CN111621152A

CN111621152A - Molding material composition for sealing element and electronic component device

Info

Publication number: CN111621152A
Application number: CN202010103704.7A
Authority: CN
Inventors: 渡边尚纪; 藏勇人
Original assignee: Kyocera Corp
Current assignee: Kyocera Corp
Priority date: 2019-02-28
Filing date: 2020-02-20
Publication date: 2020-09-04
Also published as: JP7356931B2; JP2020145424A

Abstract

SiC，Ga₂O₃The molding material composition for sealing GaN and diamond elements comprises a thermosetting resin, a curing accelerator and a filler, wherein the molding material composition for sealing is cured in a mold at 180 ℃ and 180 seconds and then post-cured outside the mold at 200 ℃ and 8 hours to obtain a cured product, the stress sigma (1) generated when the molding material composition for sealing is cured in a temperature cycle test of-40 to 250 ℃ for 1000 cycles with the cured product, the stress sigma (2) generated when the molding material composition for sealing is subjected to a heat cycle test of-40 to 250 ℃ for 1000 cycles, and the stress sigma (3) generated by irreversible shrinkage of the cured product when the molding material composition for sealing is subjected to a temperature cycle test of 1000 cycles with the cured product satisfy the formula (1), and the stress sigma (1) | + | sigma (2) | + | sigma (3) | 100.0MPa (1) | α× E₂₅

σ(3)＝(β‑α)×E₂₅₀α represents the molding shrinkage (%) of the cured product at 25 ℃ relative to the mold size, β represents the shrinkage (%) of the cured product at 25 ℃ relative to the mold size after standing at 250 ℃ for 500 hours, and E₂₅And E₂₅₀Storage elastic modulus (GPa) of the cured product at 25 ℃ and 250 ℃, CTEt, CTE1 and CTE2 are linear expansion coefficients (ppm/. degree. C.) of the lead frame wire and the cured product at a temperature lower than the glass transition temperature and higher than the glass transition temperature, and Tg is the glass transition temperature (DEG C.) of the cured product.

Description

Molding material composition for sealing element and electronic component device

Technical Field

The invention relates to SiC and Ga₂O₃A molding material composition for sealing GaN and diamond elements, and an electronic component device.

Background

Conventionally, epoxy resin molding materials have been widely used in the field of sealing electronic parts such as transistors and ICs. This is because the epoxy resin has an excellent balance among electrical characteristics, moisture resistance, mechanical characteristics, adhesiveness to an insert, and the like.

In recent years, power devices (power semiconductors) have received attention.

For power semiconductors, power conversion efficiency is one of the items that determines their performance. Heretofore, the use of silicon carbide (SiC), gallium nitride (GaN), gallium oxide (Ga) having higher conversion efficiency than conventional Si elements has been studied₂O₃) Power devices of new semiconductor materials such as diamond.

Among these, SiC and GaN can operate at higher temperatures than conventional Si elements, and particularly SiC has higher withstand voltage than Si elements, and therefore, it is expected that higher withstand voltage can be achieved with smaller elements and packages.

In particular, in automotive applications, a sealing material that can cope with a severe environment in which a large temperature change is applied is required.

For example, patent document 1 relates to a sealing resin composition containing a thermosetting resin, a low-stress agent, and a filler, and discloses a sealing resin composition in which the glass transition temperature of a cured product of the sealing resin composition satisfies a specific condition, and the linear expansion coefficient of the cured product of the sealing resin composition at a temperature equal to or higher than the glass transition temperature is α 2[ ppm/[ DEG C ]]And the flexural modulus E at 25 ℃ of the cured product₂₅[GPa]A specific condition is satisfied.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-150456

Disclosure of Invention

Problems to be solved by the invention

However, the sealing resin composition described in patent document 1 cannot sufficiently withstand use in a severe environment in automotive applications in terms of temperature cycle resistance, and thus there is still room for improvement.

The invention provides a molding material composition for sealing, which has high glass transition temperature and thermal decomposition starting temperature and excellent heat resistance. Further, the molding material composition for sealing is provided, which can obtain a cured product that has excellent adhesion to a semiconductor insert and is less likely to peel off from the semiconductor insert even when subjected to a temperature cycle test. Also disclosed is an electronic component device using such a molding material composition for sealing.

Technical scheme for solving problems

The present inventors have found that the above problems can be solved by a molding material composition for sealing which satisfies specific conditions of a stress σ (1) generated when a cured product is obtained by curing a molding material composition for sealing in a mold under conditions of 180 ℃ and 180 seconds and then post-curing the cured product outside the mold under conditions of 200 ℃ and 8 hours, a stress σ (2) generated based on the thermal history when a temperature cycle test of-40 ℃ to 250 ℃ is performed for 1000 cycles using the cured product, and a stress σ (3) generated by irreversible shrinkage of the cured product when the temperature cycle test is performed for 1000 cycles using the cured product.

That is, the present invention relates to the following.

[1] A molding material composition for sealing which comprises (A) a thermosetting resin, (B) a curing accelerator and (C) a filler,

the molding material composition for sealing satisfies the following formula (1) with a stress σ (1) generated when a cured product is obtained by curing the composition in a mold under conditions of 180 ℃ and 180 seconds and then post-curing the composition outside the mold under conditions of 200 ℃ and 8 hours, a stress σ (2) generated by the thermal history when a temperature cycle test of-40 ℃ to 250 ℃ is performed for 1000 cycles using the cured product, and a stress σ (3) generated by irreversible shrinkage of the cured product when the temperature cycle test is performed for 1000 cycles using the cured product.

