealing, more preferably 0.12% % Or less is most preferable. When the content of the (E) curing accelerator is within the above range, sufficient curability and fluidity can be obtained, and furthermore, the anti-flexural characteristic and the peeling resistance become the best characteristics.

[Other components]

The epoxy resin composition for sealing according to the present embodiment may contain the following components as required.

[A compound in which a hydroxyl group is bonded to two or more adjacent carbon atoms constituting an aromatic ring]

In the present embodiment, a compound (F) having a hydroxyl group bonded to two or more adjacent carbon atoms constituting an aromatic ring can be used. The compound (F) suppresses the reaction in the melt-kneading of the epoxy resin composition for sealing, even when a phosphorus atom-containing curing accelerator having no latent property is used as a curing accelerator for promoting the crosslinking reaction between the phenolic curing agent and the epoxy resin can do.

The inclusion of such compound (F) makes it possible to form a sealing material under high-shear conditions, thereby improving the flow characteristics of the epoxy resin composition for sealing and releasing the releasing component on the surface of the package in continuous molding, It is preferable in that it has the effect of lengthening the cleaning cycle of the mold by suppressing the accumulation of the components.

The compound (F) has an effect of improving the fluidity by lowering the melt viscosity of the epoxy resin composition for sealing, but also has the effect of improving the solderability, though the detailed mechanism is unclear.

As the compound (F), a monocyclic compound represented by the following general formula (11) or a polycyclic compound represented by the following general formula (12) can be used, and these compounds may have a substituent other than a hydroxyl group.

[Chemical Formula 20]

At least one of R ³⁵ and R ³⁹ is a hydroxyl group and the other is a substituent other than a hydrogen atom, a hydroxyl group or a hydroxyl group when the univalent group is a hydroxyl group, R ³⁶ , R ³⁷ , R ³⁸ is a substituent other than a hydrogen atom, a hydroxyl group or a hydroxyl group.)

[Chemical Formula 21]

(Wherein R ⁴⁰ and R ⁴⁶ are each a hydroxyl group and at least one of R ⁴¹ and R ⁴² is one of a substituent other than a hydrogen atom, R ⁴³ , R ⁴⁴ and R ⁴⁵ are each a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.

Specific examples of the monocyclic compound represented by the general formula (11) include, for example, catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof.

Specific examples of the polycyclic compound represented by the general formula (12) include, for example, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Of these, compounds having a hydroxyl group bonded to two adjacent carbon atoms constituting an aromatic ring are preferable in easiness of control of fluidity and curability. Further, in consideration of volatilization in the kneading step, it is more preferable to use a compound in which the mother nucleus is a naphthalene ring having low volatility and high stability of weighing. In this case, the compound (F) can specifically be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and a derivative thereof. These compounds (F) may be used alone or in combination of two or more.

The content of the compound (F) in the total epoxy resin composition for sealing is preferably 0.01 mass% or more and 1 mass% or less, more preferably 0.03 mass% or more and 0.8 mass% or less, particularly preferably 0.05 mass% Or more and 0.5 mass% or less. If the content of the compound (F) is smaller than the lower limit value, the melt viscosity of the epoxy resin composition for sealing increases and the fluidity decreases. When the content of the compound (F) is larger than the upper limit, the curing property of the epoxy resin composition for sealing is lowered, the strength of the cured product is lowered, and the coefficient of linear expansion is increased.

[Coupling agent]

The coupling agent has a function of improving the adhesion between the epoxy resin and the inorganic filler when an inorganic filler is contained in the epoxy resin composition for sealing, and for example, a silane coupling agent or the like is used.

As the silane coupling agent, various types such as anilinosilane can be used.

The lower limit of the content of the coupling agent such as a silane coupling agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more in the total epoxy resin composition for sealing. If the content is lower than the lower limit value, the interface strength between the epoxy resin and the inorganic filler is not lowered, and good solder crack resistance in the electronic component device can be obtained. The upper limit of the content of the coupling agent such as a silane coupling agent is preferably 1% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.6% by mass or less, based on the total amount of the epoxy resin composition for sealing. If the content is not more than the upper limit, the interface strength between the epoxy resin and the inorganic filler is not lowered, and good solder crack resistance in the device can be obtained. When the content of the coupling agent such as a silane coupling agent is within the above range, the water absorbency of the cured product of the epoxy resin composition for sealing does not increase and good solder crack resistance in the electronic component device can be obtained.

[Inorganic Flame Retardant]

The inorganic flame retardant has a function of improving the flame retardancy of the epoxy resin composition for sealing, and generally used inorganic flame retardant is used.

Concretely, a metal hydroxide which inhibits the combustion reaction by dehydration and endothermic combustion at the time of combustion and a composite metal hydroxide which can shorten the combustion time are preferably used.

Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and zirconium hydroxide.

The complex metal hydroxide is a hydrotalcite compound containing at least two metal elements, and at least one metal element is magnesium, and the other metal element is calcium, aluminum, tin, titanium, iron, cobalt, , Or zinc. As such a composite metal hydroxide, a magnesium hydroxide / zinc solid solution is easily available as a commercial product.

Of these, aluminum hydroxide, magnesium hydroxide and zinc solid solutions are preferred from the viewpoint of balance between soldering resistance and continuous formability.

The inorganic flame retarding agent may be used alone, or two or more kinds thereof may be used. For the purpose of reducing the influence on the continuous formability, surface treatment may be carried out by using a silicon compound such as a silane coupling agent or an aliphatic compound such as wax.

[Release Agent]

Here, the mold releasing agent has a function of releasing a molded article from a mold when molding with a transfer molding machine or the like.

