JP2022021900A - Encapsulating resin composition and electronic component equipment - Google Patents

Abstract

To provide a sealing resin composition that can prevent a support from warping, and an electronic component device produced therewith.SOLUTION: A sealing resin composition contains an epoxy resin and a curing agent and has a stress index of 220 GPa×ppm/°C or lower in a cured state.SELECTED DRAWING: None

Description

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

In recent years, as a semiconductor mounting technology using a resin encapsulant, a method called a wafer level package (WLP) has been studied. Unlike the flip-chip type method in which the semiconductor chip and the wiring board are connected to each other and packaged, this method does not require a wiring board, so that the package can be made thinner. Further, since a plurality of semiconductor chips are arranged on a support, sealed together, and then individualized for each package, they are attracting attention as a mounting technology having excellent productivity.

In WLP, since one side of a support having a relatively large area is sealed with a sealing material, warpage due to curing shrinkage of the sealing material is likely to occur. As a means for suppressing the warp of the support after sealing, an increase in the amount of the filler has been studied (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2013-10940

When the amount of the filler in the encapsulant is increased, the coefficient of thermal expansion of the encapsulant decreases and the difference from the coefficient of thermal expansion of the support becomes smaller, and the warp of the support is suppressed, but the support is large. In some cases, the effect of suppressing warpage could not be sufficiently obtained when the area was increased. Therefore, there is a demand for the development of a sealing material capable of suppressing the warp of the support from a viewpoint other than increasing the amount of the filler.
In view of the above circumstances, it is an object of the present invention to provide a sealing resin composition capable of suppressing warpage of a support, and an electronic component device obtained by using the same.

The means for solving the above problems include the following embodiments.
<1> A resin composition for encapsulation containing an epoxy resin and a curing agent and having a stress index of 220 GPa × ppm / ° C. or less in a cured state.
<2> The sealing resin composition according to <1>, wherein the difference between the Tg when molded and cured at 130 ° C. and the Tg when molded and cured at 175 ° C. is within 10 ° C.
<3> The sealing resin composition according to <1> or <2>, wherein the curing agent contains a triphenylmethane type phenol resin.
<4> The sealing resin composition according to any one of <1> to <3>, further comprising a silicone compound.
<5> The sealing resin composition according to any one of <1> to <4>, wherein the epoxy resin contains an epoxy resin having an unsubstituted biphenyl structure.
<6> The cured product of the sealing resin composition according to any one of <1> to <5>, which seals the support, the element arranged on the support, and the element. And equipped with electronic component equipment.

According to the present invention, there is provided a sealing resin composition capable of suppressing warpage of a support, and an electronic component device obtained by using the sealing resin composition.

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the present invention.

In the present disclosure, the term "process" includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
In the present disclosure, the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. Further, in the numerical range described, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, the content rate or content of each component in the composition is the same when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means the total content or content of.
In the present disclosure, the particle size of each component in the composition refers to a mixture of the plurality of particles present in the composition when a plurality of particles corresponding to each component are present in the composition, unless otherwise specified. Means the value of.

<Plastic composition for encapsulation>
The sealing resin composition of the present disclosure is a sealing resin composition containing an epoxy resin and a curing agent and having a stress index of 220 GPa × ppm / ° C. or less in a cured state.

As a result of the study by the present inventors, the amount of warpage of the support in the state where the layer is formed on one side of the support such as a semiconductor wafer by using the sealing resin composition is the stress of the sealing resin composition. It was found that there was a strong positive correlation with the index value, and that when the stress index was 220 GPa × ppm / ° C or less, the amount of warpage of the support was sufficiently small.

In the present disclosure, the "stress index" is a value expressed by the following formula.
Stress index (GPa x ppm / ° C) = E1 (GPa) x CTE1 (ppm / ° C)

In the above formula, E1 is the bending elastic modulus (GPa) at 25 ° C. of the cured product obtained by molding and curing the sealing resin composition at 175 ° C. Specifically, it is measured by the method described in Examples described later.

In the above formula, CTE1 is an average value (ppm / K) of the linear expansion coefficient (CTE) in the measurement temperature range of 40 ° C. to 80 ° C. of the cured product obtained by molding and curing the sealing resin composition at 175 ° C. Is. Specifically, it is measured by the method described in Examples described later.

As a method of controlling the stress index of the cured product of the sealing resin composition to be 220 GPa × ppm / ° C. or less, triphenylmethane type phenol resin is used as a curing agent, and the sealing resin composition is used. Addition of a silicone compound and the like can be mentioned.
When a triphenylmethane type phenol resin is used as a curing agent, the CTE1 of the cured product tends to decrease, and when a silicone compound is added, the E1 of the cured product tends to decrease. Therefore, the stress index, which is the product of E1 and CTE1, tends to decrease.

The stress index of the cured product of the sealing resin composition is more preferably 210 GPa × ppm / ° C. or less, and further preferably 200 GPa × ppm / ° C. or less, from the viewpoint of suppressing warpage of the support.
The stress index of the cured product of the sealing resin composition may be 150 GPa × ppm / ° C. or higher, 160 GPa × ppm / ° C. or higher, or 170 GPa × ppm / ° C. or higher.

The CTE1 of the cured product obtained by molding and curing the sealing resin composition at 175 ° C. is preferably 20 ppm / ° C. or less, preferably 15 ppm / ° C. or less from the viewpoint of reducing the difference in thermal expansion rate from the substrate. Is more preferable, and 12 ppm / ° C. or less is further preferable. Further, from the viewpoint of reducing the difference in thermal expansion rate from the substrate, it is preferably 3 ppm / ° C. or higher, more preferably 6 ppm / ° C. or higher, and even more preferably 8 ppm / ° C. or higher.