0.00MPa≤|σ(1)|+|σ(2)|+|σ(3)|≤100.0MPa (1)

σ(1)＝α×E₂₅

σ(3)＝(β-a)×E₂₅₀

(wherein α represents the molding shrinkage (%) of the cured product with respect to the mold size at 25 ℃), and β represents the shrinkage of the cured product with respect to the mold size at 25 ℃ after the cured product was left at 250 ℃ for 500 hours(％)，E₂₅Represents a storage elastic modulus (GPa), E at 25 ℃ of the cured product₂₅₀The storage elastic modulus (GPa) of the cured product at 250 ℃, the coefficient of linear expansion (ppm/. degree.C.) of a lead frame by CTEt, the coefficient of linear expansion (ppm/. degree.C.) of the cured product at a temperature lower than the glass transition temperature by CTE1, the coefficient of linear expansion (ppm/. degree.C.) of the cured product at a temperature higher than or equal to the glass transition temperature by CTE2, and the Tg, the glass transition temperature (degree.C.) of the cured product. ).

[2] The molding material composition for sealing according to the above [1], wherein,

the value of sigma (3) is 0.00-50.0 MPa.

[3] The molding material composition for sealing according to the above [1] or [2], wherein,

the value of sigma (1) is 0.00-30.0 MPa.

[4] The molding material composition for sealing according to any one of the above [1] to [3], wherein,

the value of alpha is 0.00-0.20%, and the value of beta-alpha is 0.00-0.40%.

[5] The molding material composition for sealing according to any one of the above [1] to [4], wherein,

the thermal decomposition starting temperature of a cured product of the molding material composition for sealing is higher than 350 ℃.

[6] The molding material composition for sealing according to any one of the above [1] to [5], wherein,

the adhesive strength of a cured product of the molding material composition for sealing is 5MPa or more.

[7] The molding material composition for sealing according to any one of the above [1] to [6],

the (C) filler comprises (C-2) a hollow structured filler.

[8] The molding material composition for sealing according to any one of the above [1] to [7],

the molding material composition for sealing further contains (D) a low-stress agent.

[9] An electronic component device, wherein,

the electronic component device comprises an element sealed with a cured product of the molding material composition for sealing of any one of [1] to [8 ].

Effects of the invention

According to the present invention, a molding material composition for sealing having a high glass transition temperature and a high thermal decomposition initiation temperature and excellent heat resistance can be provided. Further, it is possible to provide a molding material composition for sealing which can obtain a cured product that has excellent adhesion to a semiconductor insert and is less likely to peel off from the semiconductor insert even when a temperature cycle test is performed. Also disclosed is an electronic component device using such a molding material composition for sealing.

Drawings

Fig. 1 is a sectional view showing an electronic component device according to an embodiment of the present invention.

Description of reference numerals

1 lead frame

2 semiconductor element

3 adhesive layer

4 electrodes

5 lead part

6 bonding wire

7 cured product (sealing resin) of Molding Material composition for sealing

Detailed Description

The present invention will be described in detail below with reference to one embodiment.

＜SiC、Ga₂O₃Molding material composition for sealing GaN and diamond element

SiC and Ga of the present embodiment₂O₃The molding material composition for sealing GaN and diamond elements (hereinafter, simply referred to as a molding material composition for sealing) is a molding material composition for sealing, which contains (A) a thermosetting resin, (B) a curing accelerator, and (C) a filler, and satisfies the following formula (1). The stress σ (1) is generated by subjecting the molding material composition for sealing to 180 deg.C in a moldAnd stress generated when curing is performed under the condition of 180 seconds, followed by post-curing at 200 ℃ for 8 hours outside the mold to obtain a cured product. The generated stress σ (2) is a stress based on thermal history generated when a temperature cycle test of-40 ℃ to 250 ℃ is performed for 1000 cycles using the cured product. The generated stress σ (3) is a stress generated by irreversible shrinkage of the cured product when the temperature cycle test of 1000 cycles is performed using the cured product.

0.00MPa≤|σ(1)|+|σ(2)|+|σ(3)|≤100.0MPa (1)

σ(1)＝a×E₂₅

σ(3)＝(β-a)×E₂₅₀

(wherein α represents a molding shrinkage (%) of the cured product with respect to a mold size at 25 ℃), β represents a shrinkage (%) of the cured product with respect to a mold size at 25 ℃ after the cured product was left at 250 ℃ for 500 hours, E₂₅Represents a storage elastic modulus (GPa), E at 25 ℃ of the cured product₂₅₀The storage elastic modulus (GPa) of the cured product at 250 ℃, the coefficient of linear expansion (ppm/. degree.C.) of a lead frame by CTEt, the coefficient of linear expansion (ppm/. degree.C.) of the cured product at a temperature lower than the glass transition temperature by CTE1, the coefficient of linear expansion (ppm/. degree.C.) of the cured product at a temperature higher than or equal to the glass transition temperature by CTE2, and the Tg, the glass transition temperature (degree.C.) of the cured product. )

The present inventors have found that the reason why the semiconductor insert and the sealing resin (cured product) do not peel after the temperature cycle test at-40 to 250 ℃ (hereinafter, simply referred to as the temperature cycle test) is that the sum of the stresses generated is in a specific range as follows. The generated stress σ (1) is a stress generated when the adhesion force between the semiconductor insert and the cured product is molded (cured) by the molding material composition for sealing. The stress σ (2) generated is a stress based on a thermal history generated when the temperature cycle test of 1000 cycles is performed using the cured product. The stress σ (3) is a stress generated by irreversible shrinkage of the cured product when the temperature cycle test of 1000 cycles is performed using the cured product.