The release agent in this embodiment is not particularly limited as long as it is a release agent known to those skilled in the art for an epoxy resin composition for semiconductor encapsulation, for example, carnauba.

These release agents may be used alone or in combination of two or more.

The lower limit of the content of the releasing agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more in the entire epoxy resin composition for sealing. If the content of the releasing agent is the lower limit value or more, the cured product can be released from the mold at the time of molding. The upper limit of the content of the release agent is preferably 1% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.5% by mass or less, based on the total amount of the epoxy resin composition for sealing. If the content of the releasing agent is not more than the upper limit value, contamination due to the release of the releasing agent onto the surface of the molded article can be suppressed.

In addition to the above-mentioned other components, components known to those skilled in the art such as carbon black, red iron oxide, and titanium oxide may suitably be contained.

The above-mentioned epoxy resin composition for sealing according to the present invention can be obtained by uniformly mixing the curing agent, the epoxy resin and further the other components at room temperature by using, for example, a mixer or the like, Kneaded using a kneader such as a hot roll, a kneader or an extruder, and then cooled and pulverized as required, so that the desired degree of dispersion and fluidity can be adjusted.

<Thickness of each component>

The dimensions of the semiconductor package are not particularly limited, but preferably satisfy the following conditions (1) to (3).

(1) The chip height (thickness H1) is preferably 50 占 퐉 or more and 500 占 퐉 or less, and more preferably 200 占 퐉 or more and 400 占 퐉 or less.

(2) The thickness H2 of the sealing material is preferably 100 占 퐉 or more and 1000 占 퐉 or less, and more preferably 200 占 퐉 or more and 800 占 퐉 or less.

(3) The thickness H3 of the element mounting substrate is preferably 100 占 퐉 or more and 3000 占 퐉 or less, and more preferably 300 占 퐉 or more and 2000 占 퐉 or less.

The thickness H1 to the thickness H3 may be, for example, an average thickness.

By satisfying all of the above conditions (1) to (3) in the dimensions of the semiconductor package, it is possible to reduce warpage in the thin semiconductor package. That is, when the element mounting board 108 or the molding resin layer 120 becomes a thin layer, the semiconductor package tends to cause warpage residue at the time of mounting. On the other hand, in the present embodiment, it is also possible to reduce the flexural residual at the time of mounting even in such a thin semiconductor package.

(Discretization process)

Next, as shown in Fig. 3A, a solder bump 128 is formed on the opposite surface side of the element mounting board 108. Next, as shown in Fig. Thereafter, as shown in Fig. 3 (b), the semiconductor chip 116 is divided into pieces by a dicing saw 130 or the like. For example, dicing is performed along the dicing region 112 shown in Fig. 2 to separate the molded semiconductor chips 116 into pieces. Thereby, the semiconductor device 100 can be obtained.

Since the semiconductor device 100 according to the present embodiment is sealed using the above specific epoxy resin composition, the warpage is suppressed even after disconnection, and the heat resistance, solder crack resistance, resistance to temperature cycling, moisture resistance reliability And so on.

In addition, an electronic device can be obtained by mounting the semiconductor device 100 on a main board or the like.

&Lt; Second Embodiment &gt;

In the first embodiment, a method of manufacturing a semiconductor device called a "MAP method" has been described. However, the epoxy resin composition for sealing may be applied to an electronic component module (sometimes referred to as a package or PKG) It can also be applied.

That is, in Patent Document 7, an example of a vehicle-mounted single-surface sealed electronic component module is shown, and electronic components are mounted on one side of the circuit board and electrically connected to the terminals of the lead frame. The other side of the circuit board is bonded to the heat sink through the adhesive layer. An attempt has been made to prevent peeling by a design of a module structure by disclosing a molding package in which terminals of these circuit boards, electronic parts, heat sinks, and lead frames are sealed by a molding resin.

However, in the above-described electronic component, when the size of the electronic component is increased, the influence of thermal stress or the like is increased, and the electronic component itself is warped to cause peeling at each interface formed between the molding resin and the other member . As a method for solving such a problem, there is a method of lowering the coefficient of linear expansion of the sealing resin and other members (for example, a heat sink or a circuit board) by lowering the linear expansion coefficient of the molding resin, . As a method of lowering the linear expansion coefficient of the molding resin, there is a method of increasing the content of the inorganic filler, but there is a problem that the melt viscosity is increased and the fluidity is deteriorated.

That is, in the present embodiment, an epoxy resin composition containing a specific silicone resin is applied at the time of manufacturing such an electronic component module. As a result, the coefficient of linear expansion can be set in an appropriate range without causing a high melt viscosity or a low fluidity, and as a result, warping as a whole of the electronic component can be suppressed.

<Electronic component module>

4 is a longitudinal sectional view showing an example of the electronic component module of the present embodiment.

The electronic component module 1 shown in Fig. 4 is a vehicle-mounted electronic control device mounted on, for example, a transmission room or the like of an automobile and controlling the operation of the transmission. As shown in Fig. 4, the electronic component module 1 mainly includes a heat sink 5, A lead frame terminal 2, a molding resin (sealing epoxy resin) 8, a circuit board 3, and the like.

The circuit board 3 is made of, for example, bismaleimide triazine resin excellent in heat resistance and moisture resistance. The circuit board 3 is capable of supplying a current or signal from the outside or outputting a signal to the outside through the lead frame terminal 2 and the wire 6, Electronic control of the transmission or the like is performed by the electronic component 7 mounted on the base 3. Although the bismaleimide triazine resin substrate is exemplified as the circuit board 3 in this embodiment, the circuit board 3 may be composed of a ceramic substrate or the like whose surface is covered with a polyimide resin or the like.