The E1 of the cured product obtained by molding and curing the sealing resin composition at 175 ° C. is preferably 25 GPa or less, more preferably 21 GPa or less, and 19 GPa or less from the viewpoint of reducing stress. Is even more preferable. Further, from the viewpoint of crack prevention, it is preferably 5 GPa or more, more preferably 10 GPa or more, and further preferably 14 GPa or more.

The encapsulating resin composition should have excellent curability at low temperatures when low melting point solder, heat-sensitive materials (temporary fixing film, mold release film, etc.) are used in the encapsulation work. preferable.
Specifically, the difference between the glass transition temperature (Tg) when the sealing resin composition is molded and cured at 130 ° C. and the Tg when molded and cured at 175 ° C. is within 10 ° C. It is preferable, it is more preferably 7 ° C or less, and further preferably 5 ° C or less.

The Tg of the cured product of the sealing resin composition tends to be lower as the molding and curing temperatures are lower. The difference between the Tg when molded and cured at 130 ° C. and the Tg when molded and cured at 175 ° C. is within 10 ° C. that the sealing resin composition is molded and cured at a low temperature (130 ° C.). It means that the curing reaction when cured is sufficiently advanced (that is, the low temperature curing property is good).

As a method for controlling the difference between Tg when molded and cured at 130 ° C. and Tg when molded and cured at 175 ° C. is within 10 ° C., the epoxy resin has an unsubstituted biphenyl structure. The use of epoxy resin can be mentioned.

The Tg of the cured product is measured by the method described in Examples described later.

(Epoxy resin)
The epoxy resin contained in the sealing resin composition is not particularly limited and can be selected according to the desired characteristics of the sealing resin composition and the like.

Specifically, the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. A novolak type epoxy resin (phenol novolak type) which is an epoxidation of a novolak resin obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. Epoxide resin, orthocresol novolak type epoxy resin, etc.); A triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxide resin; a copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained by cocondensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; bisphenol. Diphenylmethane type epoxy resin which is a diglycidyl ether such as A and bisphenol F; biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben type epoxy resin which is a diglycidyl ether of a stilben-based phenol compound; bisphenol Sulfur atom-containing epoxy resin that is a diglycidyl ether such as S; epoxy resin that is an alcoholic glycidyl ether such as butanediol, polyethylene glycol, polypropylene glycol; and a polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid. Glysidyl ester type epoxy resin, which is a glycidyl ester; glycidylamine type epoxy resin, which is obtained by substituting an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, or isocyanuric acid with a glycidyl group; Dicyclopentadiene-type epoxy resin, which is an epoxide of a condensed resin; vinylcyclohexene epoxide, which is an epoxide of an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxide) cyclohexyl-5,5 An alicyclic epoxy resin such as 5-spiro (3,4-epoxy) cyclohexane-m-dioxane; a paraxylylene-modified epoxy resin that is a glycidyl ether of a paraxylylene-modified phenol formaldehyde; a metaxylylene-modified epoxy resin that is a glycidyl ether of a metaxylylene-modified phenol resin. A terpene-modified epoxy resin that is a glycidyl ether of a terpene-modified phenol form; a dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a dicyclopentadiene-modified phenol resin; a cyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin, which is a glycidyl ether of a ring-fragrant ring-modified phenol resin; naphthalene-type epoxy resin, which is a glycidyl ether of a naphthalene ring-containing phenol resin; Type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Aralkyl type epoxy resin obtained by epoxidizing an aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. ; And so on. Further, epoxies of silicone resin, epoxies of acrylic resin and the like can also be mentioned as epoxy resins. These epoxy resins may be used alone or in combination of two or more.

From the viewpoint of the balance between reflow resistance and fluidity, the epoxy resins include biphenyl type epoxy resin, stilben type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, and dicyclopentadiene type epoxy resin. , A triphenylmethane type epoxy resin, a copolymerized type epoxy resin, and an aralkyl type epoxy resin are preferably selected from the group.

Specific examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (II). Among the epoxy resins represented by the general formula (II), the 3,3', ^{5,5'positions} of R8 where the oxygen atom is substituted are the methyl groups at the 4 and 4'positions. , Other R ⁸ is a hydrogen atom YX-4000H (Mitsubishi Chemical Co., Ltd., trade name), all R ⁸ are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, all When R ⁸ is a hydrogen atom and when the position where the oxygen atom is substituted in R ⁸ is the 4 and 4'positions, the 3, 3', 5, 5'positions are methyl groups and the other R ^8s . YL-6121H (Mitsubishi Chemical Co., Ltd., trade name) or the like, which is a mixed product in the case where is a hydrogen atom, is available as a commercially available product.

In formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, all of which may be the same or different. n is an average value and indicates a number from 0 to 10.

Specific examples of the stilbene type epoxy resin include an epoxy resin represented by the following general formula (III). Among the epoxy resins represented by the general formula (III), the 3,3', ^{5,5'positions} of R9 where the oxygen atom is substituted are the methyl groups at the 4 and 4'positions. Yes, the other cases where R ⁹ is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and 3 of R ⁹ 's 3,3', 5, and 5'positions are methyl groups, and 1 ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), which is a mixture of one having a t-butyl group, the other R ⁹ being a hydrogen atom, and all of R ¹⁰ being hydrogen atoms, is commercially available. It is available as an item.

In formula (III), R ⁹ and R ¹⁰ represent hydrogen atoms or monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different. n is an average value and indicates a number from 0 to 10.

Specific examples of the diphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (IV). Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and the positions of R ¹² where the oxygen atom is substituted are set to the 4 and 4'positions 3,3. YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) or the like in which the', 5, 5'position is a methyl group and the other R ¹² is a hydrogen atom is available as a commercially available product.