The sum of the absolute value of the generated stress σ (1), the absolute value of σ (2), and the absolute value of σ (3) is 0.00MPa or more and 100.0MPa or less. If the sum of the absolute value of σ (1), the absolute value of σ (2), and the absolute value of σ (3) exceeds 100.0MPa, the cured product may peel off from the semiconductor embedded part after the temperature cycle test. From such a viewpoint, the sum of the absolute value of σ (1), the absolute value of σ (2), and the absolute value of σ (3) may be 80.0MPa or less, or may be 70.0MPa or less.

The generated stress σ (1) is generated when the molding material composition for sealing of the present embodiment is molded. σ (1) is a total value of "curing shrinkage" caused by a change of a liquid composition into a solid substance (cured product) at the time of molding and stress caused by "dimensional change due to post-curing" caused by post-curing under conditions of 200 ℃ and 8 hours. σ (1) is an irreversible residual stress. The σ (1) may be "0" or a positive value from the viewpoint that peeling between the semiconductor insert and the cured product is less likely to occur even when a temperature cycle test is performed using a cured product of the molding material composition for sealing. In the case of taking a "positive value", the value may be as small as possible. The term "positive value" for σ (1) means that α is a "positive value", i.e., "the size is reduced as compared with that at the time of molding". This means that "stress in the direction in which the semiconductor insert member is pressed (compression direction) acts in the molding material composition for sealing". On the other hand, when σ (1) has a "negative value", the same discussion will apply to the "stress in the direction of peeling from the insert member (tensile direction)" in the molding material composition for sealing, and the peeling is significantly promoted as compared with the stress in the compressive direction. Therefore, σ (1) is "0 (zero) or a positive value". σ (1) may be 30.0MPa or less, may be 28.0MPa or less, may be 25.0MPa or less, and may be 0.00MPa. If the value of σ (1) is 30.0MPa or less, the internal stress in the direction of compressing the cured product does not become excessively large, the adhesion force between the semiconductor insert and the cured product can be improved, and initial peeling is less likely to occur.

Here, the initial peeling in the present specification means the peelability of a cured product of the molding material composition for sealing immediately after the semiconductor embedded part is sealed with the cured product.

In addition, from the viewpoint of being difficult to cause peeling between the semiconductor insert and the cured product after the temperature cycle test, the value of α may be "0 (zero) or a positive value" in accordance with the above discussion. In the case of taking a "positive value", the value may be as small as possible. Specifically, the value of α may be 0.00 to 0.20%, and may be 0.00 to 0.15%. If the value of α is 0.00% or more, stress in the compression direction acts in the interior of the package, the adhesion force between the semiconductor insert and the cured product can be improved, and initial delamination is less likely to occur. On the other hand, if the value of α is 0.20% or less, the internal stress in the direction of compressing the cured product does not become excessively large, the adhesion force between the semiconductor insert and the cured product can be improved, and initial peeling is less likely to occur.

By setting the value of α to be within the range, the value of σ (1) can be set to be within the aforementioned range. The value of a can be achieved by selecting a thermosetting resin system as described below. The coefficient of linear expansion CTE1 of the molding material composition for sealing may be 8 ppm/DEG C to 15 ppm/DEG C, and may be 9 ppm/DEG C to 14 ppm/DEG C. Further, the glass transition temperature after the post-curing at 200 ℃ for 8 hours may be 200 ℃ or more, and may be 210 ℃ or more.

The α can be obtained by the method described in the examples.

The cured product repeats reversible expansion and contraction for a while immediately after the temperature cycle test is started, but thermal decomposition of the cured product gradually starts and irreversible contraction of the cured product starts.

The generated stress σ (2) is a thermal stress generated between cycles of repeating reversible expansion and contraction from the start of the temperature cycle test to the time when the cured product repeats reversible expansion and contraction, and is a reversible stress. The generated stress σ (3) is a stress generated by irreversible shrinkage of the cured product between 1000 cycles and a cycle from the start of thermal decomposition of the cured product.

The cycle standard for repeating reversible expansion and contraction of the cured product varies depending on the type of the thermosetting resin, and is about 50 to 400 cycles from the start of the temperature cycle test.

When the glass transition temperature (Tg) of a cured product of the molding material composition for sealing is 200 ℃ or more and less than 250 ℃, the Tg is within the temperature range of the temperature cycle test. The value σ (2) is the sum of the thermal stress generated in the region having the coefficient of linear expansion CTE1 and the thermal stress generated in the region having the coefficient of linear expansion CTE 2. On the other hand, when the Tg is 250 ℃ or higher, the Tg is within the temperature range of the temperature cycle test or higher. Therefore, the value σ (2) is a thermal stress generated in a region having a coefficient of linear expansion CTE 1.

The value σ (2) may be 35.0MPa or less, and may be 30.0MPa or less, from the viewpoint that peeling between the semiconductor insert and the cured product is less likely to occur even if the temperature cycle test is performed.

The glass transition temperature (Tg) of the cured product may be 200 ℃ or higher, and may be 210 ℃ or higher, from the viewpoint of reducing the generated stress σ (3) accompanying thermal decomposition of the resin or the like. The upper limit of the glass transition temperature may be, for example, 320 ℃ or 310 ℃.

The glass transition temperature (Tg) can be measured by Thermal Mechanical Analysis (TMA), specifically, by the method described in examples.

The coefficient of linear expansion CTE1 of the cured product can be 8 ppm/DEG C to 15 ppm/DEG C, and can be 9 ppm/DEG C to 14 ppm/DEG C. The coefficient of linear expansion CTE2 of the cured product may be as close as possible to the CTE1, from the viewpoint of the difference in coefficient of linear expansion from the semiconductor embedded part, and may be 75 ppm/DEG C or less, or may be 70 ppm/DEG C or less.