The heat sink 5 is formed, for example, in a plate shape and has a rectangular shape (rectangular shape in plan view) slightly larger than the circuit board 3, and the circuit board 3 and the lead frame terminal And has a function of dissipating the heat generated in the heat exchanger 2 to the outside. The heat sink 5 is made of, for example, a material having high thermal conductivity and easy processing. As a specific material, a sintered body of Al and SiC (Al-SiC), SiC, . The material of the heat sink 5 is not limited to these, and other materials having a heat radiation function may be used. In addition, thickness, size, shape and the like can be variously changed.

The heat sink 5 and the circuit board 3 are adhered to each other by the substrate adhesive 4. The substrate adhesive 4 for bonding the circuit board 3 and the heat sink 5 is made of, for example, a known resin adhesive or the like.

The lead frame terminal 2 is electrically connected to an electrode formed on the circuit board 3, and is made of, for example, a metal material. In the electronic component module 1 of the present embodiment, a plurality of lead frame terminals 2 are arranged around the circuit board 3, and each lead frame terminal 2 is, for example, And is indirectly connected to the electrode of the circuit board 3 through the wire 6. These lead frame terminals 2 are formed by cutting a metallic material formed in a plate shape and each function as a metal terminal (lead frame terminal).

In the present embodiment, the direction orthogonal to the plate surface of the circuit board 3 is defined as the up-and-down direction, and the mounting surface side of the electronic component 7 is directed upward and the heat sink 5 side is downward.

The molding resin (sealing resin) 8 is provided on one side of the circuit board 3, the electronic component 7, the heat sink 5, and the lead frame terminal 2 (on the side of the circuit board 3) The electronic component 7 and the circuit board 3 and the junction between the circuit board 3 and the other member are protected.

As this molding resin (sealing resin) 8, an epoxy resin composition containing the specific silicone resin shown as the first embodiment can be applied. As a result, the coefficient of linear expansion can be set in an appropriate range without causing a high melt viscosity or a low fluidity, and consequently, warping as a whole of the electronic component module 1 can be suppressed.

The entire side and the whole side surface of the circuit board 3 on the mounting surface side are covered with the molding resin 8 and the side edge portion of the substrate adhesive 4 covering the surface of the circuit board 3 is also covered with the molding resin 8 Respectively. Thus, the circuit board 3 is sealed by the molding resin 8 and the substrate adhesive 4. [ The entire outer periphery of the heat sink 5 is also covered with the molding resin 8 so that the joint portion formed by joining the lead frame terminal 2 and the heat sink 5 can be molded resin 8). When the electronic component module 1 is mounted on the transmission part, the liquid such as the ATF oil is supplied to the circuit board (not shown), and the circuit board 3 is sealed by the molding resin 8, 3) and the electronic component (7).

In the present embodiment, the electronic component of the present invention is not limited to the case described in the above description, but may be applied to various semiconductor packages of one side sealing type. For example, a ball grid array (BGA) , Quad flat-packed logic (QFN), and matrix, array, package, ball grid array (MAPBGA). In addition to the single-sided encapsulation package, a dual in-line package (DIP), a plastic lead mount chip carrier (PLCC), a quad flat package (QFP), a roasted file quad flat package ), Small Outline Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package ), TO-220 packages that incorporate power-system devices such as a package that is applied to memory or logic devices such as a chip-size package (CSP), a chip-stacked chip-size package, And can be preferably applied.

The semiconductor device manufacturing method and semiconductor device of the present invention have been described above, but the present invention is not limited thereto.

For example, an optional component capable of exhibiting the same function may be added to the epoxy resin composition for sealing used in the method for manufacturing a semiconductor device of the present invention.

The constitution of each part of the electronic component apparatus of the present invention may be replaced with any one capable of exhibiting the same function, or an arbitrary constitution may be added.

The present invention also includes the following aspects.

[1-1]

(A) an epoxy resin,

(B) a curing agent,

(C) a silicone resin,

(D) an inorganic filler,

(E) Curing accelerator

Lt; / RTI &gt;

Wherein the silicone resin (C) is a methylphenyl-type thermoplastic silicone resin and has a repeating structural unit represented by the following general formulas (a), (b), (c) and (d)

Epoxy resin composition for sealing.

[Chemical Formula 22]

(Wherein * represents a bond to Si atom in another repeating structural unit or the same repeating structural unit, R ^1a and R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, and they may be the same or different. The content of the phenyl group bonded to the Si atom is 50 mass% or more in one molecule, and the content of the OH group bonded to the Si atom is less than 0.5 mass% in one molecule).

[1-2] The epoxy resin composition for sealing according to [1-1], wherein the silicone resin (C) further comprises a repeating structural unit represented by the following formulas (e) and (f).

(23)

(Wherein * represents a bond to a Si atom in another repeating structural unit or the same repeating structural unit, and R ^1e represents a methyl group or a phenyl group.) The content of the hydrogen atom bonded to the Si atom is less than 0.5 mass% in one molecule. )

[1-3] The epoxy resin composition according to [1-1] or [1-2], wherein the silicone resin (C) has a softening point of 60 ° C. or more and 100 ° C. or less and a number average molecular weight of 1,000 or more and 10,000 or less. Composition.

[1-4] The epoxy resin composition according to any one of [1-1] to [1-3], wherein the content of the silicone resin (C) in the total epoxy resin composition for sealing is 5 mass% .