In formula (IV), R ¹¹ and R ¹² represent hydrogen atoms or monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different. n is an average value and indicates a number from 0 to 10.

Specific examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (V). Among the epoxy resins represented by the general formula (V), the ^3,3'position of R13 when the position where the oxygen atom is substituted is the 4th and 4'positions is the t-butyl group, and 6 , YSLV-120TE (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which the 6'position is a methyl group and the other R ¹³ is a hydrogen atom is available as a commercially available product.

In formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. n is an average value and indicates a number from 0 to 10.

Specific examples of the novolak type epoxy resin include an epoxy resin obtained by epoxidizing a novolak type phenol resin such as a phenol novolak resin, a cresol novolak resin, and a naphthol novolak resin by a method such as glycidyl etherification. Of these, an epoxy resin represented by the general formula (VI) is preferable. Among the epoxy resins represented by the following general formula (VI), all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group, and i = 1, ESCN-190 and ESCN-195 (Sumitomo Chemical Co., Ltd.). , Trade name), all of R ¹⁴ are hydrogen atoms, i = 0 N-770, N-775 (DIC Co., Ltd., trade name), all of R ¹⁴ are hydrogen atoms, i = 0 YDAN-1000-10C (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), which is a styrene-modified phenol novolac type epoxy resin having a certain portion and a portion where i = 1 and R15 is -CH ⁽ CH ₃ ) -Ph, All of R ¹⁴ are hydrogen atoms, i = 1, R ¹⁵ is a methyl group and i = 2, and one of R ¹⁵ is a methyl group and one is a benzyl group. HP-5600 (DIC Co., Ltd., trade name), which is a group-modified cresol novolak type epoxy resin, is available as a commercially available product.

In formula (VI), R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R ¹⁵ represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. i independently represents an integer of 0 to 3. n is an average value and indicates a number from 0 to 10.

Specific examples of the dicyclopentadiene type epoxy resin include an epoxy resin represented by the following general formula (VII). Among the epoxy resins represented by the general formula (VII), HP-7200 (DIC Corporation, trade name) and the like having i = 0 are available as commercial products.

In formula (VII), R ¹⁶ represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. i independently represents an integer of 0 to 3. n is an average value and indicates a number from 0 to 10.

The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane-type phenol resin such as a novolak-type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable, and is represented by the following general formula (VIII). The epoxy resin to be used is more preferable. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name) and EPPN-502H (Nippon Kayaku Co., Ltd., trade name) in which i is 0 and k is 0. Etc. are available as commercial products.

In formula (VIII), R ¹⁷ and R ¹⁸ represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different. i indicates an integer of 0 to 3 independently, and k indicates an integer of 0 to 4 independently. n is an average value and indicates a number from 0 to 10.

The copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound and a phenol compound and an aldehyde compound is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton. .. For example, an epoxy resin obtained by glycidyl etherifying a novolak-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable. Among the epoxy resins represented by the following general formula (IX), NC-7300 (Nippon Kayaku Co., Ltd., trade name) in which R ²¹ is a methyl group, i is 1, j is 0, and k is 0. ) Etc. are available as commercial products.

In the formula (IX), R ¹⁹ to R ²¹ represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different. i is an integer of 0 to 3 independently, j is an integer of 0 to 2 independently, and k is an integer of 0 to 4 independently. l and m are average values, respectively, and are numbers from 0 to 10, and (l + m) indicate numbers from 0 to 10. The end of the epoxy resin represented by the formula (IX) is either one of the following formulas (IX-1) or (IX-2). ^{In the formulas (IX-1) and (IX-2), the definitions of i, j and k in R 19 to} R ²¹ are the same as the definitions of i, j and k in the formula ⁽ IX). Is. n is 1 (when bonded via a methylene group) or 0 (when not bonded via a methylene group).

The epoxy resin represented by the above general formula (IX) includes a random copolymer randomly containing l structural units and m structural units, an alternating copolymer containing alternately, and a copolymer containing regularly. , Block copolymers contained in a block shape and the like. Any one of these may be used alone, or two or more thereof may be used in combination.

Specific examples of the aralkyl type epoxy resin include epoxy resins represented by the following general formulas (X) and (XI).
Among the epoxy resins represented by the following general formula (X), i is 0, R ³⁸ is a hydrogen atom NC-3000S (Nippon Kayaku Co., Ltd., trade name), i is 0, and R ³⁸ . CER-3000 (Nippon Kayaku Co., Ltd., trade name), which is a mixture of an epoxy resin in which is a hydrogen atom and an epoxy resin in which all ^R8s of the general formula (II) are hydrogen atoms at a mass ratio of 80:20, is commercially available. It is available as an item. Among the epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which i is 0, j is 0, and k is 0 is commercially available. It is available as an item.

In formulas (X) and (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R ³⁷ and R ³⁹ to R ⁴¹ represent monovalent organic groups having 1 to 18 carbon atoms, and all of them may be the same or different. i is an integer of 0 to 3 independently, j is an integer of 0 to 2 independently, k is an integer of 0 to 4 independently, and l is an integer of 0 to 6 independently. show. n is an average value, which is a number of 0 to 10 independently.