The value of σ (2) can be set to the above range by setting the coefficients of linear expansion CTE1 and CTE2 of the cured product to the above ranges, respectively. The coefficients of linear expansion CTE1 and CTE2 of the cured product can be set to fall within the above ranges by setting the content of the filler to about 65 mass% to 85 mass% of the entire molding material composition for sealing, in addition to the filler to fused silica and/or synthetic silica.

In the present embodiment, the coefficient of linear expansion CTE1 of the cured product can be determined from the slope of a tangent line at 50 to 60 ℃ in a TMA chart obtained by measurement based on Thermal Mechanical Analysis (TMA). The coefficient of linear expansion CTE2 of the cured product can be determined from the slope of the tangent line at 290 to 300 ℃ in the TMA chart. Specifically, the measurement can be performed by the method described in the examples.

From the viewpoint that peeling between the semiconductor insert and the cured product is less likely to occur even if the temperature cycle test is performed, σ (3) may be 0 (zero) or a positive value. Specifically, the pressure may be 50.0MPa or less, may be 40.0MPa or less, and may be 0.00MPa. If the value of σ (3) is 50.0MPa or less, the internal stress in the direction of compressing the cured product does not become excessively large, and peeling between the semiconductor insert and the cured product after the temperature cycle test can be made difficult to occur.

In addition, σ (3) is set to the above value from the viewpoint that peeling between the semiconductor embedded part and the cured product after the temperature cycle test is less likely to occur. Therefore, the value of (β - α) may be 0.00 to 0.40%, and may be 0.00 to 0.30%. If the value of (β - α) is 0.00% or more, the stress in the package acts in the compression direction as compared with the initial state (before the temperature cycle test), the adhesion force between the semiconductor insert and the cured product can be improved, and the peeling between the semiconductor insert and the cured product after the temperature cycle test is less likely to occur. On the other hand, if the value of (β - α) is 0.40% or less, the internal stress in the direction of compressing the cured product does not become excessively large, the adhesion force between the semiconductor insert and the cured product can be improved, and the peeling between the semiconductor insert and the cured product after the temperature cycle test is less likely to occur.

By setting the value of (β - α) to be within the range, the value of σ (3) can be set to be within the aforementioned range. The value of (β - α) can be set within the above range by setting the thermal decomposition start temperature of the cured product to 350 ℃ or higher or 360 ℃ or higher. Alternatively, the value of (β - α) may be within the above range even when a part of the filler, for example, 0.5 to 20% by mass of the filler is a hollow structure filler having an average particle diameter of about 3 to 100 μm.

The value of β may be 0.50% or less, and may be 0.40% or less. By setting the value of β to be within the range, the value of (β - α) can be set to be within the aforementioned range.

The β can be obtained by the method described in the examples.

Storage elastic modulus E at 25 ℃ of the cured product₂₅May be 8GPa to 15GPa, or 9GPa to 14 GPa. If said E is₂₅The values of σ (1), σ (2), and σ (3) may be within the above ranges, respectively.

Further, the storage elastic modulus E at 250 ℃ of the cured product₂₅₀May be 2GPa to 10GPa, or 2GPa to 9 GPa. If said E is₂₅₀The value of σ (2) may be set to be within the aforementioned range.

The storage elastic modulus can be measured by Dynamic Mechanical Analysis (DMA), and specifically, can be measured by the method described in the examples.

The molding material composition for sealing of the present embodiment includes (a) a thermosetting resin, (B) a curing accelerator, and (C) a filler.

[ (A) thermosetting resin ]

The thermosetting resin (a) used in the present embodiment is not particularly limited, but may be at least two or more selected from the group consisting of maleimide resins, phenolic resins, epoxy resins, benzoxazine resins, and cyanate ester resins, from the viewpoint of heat resistance, adhesion, and moldability.

The maleimide resin is not particularly limited as long as it is a compound containing two or more maleimide groups in one molecule, but may be a compound represented by the following general formula (I). The maleimide resin is a resin which is cured by heating to react maleimide groups to form a three-dimensional network structure. The maleimide resin can impart a high glass transition temperature (Tg) to a cured product by a crosslinking reaction, and can improve heat resistance and thermal decomposition resistance.

[ chemical formula 1]

In the general formula (I), R¹Each independently a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be substituted with a halogen atom. p is an integer of 0 to 4, and q is an integer of 0 to 3.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; substituted alkyl groups such as chloromethyl and 3-chloropropyl; alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, and the like; aryl groups such as phenyl, tolyl, and xylyl; and monovalent hydrocarbon groups such as aralkyl groups including benzyl and phenethyl.

In addition, in R¹When there are plural, the plural R¹May be the same or different from each other.

z is an integer of 0 to 10, and may be an integer of 0 to 4.

The maleimide resin represented by the general formula (I) is relatively easily subjected to an addition reaction at a temperature of 170 ℃ or higher in the presence of at least one selected from the group consisting of phenol resins and benzoxazine resins and (B) a curing accelerator described later, thereby imparting high heat resistance to a cured product of the molding material composition for sealing.

Specific examples of the maleimide resin represented by the above general formula (I) include N, N '- (4, 4' -diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and polyphenylmethanemaleimide.

The maleimide resin may be commercially available, for example, BMI containing z-0 as a main component in N, N '- (4, 4' -diphenylmethane) bismaleimide, BMI-70 (manufactured by KI chemical corporation, ケイアイ chemical corporation), BMI-1000 (manufactured by daikon chemical industry co., ltd.), BMI-2300 containing z-0 to 2 as a main component in polyphenylmethane maleimide (manufactured by daikon chemical industry co., ltd.), or the like.