[1-5] The epoxy resin composition according to any one of [1] to [5], wherein the epoxy resin (A) is at least one selected from biphenyl type epoxy resin, phenol aralkyl type epoxy resin, trisphenol methane type epoxy resin, bisphenol type epoxy resin, and anthracene type epoxy resin [ The epoxy resin composition for sealing according to any one of [1-1] to [1-4].

[1-6] The epoxy resin composition for sealing according to any one of [1-1] to [1-5], wherein the curing agent (B) is a phenol-based curing agent.

[1-7] The epoxy resin composition for sealing according to [1-6], wherein the phenolic curing agent comprises at least one of a phenol aralkyl resin or a phenol resin having a trisphenol methane skeleton.

[1-8] The curing accelerator according to any one of [1-1] to [1-7], wherein the curing accelerator (E) is at least one selected from the compounds represented by the following general formulas (1) Epoxy resin composition for sealing.

&Lt; EMI ID =

R ² , R ³ , R ⁴ and R ⁵ represent an aromatic group or an alkyl group, A represents a group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group; AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring, x represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, y is a number from 1 to 3, z is a number from 0 to 3, and x = y.

(25)

(Wherein R ⁶ is an alkyl group having 1 to 3 carbon atoms and R ⁷ is a hydroxyl group, a is a number of 0 to 5, and b is a number of 0 to 4.)

(26)

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an organic group having an aromatic ring or a heterocyclic ring (hereinafter referred to as an organic group having an aromatic ring or a heterocyclic ring) , Or an aliphatic group, and may be the same or different from each other. In the formula, R ¹² is an organic group which is bonded to the groups Y ² and Y ^{3. In the} formulas, R ¹³ represents an organic group which is 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 bind to silicon atoms to form a chelate structure Y ⁴ and Y ⁵ are proton Y ² and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure, R ¹² and R ¹³ may be the same or different, and Y ² , Y ^3, Y ^4, and Y ⁵ are the same or different from each other to be It is. Z ¹ is an organic group, or an aliphatic group having an aromatic ring or a heterocyclic ring.)

[1-9] An epoxy resin composition for semiconductor encapsulation, which comprises the epoxy resin composition for sealing according to any one of [1-1] to [1-8].

[1-10] An electronic device characterized by comprising a cured product of an epoxy resin composition for semiconductor encapsulation according to [1-9] as a sealing resin.

Example

Next, a specific embodiment of the present invention will be described.

The present invention is not limited to the description of these examples.

1. Preparation of raw materials

First, raw materials used in the epoxy resin compositions for sealing in each of Examples and Comparative Examples are shown below.

Unless otherwise stated, the blending amount of each component is referred to as "part by mass".

(Components used in Examples 1 to 15 and Comparative Examples 1 to 5 are shown below.

Epoxy resin as component (A):

Epoxy resin 1: phenol aralkyl type epoxy resin (trade name "NC-3000L &quot;, manufactured by Nippon Kayaku Co., Ltd.) having an epoxy equivalent of 276 g / eq and a biphenylene skeleton having a softening point of 52 캜. In the general formula (4), R ¹⁴ to R ¹⁵ are hydrogen atoms.

Epoxy resin 2: A biphenyl-type epoxy resin (trade name "YX-4000K &quot;, manufactured by Mitsubishi Kagaku Co., Ltd.) having an epoxy equivalent of 185 g / eq and a melting point of 108 캜. In the general formula (5), R ¹⁶ , R ¹⁷ , R ²² and R ²³ are methyl groups, and R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are hydrogen atoms.

Epoxy resin 3: phenol aralkyl type epoxy resin (trade name "NC-2000 &quot;, manufactured by Nippon Kayaku Co., Ltd.) having an epoxy equivalent of 238 g / eq and a phenylene skeleton having a softening point of 52 캜. In the general formula (6), R ²⁴ and R ²⁵ are hydrogen atoms.

Epoxy resin 4: A trisphenol methane-type epoxy resin (trade name "1032H-60" manufactured by Mitsubishi Kagaku Co., Ltd.) having an epoxy equivalent of 171 g / eq and a softening point of 59 캜. In the general formula (7), R ²⁶ is a hydrogen atom.

Epoxy resin 5: bisphenol A type epoxy resin (trade name "Epicoat YL6810 &quot;, manufactured by Mitsubishi Chemical Corp.) having an epoxy equivalent of 172 g / eq and a softening point of 45 캜. In the general formula (8), R ²⁷ is a hydrogen atom.

Epoxy resin 6: An anthracene skeleton type epoxy resin having an epoxy equivalent of 168 g / eq and a softening point of 115 占 폚 (trade name "Epikote YL7310", manufactured by Mitsubishi Kagaku). In the general formula (9), R &lt; ²⁸ &gt; is a hydrogen atom.

(B) is a phenolic curing agent:

Phenolic curing agent 1: A phenol aralkyl resin having a biphenylene skeleton having a hydroxyl group equivalent of 198 g / eq and a softening point of 64.5 DEG C (trade name "GPH-65", manufactured by Nippon Kayaku Co., Ltd.). In the general formula (13), R ⁴⁷ is 4,4'-dimethylenebiphenyl.

Phenol-based curing agent 2: phenol resin having a hydroxyl group equivalent of 97 g / eq and a trisphenol-methane skeleton having a softening point of 110 ° C (trade name "MEH-7500" manufactured by Meiwa Kasei Co., Ltd.). In the general formula (13), R ⁴⁷ is hydroxyphenylmethylene.

Phenolic curing agent 3: A phenol aralkyl resin having a phenylene skeleton having a hydroxyl equivalent of 175 g / eq and a softening point of 66.5 DEG C (trade name: "MEH-7800SS &quot;, manufactured by Meiwa Kasei Co., Ltd.). In the general formula (13), R ⁴⁷ is p-xylylene.