Regarding ^R8 to ^R21 and ^R37 to R41 in the general formulas ⁽ II) to (XI), "all may be the same or different" means, for example, 8 to 8 in the formula (II). It means that all 88 ^R8s may be the same or different. It also means that the other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ may all be the same or different for each number included in the equation. Further, R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ may be the same or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.
Further, the organic group having 1 to 18 carbon atoms in the general formulas (III) to (XI) is preferably an alkyl group or an aryl group.
Regarding ^R8 to ^R21 and ^R37 to R41 in the general formulas ⁽ II) to (XI), "all may be the same or different" means, for example, 8 to 8 in the formula (II). It means that all 88 ^R8s may be the same or different. It also means that the other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ may all be the same or different for each number included in the equation. Further, R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ may be the same or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.
Further, the organic group having 1 to 18 carbon atoms in the general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

N in the above general formulas (II) to (XI) is an average value, and it is preferable that each is independently in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the curable resin composition during melt molding decreases, filling failure, and deformation of the bonding wire (gold wire connecting the element and the lead). Etc. tend to be suppressed. It is more preferable that n is set in the range of 0 to 4.

From the viewpoint of curing reactivity at low temperature, the epoxy resin preferably contains an epoxy resin having a structure represented by the following general formula (A) (unsubstituted biphenyl structure). The epoxy resin having an unsubstituted biphenyl structure may further have a structure (triphenylmethane structure or the like) other than the unsubstituted biphenyl structure.

In the general formula (A), * represents a bond position with an adjacent atom, and at least one of * represents a bond position with an epoxy-containing group.

Even if the sealing resin composition contains only an epoxy resin having an unsubstituted biphenyl structure as an epoxy resin, an epoxy resin having an unsubstituted biphenyl structure as an epoxy resin and an epoxy resin other than an epoxy resin having an unsubstituted biphenyl structure are used. May include.
When the epoxy resin contains an epoxy resin having an unsubstituted biphenyl structure and an epoxy resin other than the epoxy resin having an unsubstituted biphenyl structure, the proportion of the epoxy resin having the unsubstituted biphenyl structure is 30% by mass or more of the entire epoxy resin. It is preferably 40% by mass or more, more preferably 50% by mass or more.

The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and is preferably 150 g / eq to 500 g / eq. Is more preferable.

When the epoxy resin is a solid, its softening point or melting point is not particularly limited. From the viewpoint of handleability when preparing the sealing resin composition, the temperature is preferably 50 ° C to 130 ° C.

The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring ball method) according to JIS K 7234: 1986.

The content of the epoxy resin in the sealing resin composition is preferably 0.5% by mass to 50% by mass, preferably 2% by mass to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like. % Is more preferable.

(Hardener)
The curing agent contained in the sealing resin composition is not particularly limited and can be selected according to the desired characteristics of the sealing resin composition and the like.

Specific examples of the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polypeptide curing agent, a polyaminoamide curing agent, an isocyanate curing agent, a blocked isocyanate curing agent and the like. From the viewpoint of achieving both curability and pot life, at least one selected from the group consisting of a phenol curing agent, an amine curing agent and an acid anhydride curing agent is preferable, and from the viewpoint of electrical reliability, a phenol curing agent is more preferable. preferable.

Examples of the phenol curing agent include a phenol resin having two or more phenolic hydroxyl groups in one molecule and a polyhydric phenol compound. Specifically, polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and the like. At least one phenolic compound selected from the group consisting of the phenol compounds of the above and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are acidic. Novolac-type phenol resin obtained by condensation or co-condensation under a catalyst; phenol-aralkyl resin synthesized from the above-mentioned phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc., aralkyl-type phenol such as naphthol-aralkyl resin. Resin; paraxylylene and / or metaxylylene-modified phenol resin; melamine-modified phenol resin; terpen-modified phenol resin; dicyclopentadiene-type phenol resin and dicyclopentadiene-type naphthol synthesized by copolymerization of the above phenolic compound with dicyclopentadiene. Resin; Cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified phenol resin; Biphenyl-type phenol resin; Obtained by condensing or co-condensing the above phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst. The triphenylmethane type phenol resin to be used; a phenol resin obtained by copolymerizing two or more of these types can be mentioned. These phenol curing agents may be used alone or in combination of two or more.

Among the phenol hardeners, from the viewpoint of reflow resistance, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, benzaldehyde type phenol resin and aralkyl type phenol resin copolymerized phenol resin, and At least one selected from the group consisting of novolak-type phenolic resins is preferable. From the viewpoint of low-temperature fast-curing property, a novolak-type phenol resin is more preferable.

Specific examples of the aralkyl-type phenol resin include phenol resins represented by the following general formulas (XII) to (XIV).

In formulas (XII) to (XIV), R ²³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R ²² , R ²⁴ , R ²⁵ and R ²⁸ represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different. R ²⁶ and R ²⁷ represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i is an integer of 0 to 3 independently, j is an integer of 0 to 2 independently, k is an integer of 0 to 4 independently, and p is an integer of 0 to 4 independently. be. n is an average value, which is a number of 0 to 10 independently.

Among the phenolic resins represented by the above general formula (XII), MEH-7851 (Meiwa Kasei Co., Ltd., trade name) in which i is 0 and R ²³ is all hydrogen atoms is available as a commercially available product. ..

Among the phenolic resins represented by the above general formula (XIII), XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Kasei Co., Ltd.) in which i is 0 and k is 0. Product name) etc. are available as commercial products.

Among the phenolic resins represented by the above general formula (XIV), SN-170 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which j is 0, k is 0, and p is 0, and j is 0. Yes, SN-395 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which k is 1, R ²⁷ is a hydroxyl group, and p is 0 is available as a commercially available product.

Specific examples of the dicyclopentadiene-type phenol resin include a phenol resin represented by the following general formula (XV).

In formula (XV), R ²⁹ represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. i independently represents an integer of 0 to 3. n is an average value and indicates a number from 0 to 10.

Specific examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XVI).

In the formula (XVI), R ³⁰ and R ³¹ represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different. i is an integer of 0 to 3 independently, and k is an integer of 0 to 4 independently. n is an average value and is a number from 0 to 10.