As the maleimide resin, a maleimide resin represented by the general formula (I) and a maleimide resin other than the maleimide resin represented by the general formula (I) may be used in combination. Examples of the maleimide resin which can be used in combination include m-phenylene bismaleimide, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane, and 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane. Other than these, a maleimide resin known in the past may be used in combination. When a maleimide resin other than the maleimide resin represented by the above general formula (I) is blended, the blending amount thereof may be 30 parts by mass or less, and may be 20 parts by mass or less, relative to 100 parts by mass of the maleimide resin represented by the above general formula (I).

The phenolic resin is not limited by a molecular structure, a molecular weight, and the like as long as it has two or more phenolic hydroxyl groups per molecule, and resins generally used as sealing materials for electronic parts can be widely used. Examples of the phenol resin include phenol novolac resins, phenol xylene resins, cresol novolac resins, aralkyl type phenol resins, cyclopentadiene type phenol resins, triphenol alkane type phenol resins, triphenyl methane type phenol resins, naphthalene type phenol resins, biphenyl type phenol resins, and the like. Among them, from the viewpoint of glass transition temperature (Tg), a triphenylmethane type phenol resin and a naphthalene type phenol resin may be used, and from the viewpoint of thermal decomposition, a biphenyl type phenol resin may be used. These may be used alone or in combination of two or more.

The softening point of the phenolic resin may be 55 to 120 ℃ or 60 to 110 ℃ from the viewpoint of productivity of the molding material composition for sealing, flow characteristics, or the like.

The softening point in the present specification means "ring and ball softening point" and is a value measured according to ASTM D36.

The triphenylmethane-type phenol resin may be a phenol resin having a triphenylmethane skeleton represented by the following general formula (II), and the naphthalene-type phenol resin may be a phenol resin having a naphthalene skeleton represented by the following general formula (III).

[ chemical formula 2]

(wherein x is 0 to 10.)

[ chemical formula 3]

(wherein y1 is 0 to 10.)

In the general formula (II), x is 0-10, and may be 1-4. In the general formula (III), y1 is 0 to 10, and may be 0 to 3.

The phenol resin represented by the general formula (II) is MEH-7500 (manufactured by Minghe Kasei Co., Ltd.), the phenol resin represented by the general formula (III) is SN-485 (manufactured by Nippon iron King chemical Co., Ltd.), and the biphenyl type phenol resin is MEH-7851 (manufactured by Minghe Kasei Co., Ltd.), and they are each available as a commercially available product.

The epoxy resin is not limited by a molecular structure, a molecular weight, and the like as long as it has two or more epoxy groups per molecule, and resins generally used as sealing materials for electronic components can be widely used. Examples of the epoxy resin include a biphenyl type epoxy resin, a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, a triphenol methane type epoxy resin, a heterocyclic type epoxy resin such as a triazine nucleus-containing epoxy resin, a diphenylethylene type bifunctional epoxy resin, a naphthalene type epoxy resin, a dihydroxy naphthalene novolac type epoxy resin, a condensed ring aromatic hydrocarbon-modified epoxy resin, and an alicyclic type epoxy resin. Among them, from the viewpoint of glass transition temperature (Tg), triphenylmethane type epoxy resins and naphthalene type epoxy resins are preferable, and from the viewpoint of thermal decomposition, biphenyl type epoxy resins are preferable.

These epoxy resins may be used alone or in combination of two or more.

The softening point of the epoxy resin may be 40 to 130 ℃ and may be 50 to 110 ℃ from the viewpoint of improving productivity and fluidity of the molding material composition for sealing.

The triphenylmethane type epoxy resin may be an epoxy resin having a triphenylmethane skeleton represented by the following general formula (IV), and the naphthalene type epoxy resin may be an epoxy resin having a naphthalene skeleton represented by the following general formula (V) or (VI).

[ chemical formula 4]

(wherein n1 is 0 to 10.)

[ chemical formula 5]

(wherein n2 is 0 to 10.)

[ chemical formula 6]

In the general formula (IV), n1 is 0 to 10, and may be 0 to 3. In the general formula (V), n2 is 0 to 10, and may be 0 to 3.

The epoxy resin represented by the general formula (IV) is EPPN-502H (manufactured by Nippon Kagaku Co., Ltd.), the epoxy resin represented by the general formula (V) is ESN-375 (manufactured by Nippon Kagaku K.K.), the epoxy resin represented by the general formula (VI) is HP-4710 (manufactured by DIC Co., Ltd.), and the biphenyl type epoxy resin is NC-3000 (manufactured by Nippon Kagaku K.K.), and they are commercially available.

The benzoxazine resin is not particularly limited as long as it is a compound having two or more benzoxazine rings in one molecule and being polymerizable, but may be a compound represented by the following general formula (VII) from the viewpoint of glass transition temperature (Tg).

[ chemical formula 7]

In the general formula (VII), X1 is an alkylene group having 1 to 10 carbon atoms, an oxygen atom or a direct bond. R²And R³Each independently a hydrocarbon group having 1 to 10 carbon atoms.

The number of carbon atoms of the alkylene group of X1 is 1 to 10, and may be 1 to 3. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Among them, methylene, ethylene and propylene may be mentioned, and methylene may be mentioned.

As R²And R³Examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, and the like; aryl groups such as phenyl, tolyl, and xylyl; benzyl, phenethyl, and the likeAralkyl groups and the like.