(27)

(D), inorganic filler:

Inorganic filler 1: fused spherical silica (trade name "FB560 ", manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter 30 m). The average particle diameter in the present invention was measured using a laser diffraction scattering type particle size distribution analyzer SALD-7000 manufactured by Shimadzu Corporation.

Inorganic filler 2: fused spherical silica (trade name "SO-25R" manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm).

Curing accelerator which is component (E):

As the curing accelerator 1, a curing accelerator represented by the following formula (14) was prepared.

(28)

[Synthesis method of curing accelerator 1]

37.5 g (0.15 mol) of 4,4'-bisphenol S and 100 ml of methanol were introduced into a separable flask equipped with a stirrer, and dissolved with stirring at room temperature. To 50 ml of methanol, 4.0 g ) Was added to the solution. Subsequently, a solution prepared by dissolving 41.9 g (0.1 mole) of tetraphenylphosphonium bromide in 150 ml of methanol was added. Stirring was continued for a while, and 300 ml of methanol was added, and then the solution in the flask was added dropwise to a large amount of water with stirring to obtain a white precipitate. The precipitate was filtered and dried to obtain curing accelerator 1 as a white crystal.

As the curing accelerator 2, a curing accelerator represented by the following formula (15) was prepared.

[Chemical Formula 29]

[Synthesis method of curing accelerator 2]

12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide and 100 ml of methanol were introduced into a separable flask equipped with a stirrer and a cooling tube, and stirred to uniformly dissolve . When sodium hydroxide solution in which 1.60 g (0.04 ml) of sodium hydroxide is dissolved in 10 ml of methanol is slowly dropped in the flask, crystals precipitate. The precipitated crystals were filtered, washed with water and vacuum-dried to obtain Curing Accelerator 2.

As the curing accelerator 3, a curing accelerator represented by the following formula (16) was prepared.

(30)

[Synthesis method of curing accelerator 3]

249.5 g of phenyltrimethoxysilane and 384.0 g of 2,3-dihydroxynaphthalene were added to and dissolved in a flask containing 1800 g of methanol, followed by dropwise addition of 231.5 g of a 28% sodium methoxide-methanol solution under stirring at room temperature . Further, a solution prepared by dissolving 503.0 g of tetraphenylphosphonium bromide prepared in advance in 600 g of methanol is added dropwise with stirring at room temperature to precipitate crystals. The precipitated crystals were filtered, washed with water and vacuum-dried to obtain Curing Accelerator 3 of a peach white color crystal.

As the curing accelerator 4, a compound obtained by adding 1,4-benzoquinone and triphenylphosphine represented by the following formula (17) was prepared.

(31)

[Synthesis method of curing accelerator 4]

6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 ml of acetone were introduced into a separable flask equipped with a condenser and a condenser, and the mixture was reacted at room temperature under stirring. The precipitated crystals were washed with acetone, filtered, and dried to obtain hardening accelerator 4 of dark green crystals.

(Silane coupling agent)

As the silane coupling agent 1, N-phenyl-3-aminopropyltrimethoxysilane (trade name "KBM-573", manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared.

Silicone Resin (C): The following silicone resins 1 to 7 were washed with water at 100 占 폚 for 2 hours, sufficiently dried and then used.

Silicone resin 1: methylphenyl silicone resin having a phenyl group content of 55 mass% bonded to Si atom, 0.3 mass% of OH group bonded to Si atom and 0.1 mass% of hydrogen atom bonded to Si atom (synthesized by the following synthesis method). Number average molecular weight: 2900, softening point: 90 DEG C)

[Synthesis method of silicone resin 1]

87.0 g (0.39 mol) of phenyltriclorosilane, 45.2 g (0.18 mol) of diphenyldichlorosilane, 37.4 g (0.25 mol) of methyltrichlorosilane, 0.5 g of methyltrimethoxysilane were added to a 1 L flask equipped with a stirrer, 23.0 g (0.18 mol) of dimethyldichlorosilane and 150 g of toluene were introduced, and the mixture was heated to an internal temperature of 40 DEG C in an oil bath. 64 g (2 mol) of methanol was introduced into a dropping funnel, and the mixture was added dropwise to the flask while stirring for 1 hour, and the reaction was allowed to proceed while removing hydrogen chloride gas generated during the alkoxylation reaction. After completion of the dropwise addition, agitation was further continued at an internal temperature of 40 DEG C for 1 hour. Next, 12 g (0.7 mol) of water was introduced into the dropping funnel, and the solution was added dropwise to the flask with stirring for 1 hour to progress the reaction while removing the hydrogen chloride gas generated during the hydrolysis and condensation reaction from the system. After completion of the dropwise addition, stirring was further continued at an internal temperature of 40 캜 for 1 hour to progress the dehydration condensation reaction of the produced silanol groups, followed by aging. Then, by distillation under reduced pressure, toluene, excess methanol, unreacted water, Hydrogen was removed to obtain 102 g of solid silicone resin 1.