Specific examples of the copolymerized phenol resin of the benzaldehyde type phenol resin and the aralkyl type phenol resin include a phenol resin represented by the following general formula (XVII).

In the formula (XVII), R ³² to R ³⁴ represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different. i is an integer of 0 to 3 independently, k is an integer of 0 to 4 independently, and q is an integer of 0 to 5 independently. l and m are average values, respectively, and are independently numbers from 0 to 11. However, the total of l and m is a number of 1 to 11.

Specific examples of the novolak-type phenol resin include a phenol resin represented by the following general formula (XVIII).

In formula (XVIII), ^R35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R ³⁶ represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. i independently represents an integer of 0 to 3. n is an average value and indicates a number from 0 to 10.

The "all may be the same or different" described for R ²² to R ³⁶ in the above general formulas (XII) to (XVIII) is, for example, that all i R ^22s in the formula (XII) are the same. But it means that they can be different from each other. It means that all of the other R ²³ to R ³⁶ may be the same or different from each other for each number included in the equation. Further, R ²² to R ³⁶ may be the same or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

N in the above general formulas (XII) to (XVIII) is preferably in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the sealing resin composition at the time of melt molding tends to be low. The average n in one molecule is preferably set in the range of 0 to 4.

From the viewpoint of reducing the stress index of the cured product, the curable resin composition preferably contains a triphenylmethane-type phenol resin (polyfunctional phenol resin) as a curing agent.

The curable resin composition may contain only a triphenylmethane-type phenol resin as a curing agent, and may contain a triphenylmethane-type phenol resin as a curing agent and a curing agent other than the triphenylmethane-type phenol resin.
When a triphenylmethane-type phenol resin and a curing agent other than the triphenylmethane-type phenol resin are contained as the curing agent, the ratio of the triphenylmethane-type phenol resin is preferably 50% by mass or more of the total curing agent, 60. It is more preferably 70% by mass or more, and further preferably 70% by mass or more.

The functional group equivalent of the curing agent (hydroxyl equivalent in the case of the phenol curing agent) is not particularly limited. From the viewpoint of balance of various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

When the curing agent is a solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the sealing resin composition, the temperature is more preferably 50 ° C. to 130 ° C. ..

The melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.

The equivalent ratio of the epoxy resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (the number of functional groups in the curing agent / the number of functional groups in the epoxy resin) is not particularly limited. It is preferable to set it in the range of 0.5 to 2.0, and more preferably set it in the range of 0.6 to 1.3 from the viewpoint of suppressing each unreacted component to a small amount. From the viewpoint of moldability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

(Curing accelerator)
The sealing resin composition may contain a curing accelerator. The type of the curing accelerator is not particularly limited, and conventionally known ones can be used. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonen, 5,6-dibutylamino-1,8-diaza-bicyclo. (5, 4, 0) Cycloamidine compounds such as undecene-7, tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and 2-methylimidazole. , 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2'-methylimidazolyl- (1'))-ethyl-s-triazine, 2-heptadecylimidazole, etc. Organic phosphin compounds such as imidazole compounds, trialkylphosphin (tributylphosphin, etc.), dialkylarylphosphin (dimethylphenylphosphine, etc.), alkyldiarylphosphin (methyldiphenylphosphine, etc.), triphenylphosphine, alkyl group-substituted triphenylphosphine, and these. The organic phosphorus compounds of imidazole, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl A molecule to which a quinone compound such as -1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, or a compound having a π bond such as diazophenylmethane or a phenol resin is added. Examples include compounds having internal polarization and derivatives thereof. Further, phenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate can be mentioned. The curing accelerator may be used alone or in combination of two or more.

From the viewpoint of accelerating the reaction between the epoxy resin and the curing agent at a low temperature, the sealing resin composition preferably contains an imidazole compound.

When the sealing resin composition contains a curing accelerator, the amount thereof is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (total of epoxy resin and curing agent). It is more preferably 1 part by mass to 15 parts by mass. When the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.

(Inorganic filler)
The sealing resin composition may contain an inorganic filler. In particular, when the sealing resin composition is used as a sealing material for a semiconductor package, it is preferable to include an inorganic filler.

The type of the inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, verilia, zirconia, zircon, fosterite, steatite, spinel, mulite. , Titania, talc, clay, mica and other inorganic materials. An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate. Of these, molten silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The inorganic filler may be used alone or in combination of two or more. Examples of the state of the inorganic filler include unpowdered, beads made by spheroidizing the powder, and fibers.

When the sealing resin composition contains an inorganic filler, the content thereof is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 80% by volume, and 40% by volume to 70% by volume of the entire sealing resin composition. % Is more preferable. When the content of the inorganic filler is 30% by volume or more of the entire sealing resin composition, the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire sealing resin composition, an increase in the viscosity of the sealing resin composition is suppressed, the fluidity is further improved, and the moldability is improved. It tends to be.

The average particle size of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 10 μm, and more preferably 0.5 μm to 5 μm. When the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the sealing resin composition tends to be more suppressed. When the volume average particle diameter is 10 μm or less, the filling property into a narrow gap tends to be further improved. The volume average particle size of the inorganic filler can be measured as the volume average particle size (D50) by a laser diffraction / scattering method particle size distribution measuring device.