In addition, in R²And R³In the case where there are plural, plural R²And a plurality of R³The components may be the same or different.

m1 is an integer of 0 to 4, 0 to 2 or 0. m2 is an integer of 0 to 4, 0 to 2 or 0.

Specific examples of the benzoxazine resin represented by the general formula (VII) include resins represented by the following formulas (VII-1) to (VII-4). These resins may be used alone or in combination of two or more.

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

As the benzoxazine resin, the benzoxazine resin represented by the formula (VII-1) may be mentioned. In the benzoxazine resin represented by the general formula (VII), the content of the benzoxazine resin represented by the formula (VII-1) may be 50 to 100% by mass, may be 60 to 100% by mass, and may be 70 to 100% by mass.

The benzoxazine resin represented by the formula (VII-1) can be obtained as a commercially available product such as benzoxazine P-d (manufactured by Shikoku Kagaku K.K.).

The cyanate resin includes, for example, a cyanate monomer having at least two cyanate groups in one molecule (hereinafter, simply referred to as a cyanate monomer). The cyanate ester monomer is particularly advantageous for adhesion.

In the present embodiment, the "cyanate ester monomer" refers to a cyanate ester compound having no structure in which a part of the molecular structure is repeated in the molecule.

The cyanate ester monomer is not particularly limited as long as it has at least two cyanate groups in one molecule. Examples thereof include compounds having two cyanate groups in one molecule, such as bis (4-cyanate-phenyl) methane, 1, 1-bis (4-cyanate-phenyl) ethane, 2-bis (4-cyanate-phenyl) propane, bis (3-methyl-4-cyanate-phenyl) methane, and bis (3, 5-dimethyl-4-cyanate-phenyl) methane, and compounds having three cyanate groups in one molecule, such as bis (3, 5-dimethyl-4-cyanate-phenyl) -4-cyanate-phenyl-1, 1, 1-ethane. Other compounds than these, which are known in the art, may be used.

Specific examples of the cyanate ester monomer include Primaset LECy (manufactured by nippon sand co., ltd. (ロンザジャパン)) containing 1, 1-bis (4-cyanate phenyl) ethane as a main component, and cytestar (registered trademark) TA (manufactured by mitsubishi gas chemical corporation) containing 2, 2-bis (4-cyanate phenyl) propane as a main component, which are commercially available.

As for the (a) thermosetting resin, thermosetting resins other than the above maleimide resin, phenolic resin, epoxy resin, benzoxazine resin and cyanate resin may be used in combination within a range not departing from the gist of the present invention. For example, when a cyanate monomer is used as the thermosetting resin (a), a cyanate resin having a repeating structure in a molecule such as novolac-type cyanate may be used in combination.

When a maleimide resin, a phenol resin, an epoxy resin, a benzoxazine resin, and a cyanate ester resin are used in combination with a thermosetting resin other than these resins as the (a) thermosetting resin, the content of the maleimide resin, phenol resin, epoxy resin, benzoxazine resin, and cyanate ester resin relative to the total amount of the (a) thermosetting resin may be 80 mass% or more, may be 90 mass% or more, and may be 95 mass% or more.

The content of the thermosetting resin (a) may be 10 to 30% by mass, or 15 to 25% by mass, based on the total amount of the molding material composition for sealing. If the content of (a) the thermosetting resin is 10 mass% or more, molding is possible from the viewpoint of flow characteristics and the like, and if the content of (a) the thermosetting resin is 30 mass% or less, insulation properties such as flame resistance and corrosion resistance can be improved.

[ (B) curing Accelerator ]

The curing accelerator (B) used in the present embodiment is not particularly limited, and those generally used as sealing materials for electronic components can be widely used. Examples of the curing accelerator (B) include (B-1) a phosphorus-based curing accelerator and (B-2) an imidazole-based curing accelerator, and these may be used in combination from the viewpoint of balance between adhesiveness and moldability.

In the present embodiment, the "imidazole-based curing accelerator" has the same meaning as that of the imidazole compound containing a nitrogen atom in the 1-and 3-positions of the five-membered ring.

The (b-1) phosphorus-based curing accelerator mainly has an action of accelerating a crosslinking reaction of the maleimide resin and the phenolic resin and/or benzoxazine resin, a crosslinking reaction of the phenolic resin and/or benzoxazine resin and the epoxy resin, a trimerization reaction of the cyanate resin, and the like. The phosphorus-based curing accelerator (b-1) indirectly reduces self-polymerization reaction between the maleimide resins by accelerating these reactions, and has an effect of suppressing the occurrence of peeling stress with respect to the semiconductor embedded part.

Examples of the phosphorus-based curing accelerator (b-1) include tertiary phosphines such as triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (2, 4-dimethylphenyl) phosphine, tris (2,4, 6-trimethylphenyl) phosphine, tributylphosphine, and methyldiphenylphosphine, and tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium tetraphenylborate and tetrabutylphosphonium tetrabutylborate. These may be used alone or in combination of two or more. The conventionally known phosphorus-based curing accelerators other than these can be used alone or in combination of two or more.

The imidazole curing accelerator (b-2) mainly accelerates the self-polymerization reaction of the maleimide resin and improves the moldability of the molding material composition for sealing. The imidazole-based curing accelerator (b-2) can provide the molding material composition for sealing of the present embodiment with good curability and moldability by accelerating curing in the presence of the epoxy resin.

Examples of the imidazole-based curing accelerator (b-2) include 2-methylimidazole, 2-ethylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-dihydroxymethylimidazole, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. These may be used alone or in combination of two or more. In addition, conventionally known imidazole-based curing accelerators other than the above-mentioned one may be used.