Silicone Resin 2: methylphenyl silicone resin (manufactured by Toray Dow Corning Co., Ltd.) having a phenyl group content of 57 mass% bonded to Si atom, a content of OH group bonded to Si atom of 0.3 mass% and a content of hydrogen atom bonded to Si atom of 0.07 mass% 233 FLAKE ", number average molecular weight 1500 (weight average molecular weight 2200), softening point 80 DEG C)

Silicone resin 3: methylphenyl silicone resin (manufactured by Toray Dow Corning Co., Ltd.) having a phenyl group content of 54 mass% bonded to Si atom, a content of OH group bonded to Si atom of 0.3 mass%, and a content of hydrogen atom bonded to Si atom of 0.06 mass% Quot; 249 FLAKE ", number average molecular weight 1600 (weight average molecular weight 3400), softening point 85 DEG C)

Silicone resin 4: methylphenyl silicone resin (manufactured by Toray Dow Corning Co., Ltd.) having a phenyl group content of 45 mass% bonded to Si atom, a content of OH group bonded to Si atom of 0.3 mass% and a content of hydrogen atom bonded to Si atom of 0.06 mass% Quot; 220 FLAKE ", number average molecular weight 3000, softening point 100 DEG C)

5: a dimethyl type silicone rubber (trade name "CF2152 ", trade name, manufactured by Toray Dow Corning Co., Ltd.) having a phenyl group content of 0 mass% bonded to a Si atom and a content of OH groups bonded to Si atoms of 0.1 mass%

Silicone Resin 6: methylphenyl type silicone resin (trade name: "217FLAKE ", product number: 217 FLAKE, number average molecular weight: 1100, softening point: 1100) having a phenyl group content of 57 mass% bonded to a Si atom and an OH group content of 6 mass% 75 ° C)

Silicone Resin 7: Propylphenyl type silicone resin (trade name: "SH6018 ", trade name, manufactured by Toray Dow Corning Co., Ltd.) having a phenyl group content of 54 mass% bonded to a Si atom and an OH group content of 0.3 mass% Softening point 100 캜)

(Releasing agent)

As release agent 1, carnauba (Nikko Pine Co., Ltd., trade name "Nikko Carnauba") was prepared.

(coloring agent)

As the colorant 1, carbon black (manufactured by Mitsubishi Kagaku Co., Ltd., trade name "MA600") was prepared.

2. Preparation of Epoxy Resin Composition for Sealing

[Example 1]

(8.00 parts by mass), phenol-based curing agent 1 (5.00 parts by mass), inorganic filler 1 (75.00 parts by mass), inorganic filler 2 (10.00 parts by mass), curing accelerator 4 (0.20 parts by mass), silane coupling agent (0.20 parts by mass), Release Agent 1 (0.20 parts by mass), Silicone Resin 1 (1.00 parts by mass) and Colorant 1 (0.40 parts by mass) were weighed and mixed using a mixer. And two rolls at 25 DEG C to obtain a kneaded product. Then, this kneaded product was cooled and pulverized to obtain an epoxy resin composition for sealing of Example 1.

[Examples 2 to 15 and Comparative Examples 1 to 5]

Epoxy resin compositions for sealing of Examples 2 to 15 and Comparative Examples 1 to 5 were obtained in the same manner as in Example 1 except that kinds and blend amounts of the raw materials were changed as shown in Tables 1 and 2.

3. Evaluation

The epoxy resin compositions for sealing in each of the examples and comparative examples were evaluated by the following methods.

3-1. Evaluation of Spiral Flow (SF)

A mold for spiral flow measurement according to ANSI / ASTM D 3123-72 was charged at 175 占 폚, an injection pressure of 6.9 MPa, and a holding time of 120 (KTS-15) using a low-pressure transfer molding machine (KTS-15 manufactured by Kotakiseki Co., Sec, the epoxy resin composition for sealing of each of the examples and the comparative examples was injected, and the flow field (flow length) was measured to obtain spiral flow.

The spiral flow is a parameter of fluidity, and a large value is good fluidity. In order to apply the invention to a semiconductor package for a vehicle and to seal the module, it is preferable that the distance is 100 cm or more.

3-2. Evaluation of melt viscosity

The sample was put into a cylinder with a flow rate tester (manufactured by Shimadzu Seisakusho Co., Ltd., trade name "CFT-500D"), and the plunger was lowered at a pressure of 40 kgf / cm ^{2. The} sample was passed through a nozzle die 1 mm). The viscosity of the solution was measured. The unit is Pa · s.

3-3. Evaluation of the glass transition temperature (hereinafter referred to as Tg), the linear expansion coefficient? 1 (the linear expansion coefficient in the temperature region below Tg),? 2 (the linear expansion coefficient in the temperature region above Tg)

Each of the epoxy resin compositions for sealing according to each of the examples and comparative examples was molded by using a transfer molding machine (50 tons transfer press manufactured by Tosoh Corporation) at a mold temperature of 175 占 폚, an injection pressure of 6.9 MPa, a curing time of 90 seconds, A 4 mm x 3 mm test piece was molded and post cured at 175 캜 for 4 hours. The glass transition temperature, the coefficient of linear expansion? 1 and the coefficient of linear expansion? 2 of the test piece were measured using a thermomechanical analyzer (trade name: "TMA-120" manufactured by Seiko Denshi Co., Ltd., temperature rise rate 5 ° C./min). Tg is the intersection of the tangent line at 30 캜 and 280 캜. The unit of linear expansion coefficient is (/ C).

3-4. Evaluation of warpage

(Thick package)

(Molding part 75 mm x 65 mm, thickness 6.7 mm, thickness: 1.6 mm) was molded by using a transfer molding machine (30 ton transfer press manufactured by Gottsu Seiki KK) at a mold temperature of 175 ° C, an injection pressure of 6.9 MPa, and a curing time of 2 minutes. The circuit board was made of a FR-4 (Flame Retardant Type 4) substrate of 55 mm × 55 mm and a thickness of 1.6 mm, a heat sink of 60 mm × 60 mm, an aluminum material of 1.5 mm in thickness, a copper lead frame, Line) was molded to obtain a semiconductor device. After 10 obtained semiconductor devices were cooled to room temperature, the displacement in the height direction was measured in a diagonal direction of the molding portion of the semiconductor device using a surface roughness meter, and the value with the greatest difference in deviation was defined as the amount of deflection. Further, after post-curing at 175 ° C for 4 hours, the amount of warpage was measured in the same manner. The unit is μm. And when it was 100 m or more, it was judged to be defective.