The volume average particle size of the sealing resin composition or the cured product thereof can be measured by a known method. For example, an inorganic filler is extracted from a sealing resin composition or a cured product using an organic solvent, nitric acid, aqua regia, etc., and sufficiently dispersed by an ultrasonic disperser or the like to prepare a dispersion liquid. Using this dispersion, the volume average particle size of the inorganic filler can be measured from the volume-based particle size distribution measured by the laser diffraction / scattering method particle size distribution measuring device. Alternatively, the volume average particle size of the inorganic filler is measured from the volume-based particle size distribution obtained by observing the cross section obtained by embedding the cured product in a transparent epoxy resin or the like and polishing it with a scanning electron microscope. Can be done. Further, it can be measured by continuously observing a two-dimensional cross section of the cured product and performing a three-dimensional structural analysis using a FIB device (focused ion beam SEM) or the like.

From the viewpoint of the fluidity of the sealing resin composition, the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably widely distributed.

[Various additives]
In addition to the above-mentioned components, the sealing resin composition may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, a colorant, and a stress relaxation agent exemplified below. The sealing resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.

(Coupling agent)
When the sealing resin composition contains an inorganic filler, a coupling agent may be contained in order to enhance the adhesiveness between the resin component and the inorganic filler. Examples of the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane and vinylsilane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. ..

When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 part by mass to 5 parts by mass, and 0.1 part by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably about 2.5 parts by mass. When the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

(Ion exchanger)
The sealing resin composition may contain an ion exchanger. In particular, when the sealing resin composition is used as a sealing molding material, an ion exchanger may be included from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device provided with the sealed element. preferable. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.

Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _{X / 2}・ mH ₂ O …… (A)
(0 <X≤0.5, m is a positive number)

When the sealing resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the resin component.

(Release agent)
The sealing resin composition may contain a mold release agent from the viewpoint of obtaining good mold release property from the mold at the time of molding. The release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester-based waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. As the release agent, one type may be used alone or two or more types may be used in combination.

When the sealing resin composition contains a mold release agent, the amount thereof is preferably 0.01 part by mass to 15 parts by mass, more preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component. When the amount of the mold release agent is 0.01 part by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained. When it is 15 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardants)
The sealing resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like. The flame retardant may be used alone or in combination of two or more.

When the sealing resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 part by mass to 300 parts by mass, and more preferably 2 parts by mass to 150 parts by mass with respect to 100 parts by mass of the resin component.

(Colorant)
The sealing resin composition may further contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. As the colorant, one type may be used alone or two or more types may be used in combination.

(Stress relaxation agent)
The sealing resin composition may contain a stress relaxation agent. By containing a stress relaxation agent, it is possible to further reduce the warpage deformation of the package and the occurrence of package cracks. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexible agents). Specifically, thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), and acrylic. Rubber particles such as rubber, urethane rubber, silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. Examples include rubber particles having a structure. As the stress relaxation agent, one type may be used alone or two or more types may be used in combination.

Among the stress relaxation agents, silicone-based stress relaxation agents are preferable. Examples of the silicone-based stress relieving agent include those having an epoxy group, those having an amino group, those obtained by modifying these with a polyether, and the like, and silicone compounds such as a silicone compound having an epoxy group and a polyether silicone compound are more suitable. preferable.

(Preparation method of resin composition for encapsulation)
The method for preparing the sealing resin composition is not particularly limited. As a general method, a method of sufficiently mixing a predetermined amount of components with a mixer or the like, melt-kneading with a mixing roll, an extruder or the like, cooling and pulverizing can be mentioned. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder or the like preheated to 70 ° C. to 140 ° C., cooled and pulverized. Can be mentioned.

The sealing resin composition is preferably solid at normal temperature and pressure (for example, 25 ° C. and atmospheric pressure). When the sealing resin composition is a solid, the shape is not particularly limited, and examples thereof include powder, granules, and tablets. When the sealing resin composition is in the shape of a tablet, it is preferable that the dimensions and mass are suitable for the molding conditions of the package from the viewpoint of handleability.

(Use of encapsulating resin composition)
The sealing resin composition can be used as a sealing material for various electronic component devices.
Since the sealing resin composition of the present embodiment has an excellent effect of suppressing warpage of the support, a relatively large area is sealed (for example, a sealing step is performed before the package is individualized). It is also suitably used for mounting technology. Examples of such mounting technology include wafer level packaging technologies such as FO-WLP (Fan Out Wafer Level Package) and WI-WLP (Fan In Wafer Level Package).

Examples of the method for encapsulating the semiconductor chip using the encapsulating resin composition include a compression molding method, a transfer molding method, an injection molding method, and the like, and any of these can be adopted.

The material of the support to be sealed using the sealing resin composition is not particularly limited. For example, semiconductors such as silicon, glass, ceramics and the like can be mentioned. The shape of the support is not particularly limited, and may be a disk shape (wafer) or another shape. The area of the support is not particularly limited, but the sealing resin composition of the present embodiment is excellent in the effect of suppressing the warp of the support, and therefore may have a relatively large area. For example, a wafer having a diameter of 12 inches or more may be used.

The sealing thickness when sealing using the sealing resin composition is not particularly limited, and can be selected according to the size of the semiconductor chip to be sealed and the like. Since the sealing resin composition of the present embodiment has an excellent effect of suppressing warpage of the support, it can be suitably used even when the sealing thickness is large (for example, 200 μm to 1000 μm).

<Electronic component equipment>
The electronic component device of the present disclosure includes a support, an element arranged on the support, and a cured product of the above-mentioned sealing resin composition that seals the element.
Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, support members such as organic substrates, active elements such as semiconductor chips, transistors, diodes, and thyristers, capacitors, and resistors. , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with a sealing resin composition.
More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a sealing resin composition or the like. DIP (Dual Inline Package), PLCC (Plastic Readed Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (SmallOdlinePack) TS- General resin-sealed ICs such as Outline Package) and TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with a bump is sealed with a sealing resin composition. A COB (Chip On Board) module, a hybrid IC, or a multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like to a wiring formed on a support member is sealed with a sealing resin composition. Chip module, etc .; After mounting the element on the surface of the support member having terminals for connecting the wiring board on the back surface and connecting the element and the wiring formed on the support member by bump or wire bonding, the resin composition for sealing Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which an element is sealed with an object. Further, the sealing resin composition can also be preferably used in the printed wiring board.