The imidazole-based curing accelerator (b-2) may be suitably selected and used as required. From the viewpoint of the balance between moldability of the molding material composition for sealing and adhesion between a cured product of the composition and a semiconductor embedded part, two or more compounds having relatively high active temperature, such as 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine and 2-phenyl-4-methyl-5-hydroxymethylimidazole, can be used alone or in combination. Specifically, the reaction initiation temperature when the (b-2) imidazole-based curing accelerator is reacted with the bisphenol a-type epoxy resin (liquid) at a mass ratio of 1/20 may be 5 ℃ or higher and less than 175 ℃, 100 ℃ or higher and less than 160 ℃, and 100 ℃ or higher and less than 150 ℃.

Here, the reaction initiation temperature refers to a temperature at which, when a composition containing (b-2) the imidazole-based curing accelerator and the bisphenol a-type epoxy resin is heated at a temperature increase rate of 10 ℃/min by DSC, the tangent to the most acute peak portion intersects with the temperature axis in the rising curve of the exothermic peak or endothermic peak.

If the reaction initiation temperature of the imidazole-based curing accelerator (b-2) is 85 ℃ or higher, the peeling from the semiconductor embedded part can be reduced, and if the reaction initiation temperature is less than 175 ℃, the moldability of the molding material composition for sealing can be improved.

The content of the curing accelerator (B) may be 0.1 to 1.0% by mass, and may be 0.1 to 0.5% by mass, based on the total amount of the molding material composition for sealing. If the content of the curing accelerator (B) is 0.1% by mass or more, the moldability of the molding material composition for sealing can be improved, and if it is 1.0% by mass or less, the flowability can be improved.

When the (B-1) phosphorus-based curing accelerator and the (B-2) imidazole curing accelerator are used in combination as the curing accelerator (B), the content ratio [ (B-1)/(B-2) ] of the (B-1) phosphorus-based curing accelerator to the (B-2) imidazole curing accelerator may be 3/1 to 1/3, 2/1 to 1/3, and 2/1 to 1/2 in terms of mass ratio. If the component (b-1) is contained in a large amount, moldability may become insufficient, and if the component (b-2) is contained in a large amount, adhesion between a cured product of the molding material composition for sealing and the semiconductor embedded part may become insufficient.

[ (C) Filler ]

The filler (C) used in the present embodiment is not particularly limited, and conventionally known fillers can be used. Examples of the filler (C) include (C-1) an inorganic filler and (C-2) a hollow-structure filler, but particularly from the viewpoint of reducing the stress [ sigma ] (3) caused by dimensional change in a temperature cycle test, the inorganic filler (C-1) and the hollow-structure filler (C-2) may be used in combination.

The "hollow structured packing" in the present embodiment refers to a packing having one or two or more hollow structures inside the packing.

Examples of the inorganic filler (c-1) (excluding silicone powder as the low-stress agent (D) described later) include crystalline silica, fused silica, synthetic silica, alumina, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, and barium titanate. From the viewpoint of fluidity and reliability, crystalline silica, fused silica, or synthetic silica may be used, or fused spherical silica or synthetic silica may be used as a main component.

The average particle diameter of the inorganic filler (c-1) may be 5 to 30 μm, 6 to 25 μm, or 8 to 20 μm. When the average particle diameter is 5 μm or more, moldability can be improved, and when 30 μm or less, mechanical strength can be improved.

In the present specification, the average particle size refers to a median value (D50) measured by a laser diffraction scattering method (for example, SALD-3100, a device name manufactured by Shimadzu corporation).

The content of the (C-1) inorganic filler may be 70 to 100% by mass, 80 to 99% by mass, or 90 to 99% by mass based on the total amount of the (C) filler, from the viewpoints of linear expansion coefficient, mechanical strength, and the like.

The hollow structured filler (c-2) can reduce the stress σ (3) by reducing the (initial) generated stress σ (1) generated along with the dimensional change (molding shrinkage) accompanying the curing of the molding material composition for sealing and reducing the shrinkage β after the molding material composition is left at 250 ℃ for 500 hours.

The hollow structured filler (c-2) is not particularly limited, and inorganic hollow structured fillers such as so-called hollow glass and hollow silica containing soda-lime glass, borosilicate glass, aluminum silicate, mullite, quartz or the like as a main component, and fillers having a siloxane bond-linked structure of (CH)₃SiO_3/2)_nA silicone hollow-structure filler containing a silicone compound such as the three-dimensional network silsesquioxane compound as a main component.

The term "silsesquioxane compound" as used herein means a Compound Having (CH) groups crosslinked by siloxane bonds₃SiO_3/2)_nThree of representationA compound having a network structure and having a side chain having an organic functional group such as methyl group or phenyl group, wherein the proportion of the side chain having a methyl group is 80% or more.

Among the "hollow-structure fillers", particularly, the inorganic hollow-structure filler and the silicone hollow-structure filler have high heat resistance of the hollow-structure filler itself, and thus can be used for a molding material composition for sealing having higher heat resistance.

The elastic modulus of the hollow structured filler (c-2) may be 0.1GPa to 15GPa, or 0.2GPa to 12 GPa. Among these, the inorganic hollow-structure filler such as hollow glass and hollow silica having a relatively high elastic modulus tends to be relatively high in suppressing shrinkage during curing of the sealing resin, and thus stress generated during curing is reduced. Further, a silicone-based hollow-structure filler such as a silsesquioxane compound having a relatively low elastic modulus is preferable because the elastic modulus of the sealing material can be lowered by adding a small amount, and the tendency to relax stress during thermal shrinkage is high. The combination of an inorganic hollow structure filler such as hollow glass or hollow silica and a silicone hollow structure filler such as a silsesquioxane compound is one of the present embodiments, and the present embodiments can reduce peeling from a semiconductor embedded part even when a relatively small amount of the filler is added, and can also be applied to a sealing resin which requires high heat resistance.