(Thin package)

Semiconductor devices each having a size of 10 mm x 9 mm and a thickness of 294 m were allocated and arranged in units of 14 mm x 14 mm arranged in 4 x 13 (length x width) on a multi-faceted printed circuit board having a thickness of 300 m The substrate on which the element was mounted was placed in a mold of a compression molding machine (compression molding press manufactured by TOWA CO., LTD.), The sealing material was put in a cavity for forming the sealing portion of the mold and compression molding was carried out for 2 minutes at a temperature of 175 캜 Thereby obtaining a sealed substrate.

The obtained sealing substrate had a size of the sealing portion of 55 mm x 190 mm (length x width) and a thickness of the sealing portion of 500 m.

After the obtained sealed sealing substrate was cooled to room temperature, the displacement in the height direction was measured in a diagonal direction of the molded part of the sealing substrate using a surface roughness meter, and the largest value of the displacement vehicle was defined as a deflection amount.

The obtained sealing substrate was cut using a dicing saw (manufactured by DISCO), and divided (diced) for each unification unit. A plurality of discrete semiconductor devices were obtained. The displacement of the semiconductor device in the height direction was measured by using a surface roughness meter, and the maximum value of the displacement vehicle was set as the bending amount.

3-5. Evaluation of solder crack resistance

(TEG ELEMENT GROUP) chip (6.0 mm x 6.0 mm x 0.35 mm thick) having an electrode pad made of aluminum was placed in an 80 pQFP (copper lead frame, package external number: 14 mm x 20 mm x 2 mm thickness, 6.5 mm), and the aluminum electrode pad of the TEG chip and the electrode pad of the substrate were wire-bonded using copper wire 4N (copper purity 99.99 wt%). Using the low-pressure transfer molding machine ("GP-ELF" manufactured by Daiichi Seiko Co., Ltd.) under the conditions of a mold temperature of 175 ° C, an injection pressure of 9.8 MPa and a curing time of 70 seconds, Molded with the epoxy resin composition for encapsulation of any one of Examples 1 to 5 and post-cured at 175 캜 for 4 hours to obtain 80 pQFP.

Six 80pQFPs were subjected to a humidification treatment at 60 DEG C and a relative humidity of 60% for 168 hours, followed by an IR reflow treatment at 260 DEG C for 10 seconds. The peeling and cracks in the package were confirmed by an ultrasonic flaw detector (trade name "mi-scopehyper II" manufactured by Hitachi Genki Fine-Tec Co., Ltd.), and no cracks, no peeling on the chip circuit surface, And the number of failed semiconductor devices was counted.

3-6. Evaluation of temperature cycle resistance

Ten packages of the same type as those of the bending evaluation were prepared and packaged in a temperature cycle tester (trade name: THERMAL SHOCK CHAMBER TSA-101S, manufactured by ESPEC Co., Ltd.) Cycle, and subjected to a 1000-cycle temperature cycle treatment. The presence or absence of cracking in the inside of the semiconductor device was confirmed by an ultrasonic flaw detector (trade name "mi-scope hyper II ", manufactured by Hitachi Genki Fine Tec Co., Ltd.), and there was no crack, no peeling on the chip circuit surface, The number of failed semiconductor devices was counted as the acceptance that the area was 5% or less.

3-7. Assessment of Intrinsic Safety (HAST)

A TEG (TEST ELEMENT GROUP, one chip three circuit) chip (3.0 x 3.5 mm) having aluminum electrode pads was mounted on an island portion of 16 pSOP (copper lead frame, package external number: 7.2 mm x 11.5 mm x 1.95 mm thickness) , And the aluminum electrode pads of the TEG chip and the electrode pads of the substrate were wire-bonded using a copper wire 4N (copper purity 99.99 wt%) so as to be daisy-chain connected. Using the low pressure transfer molding machine (trade name: KTS-125, manufactured by Gottsu Seiki Co., Ltd.) under the conditions of a mold temperature of 175 ° C, an injection pressure of 6.9 MPa and a curing time of 2 minutes, And a sealing epoxy resin composition for a sealing of any one of Comparative Examples 1 to 5 to form a 16pSOP package. This package was post-cured at 175 DEG C for 4 hours to obtain a semiconductor device.

HAST test was carried out in accordance with IEC68-2-66 using six 16pSOPs. The test conditions were as follows: 140 ° C. 85% RH, DC 20 V, 40 hours, 80 hours, 120 hours, 160 hours, 200 hours, and 240 hours to detect the open failure of the circuit, (10 packages x 3 circuits = 30 circuits are detected), and an average failure time (MTTF: Mean Time To Failure, hereinafter referred to as MTTF) was calculated to obtain an average value of six 16pSOPs.

3-8. Evaluation of internal combustion test

A test piece (127 mm x 12.7 mm x 3.2 mm) was molded at a molding temperature of 175 DEG C, a pressure of 6.9 MPa, and a curing time of 120 seconds using a transfer molding machine (30 ton transfer press manufactured by KOTAKI SEIKI Co., Ltd.) , And post-curing was carried out under the condition of 4 hours to obtain a test piece. The test piece was subjected to a combustion test according to the UL-94 test method, and the total of the five test pieces after the test piece was evaluated as the total test piece time.