Examples of the method for sealing the electronic component device using the sealing resin composition include a low-pressure transfer molding method, an injection molding method, and a compression molding method. Among these, the low pressure transfer molding method is common.
Further, a method called Molded Underfill (MUF) can be mentioned. Mold underfill is a method of collectively sealing the gap between the semiconductor chip and the substrate (underfill) and sealing the upper part of the semiconductor chip (overmolding).

<Rearranged wafer>
The rearranged wafer of the present disclosure includes a support, an element arranged on the support, and a cured product of the above-mentioned sealing resin composition that seals the element.

Since the rearranged wafer is sealed with the cured product of the sealing resin composition of the present disclosure, the warp of the support is suppressed. Therefore, even a support having a relatively large area can be suitably used. For example, the support may be a wafer having a diameter of 12 inches or more.

The thickness of the cured product of the sealing resin composition that seals the element is not particularly limited, and can be selected according to the size of the element to be sealed and the like. Since the sealing resin composition is excellent in the effect of suppressing the warp of the support, it is suitably used even when the sealing thickness is large (for example, 200 μm to 1000 μm).

(Manufacturing method of electronic component equipment)
After manufacturing the above-mentioned rearranged wafer, the rearranged wafer can be separated into individual pieces to manufacture an electronic component device.
Specifically, a step of arranging the element on the support, a step of arranging the sealing resin composition described above on the support on which the element is arranged, and a sealing arranged on the support. An electronic component device can be manufactured by a method including a step of curing the stopping resin composition to seal the element and a step of disassembling the support.

In the above method, the warp of the support is suppressed even after the sealing resin composition is cured to seal the element. Therefore, the occurrence of misalignment in the process after sealing is small, and the yield of the product is excellent.

The method of arranging the sealing resin composition on the support on which the element is arranged is not particularly limited. For example, when the sealing resin composition is in the form of powder, the sealing resin composition may be sprayed on the support.

The method of curing the sealing resin composition arranged on the support to seal the element is not particularly limited. For example, it may be performed by compression molding. The compression molding is performed, for example, using a compression molding machine under conditions of a predetermined pressure (for example, 2 MPa to 10 MPa), temperature (for example, 120 ° C. to 150 ° C.) and time (for example, 200 seconds to 600 seconds). Can be done.

Hereinafter, the above embodiments will be specifically described with reference to Examples, but the scope of the above embodiments is not limited to these Examples.

<Preparation of resin composition>
The components shown below are premixed (dry blended) at the blending ratio (parts by mass) shown in Table 1, kneaded with a twin-screw kneader at a kneading temperature of 80 ° C., and cooled and pulverized to produce a powdery resin composition. did.

The details of the materials shown in Table 1 are as follows.
(A) Epoxy resin Epoxy resin 1: An epoxy resin having an unsubstituted biphenyl structure and a triphenylmethane structure, an epoxy equivalent of 175 g / eq, and a softening point of 60 ° C to 100 ° C.
Epoxy resin 2: 4,4'-biphenyldiylbis (glycidyl ether) and 3,3', 5,5'-tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl Mixture (mass ratio 1: 1) (Mitsubishi Chemical Co., Ltd., trade name "YL6121HA"), epoxy equivalent 170-180 g / eq, softening point 105 ° C.
Epoxy resin 3: Triphenylmethane type epoxy resin (Nippon Kayaku Co., Ltd., trade name "EPPN-501HY"), epoxy equivalent 169 g / eq, softening point 60 ° C.
Epoxy resin 4: Biphenyl type epoxy resin, epoxy equivalent 196 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")

(B) Hardener Hardener 1: Orthocresol novolak resin (Meiwa Kasei Co., Ltd., trade name "MEH5100-5S"), hydroxyl group equivalent 116 g / eq, softening point 64 ° C.
Curing agent 2: Triphenylmethane type phenol resin (Meiwa Kasei Co., Ltd., trade name "MEH7500-3S"), hydroxyl group equivalent 103 g / eq, softening point 83 ° C.
Curing agent 3: Phenol novolac resin (Meiwa Kasei Co., Ltd., trade name "H-4"), hydroxyl group equivalent 106 g / eq, softening point 83 ° C.

(C) Curing accelerator Curing accelerator 1: p-benzoquinone adduct of triphenylphosphine Curing accelerator 2: 2-Phenyl-4-methylimidazole

(D) Coupling agent Coupling agent 1: 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503")
Coupling agent 2: Phenylaminotrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")

(E) Release agent Release agent: Montanic acid ester wax

(F) Colorant Pigment: Carbon black

(G) Additives Silicone compound 1: Liquid silicone having an epoxy group and a polyether group in the side chain Silicone compound 2: Silicone having an epoxy group and a dimethylsiloxane structure Silicone compound 3: Polymer of siloxane and caprolactone Modified agent: Styline・ Inden copolymer resin

(H) Inorganic filler Inorganic filler 1: Spherical molten silica (volume average particle diameter 6.5 μm)
Inorganic filler 2: Fine spherical molten silica (volume average particle diameter 0.5 μm)

<Evaluation>
The following tests were carried out using the prepared resin composition. The results are shown in Table 2.

[Liquidity (spiral flow test)]
A spiral flow test was performed as an index for evaluating liquidity. Specifically, the flow distance (cm) of the resin composition at a curing time of 120 seconds / 175 ° C. was determined at a molding pressure of 6.9 MPa using a spiral flow measuring die according to EMMI-1-66. rice field.

[Hardness at heat]
A test piece (disk having a diameter of 50 mm and a thickness of 3 mm) was molded by a transfer molding machine at a mold temperature of 130 ° C. and a molding pressure of 6.9 MPa under the condition of a curing time of 200 seconds. Immediately after molding, the hardness (hardness at heat) of the test piece was measured using a Shore D type hardness tester.

[warp]
A molded product having a thickness of 300 μm was molded on a 12-inch silicon wafer using a compression molding device (CPM1080 TOWA) at a mold temperature of 130 ° C. and a curing time of 400 seconds. The warp (μm) of the obtained molded product was measured using a moire measuring device (Acrometrix APX, Akrometrix), and the obtained value was taken as AM (after molding) warpage. After the molded product was completely cured at 175 ° C. for 6 hours, the warp (μm) was measured using a moire measuring device, and the obtained value was defined as AC (after curing) warpage.

[Bending modulus]
A test piece having a shape of 127 mm × 12.7 mm × 4 mm was produced by a transfer molding machine under the conditions of a mold temperature of 175 ° C., a forming pressure of 6.9 MPa, and a curing time of 90 seconds. Then, post-curing was performed at 175 ° C. for 6 hours. Next, a three-point support type bending test based on JIS-K-7171 (2016) was performed at 25 ° C. using Tencilon (A & D Co., Ltd.) to determine the flexural modulus E1 (GPa) of the test piece at 25 ° C.
The flexural modulus is defined by the following equation. In the following formula, E is the flexural modulus (GPa), P is the load cell value (N), y is the displacement amount (mm), l is the span = 64 mm, w is the test piece width = 12.7 mm, and h is the test piece. Thickness = 4 mm.

[Molding shrinkage rate]
A test piece having a shape of 127 mm × 12.7 mm × 6.4 mm was produced by a transfer molding machine under the conditions of a mold temperature of 175 ° C., a forming pressure of 6.9 MPa, and a curing time of 90 seconds. Then, post-curing was performed at 175 ° C. for 6 hours. Next, the molding shrinkage rate МS (%) was calculated from the following formula, where d is the dimension of the obtained test piece and D is the dimension of the mold measured at room temperature (25 ° C.).

[Tg and CTE1 (175 ° C molded / cured product)]
A 4 mm × 4 mm × 20 mm molded product was obtained by a transfer molding machine under the conditions of a mold temperature of 175 ° C., a curing time of 90 seconds, and a molding pressure of 6.9 MPa. The obtained molded product was completely cured at 175 ° C. for 6 hours, and the linear expansion coefficient (CTE) was measured using a thermomechanical analyzer (NETZSCH, TMA4000SE). The measurement temperature range was 30 ° C to 260 ° C, and the temperature rising rate was 10 ° C / min.
The average value of CTE in the range of 40 ° C. to 80 ° C. was defined as CTE1, and the average value of CTE in the range of 200 ° C. to 240 ° C. was defined as CTE2.
The intersection of the tangent of CTE in the range of 40 ° C to 80 ° C and the tangent of CTE in the range of 200 ° C to 240 ° C was defined as the glass transition temperature (Tg).

[Tg and CTE1 (130 ° C molded / cured product)]
A 4 mm × 4 mm × 20 mm molded product was obtained by a transfer molding machine under the conditions of a mold temperature of 130 ° C., a curing time of 300 seconds, and a molding pressure of 6.9 MPa. The obtained molded product was cured at 130 ° C. for 6 hours, and the linear expansion coefficient (CTE) was measured using a thermomechanical analyzer (NETZSCH, TMA4000SE). The measurement temperature range was 30 ° C to 260 ° C, and the temperature rising rate was 10 ° C / min.
The average value of CTE in the range of 40 ° C. to 80 ° C. was defined as CTE1, and the average value of CTE in the range of 200 ° C. to 240 ° C. was defined as CTE2.
The intersection of the tangent of CTE in the range of 40 ° C to 80 ° C and the tangent of CTE in the range of 200 ° C to 240 ° C was defined as the glass transition temperature (Tg).

The "stress index" in the table is the flexural modulus E1 at 25 ° C of the cured product obtained by molding and curing the resin composition at 175 ° C. and the curing obtained by molding and curing the resin composition at 175 ° C. It is a value calculated from CTE1 of an object.
The "hardener polyfunctional ratio" in the table is the ratio (mass%) of "hardener 2" to the entire hardener.

As shown in Table 2, the resin composition of the example in which the stress index of the cured product is 220 GPa × ppm / ° C or less is compared with the resin composition of the comparative example in which the stress index of the cured product exceeds 220 GPa × ppm / ° C. , The amount of warpage in the state where the layer is formed on the semiconductor wafer is effectively suppressed.

Claims (6)

A resin composition for encapsulation containing an epoxy resin and a curing agent and having a stress index of 220 GPa × ppm / ° C. or less in a cured state. The sealing resin composition according to claim 1, wherein the difference between the Tg when molded and cured at 130 ° C. and the Tg when molded and cured at 175 ° C. is within 10 ° C. The sealing resin composition according to claim 1 or 2, wherein the curing agent contains a triphenylmethane type phenol resin. The sealing resin composition according to any one of claims 1 to 3, further comprising a silicone compound. The sealing resin composition according to any one of claims 1 to 4, wherein the epoxy resin contains an epoxy resin having an unsubstituted biphenyl structure. A support, an element arranged on the support, and a cured product of the sealing resin composition according to any one of claims 1 to 5, which seals the element. Electronic component equipment to be equipped.