The evaluation results of the epoxy resin compositions for sealing in each of the examples and comparative examples thus obtained are shown in the following Tables 1 and 2, respectively.

[Table 1]

[Table 2]

As shown in Tables 1 and 2, the epoxy resin composition for sealing according to each of the examples containing (C) silicone resin had a low viscosity and a high flow characteristic (spiral flow), and the epoxy resin composition for sealing The cargo exhibits excellent balance with a high glass transition temperature (Tg), low thermal expansion coefficient (? 2) and sufficient flame resistance, and furthermore, the semiconductor device which is sealed with the epoxy resin composition for sealing has a small room temperature bending, Resistance to solder cracking, resistance to temperature cycling, and moisture resistance reliability).

On the other hand, in Comparative Example 1, (C) silicone resin was not contained and instead, the amount of inorganic filler used was increased, so that high Tg,? 1,? 2 and flexural behavior were good, but the flowability, melt viscosity, , The temperature cycle resistance and the moisture resistance reliability were inferior. In Comparative Example 2 and Comparative Example 3, since the silicone resin having a phenyl group bonded to the Si atom contained in one molecule is less than 50 mass% is used, the fluidity is the same as in Examples, but Tg,? 1,? 2, The results were poor resistance to solder cracking, resistance to temperature cycling, and moisture resistance. In Comparative Example 4, since the methylphenyl type silicone resin containing a large amount of OH groups bonded to Si atoms was used, the rise in the melt viscosity was large, and the result was poor resistance to solder cracking, resistance to temperature cycle, and moisture resistance. In Comparative Example 5, since the propylphenyl-type silicone resin was used, flowability and warpage control characteristics were good, but the flame retardancy was poor.

This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2013-145061, filed on July 11, 2013, the entire disclosure of which is incorporated herein by reference.

Claims (9)

A preparation step of preparing an element mounting board having a plurality of package areas partitioned by a dicing area;
Mounting a semiconductor chip on each of the package areas of the element mounting board;
A molding step of simultaneously molding the semiconductor chip with an epoxy resin composition for sealing,
A dicing step is performed along the dicing region to separate the semiconductor chips into individual pieces
/ RTI &gt;
The above-mentioned epoxy resin composition for sealing,
(A) an epoxy resin,
(B) a curing agent,
(C) a silicone resin,
(D) an inorganic filler,
(E) Curing accelerator
/ RTI &gt;
Wherein the silicone resin (C) is a methylphenyl-type thermoplastic silicone resin and has a repeating structural unit represented by the following general formulas (a), (b), (c) and (d) &Lt; / RTI &gt;
[Chemical Formula 1]

(Wherein * represents a bond to Si atom in another repeating structural unit or the same repeating structural unit, R ^1a and R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, and they may be the same or different. The content of the phenyl group bonded to the Si atom is 50 mass% or more in one molecule, and the content of the OH group bonded to the Si atom is less than 0.5 mass% in one molecule). The method according to claim 1,
Wherein the (C) silicone resin further has a repeating structural unit represented by the following general formulas (e) and (f).
(2)

(Wherein * represents a bond to a Si atom in another repeating structural unit or the same repeating structural unit, and R ^1e represents a methyl group or a phenyl group.) The content of the hydrogen atom bonded to the Si atom is less than 0.5 mass% in one molecule. ) The method according to claim 1 or 2,
Wherein the softening point of the silicone resin (C) is 60 占 폚 or more and 100 占 폚 or less and the number average molecular weight is 1000 or more and 10000 or less. The method according to any one of claims 1 to 3,
Wherein the content of the silicone resin (C) in the total epoxy resin composition for sealing is not less than 0.1% by mass and not more than 5% by mass. The method according to any one of claims 1 to 4,
Wherein the epoxy resin (A) is at least one selected from the group consisting of a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a trisphenol methane type epoxy resin, a bisphenol type epoxy resin and an anthracene type epoxy resin. The method according to any one of claims 1 to 5,
Wherein the (B) curing agent is a phenol-based curing agent. The method of claim 6,
Wherein the phenolic curing agent comprises at least one of a phenol aralkyl resin or a phenol resin having a trisphenol methane skeleton. The method according to any one of claims 1 to 7,
Wherein the curing accelerator (E) is at least one selected from the compounds represented by the following general formulas (1) to (3).
(3)

R ² , R ³ , R ⁴ and R ⁵ represent an aromatic group or an alkyl group, A represents a group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group; AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring, x represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, y is a number from 1 to 3, z is a number from 0 to 3, and x = y.
[Chemical Formula 4]

(Wherein R ⁶ is an alkyl group having 1 to 3 carbon atoms and R ⁷ is a hydroxyl group, a is a number of 0 to 5, and b is a number of 0 to 4.)
[Chemical Formula 5]

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an organic group having an aromatic ring or a heterocyclic ring (hereinafter referred to as an organic group having an aromatic ring or a heterocyclic ring) , Or an aliphatic group, and may be the same or different from each other. In the formula, R ¹² is an organic group which is bonded to the groups Y ² and Y ^{3. In the} formulas, R ¹³ represents an organic group which is 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 bind to silicon atoms to form a chelate structure Y ⁴ and Y ⁵ are proton Y ² and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure, R ¹² and R ¹³ may be the same or different, and Y ² , Y ^3, Y ^4, and Y ⁵ are the same or different from each other to be It is. Z ¹ is an organic group, or an aliphatic group having an aromatic ring or a heterocyclic ring.) A semiconductor device obtained by the manufacturing method according to any one of claims 1 to 8.

Images