The elastic modulus of the hollow structured filler (c-2) in the present embodiment can be measured, for example, by a dynamic microhardness tester.

The hollow-structure filler (c-2) may be an inorganic hollow-structure filler containing at least one selected from silica, alumina, and silica-alumina compounds and/or a silicone hollow-structure filler containing a silsesquioxane compound, from the viewpoint of reducing the stress σ (3) generated particularly by dimensional change in a temperature cycle test. The filler may be an inorganic hollow-structure filler containing at least one selected from silica-alumina compounds and alumina.

The (c-2) hollow structured filler that can be used in the present embodiment is preferably free of an alkali metal and/or an alkaline earth metal from the viewpoint of reducing corrosion of the semiconductor insert due to ionic impurities. In the case where the mixing-in cannot be prevented, it is preferable to reduce the mixing-in as much as possible.

(c-2) the hollow structured filler contains at least one selected from silica, alumina and silica-alumina compounds, and as a material containing a small amount of alkali metal, alkaline earth metal and the like, for example, Kainospheres (カイノスフィアーズ) (trade name, manufactured by Kansaitake corporation, Kansai マテック, and trade name) containing aluminum silicate and mullite (a compound of silica and alumina) as main components, E-SPHERES (イースフィアーズ) (trade name, manufactured by Pacific Cement corporation, Pacific セメント, and the like) are commercially available. Further, as the silicone hollow structure filler (silsesquioxane compound filler) containing a silsesquioxane compound, for example, NH-SBN04 (trade name, manufactured by shinshin-kaki corporation, japan リカ corporation)) containing polymethylsilsesquioxane as a main component is commercially available.

The hollow structured filler (c-2) may have an average particle diameter of 3 to 100 μm, or 3 to 60 μm, from the viewpoint of reducing peeling from the semiconductor embedded part and achieving both of productivity and moldability of the molding material composition for sealing. If the average particle diameter is 3 μm or more, peeling is reduced, and if the average particle diameter is 100 μm or less, the productivity and moldability of the molding material composition for sealing are improved.

As the hollow structured filler having an average particle diameter of 3 μm to 100 μm, Kainospheres 75 (average particle diameter 35 μm) and the like of Kainospheres series (trade name, manufactured by Katsumadai corporation, Katsumadai マテック, Inc.) and E-SPHERES SL75 (average particle diameter 55 μm) and E-SPHERES SL125 (average particle diameter 80 μm) and the like of E-SPHERES series (trade name, manufactured by Pacific Cement Co., Ltd., Pacific セメント, Inc.) are commercially available. Further, commercially available glass microspheres K37 (average particle size 45 μ M), iM30K (average particle size 16 μ M) (manufactured by 3M Japan K.K. (スリーエム & ジャパン Co., Ltd)), NH-SBN04 (average particle size 4 μ M, manufactured by Hishin Kagaku K.K. (Hishin リカ Co., Ltd)), and the like can be used.

When the molding material composition for sealing of the present embodiment contains (C-2) the hollow-structure filler, the content thereof may be 0.5 to 30% by mass, 1 to 20% by mass, or 1 to 10% by mass, based on the total amount of the filler (C). If the content of the hollow structure filler (c-2) is 0.5 mass% or more, the peeling from the semiconductor embedded part is reduced particularly with the reduction of the generated stress σ (3), and if it is 30 mass% or less, the moldability and the insulation property can be improved and the decrease in thermal conductivity can be reduced. In particular, when the hollow structured filler (C-2) contains a silsesquioxane compound, the content thereof may be 0.5 to 10% by mass, 1 to 6% by mass, or 1.2 to 5% by mass, based on the total amount of the filler (C).

The content of the filler (C) may be 60 to 90 mass%, 65 to 85 mass%, or 70 to 80 mass% based on the total amount of the molding material composition for sealing. If the content of the filler (C) is 60 mass% or more, the difference in linear expansion coefficient required for securing mechanical strength and reducing separation from the semiconductor embedded part can be secured, and if 90 mass% or less, moldability such as flow characteristics can be brought within an appropriate range.

The molding material composition for sealing of the present embodiment may further contain (D) a low-stress agent from the viewpoint of reducing peeling from the semiconductor embedded part. Examples of the low-stress agent (D) include silicone compounds such as silicone powder, silicone oil, and silicone rubber; a polybutadiene compound; acrylonitrile-butadiene copolymers such as acrylonitrile-carboxyl terminated butadiene copolymers, and the like. Among them, silicone powder containing polymethylsilsesquioxane or the like as a main component, which has relatively high heat resistance, may be used. These may be used alone or in combination of two or more.

The average particle diameter of the silicone powder may be 0.5 μm or more and less than 5 μm, and may be 1 μm or more and 4 μm or less.

When the (D) low-stress agent is used, the content of the (D) low-stress agent may be 0.5 to 10% by mass, or 1 to 6% by mass, based on the total amount of the molding material composition for sealing. If the content of the (D) low-stress agent is 0.5 mass% or more, peeling can be reduced in terms of reducing the elastic modulus and improving the adhesion force, and if it is 10 mass% or less, deterioration of moldability such as flow characteristics can be prevented.

The molding material composition for sealing of the present embodiment may contain a silane coupling agent from the viewpoints of moisture resistance, mechanical strength, adhesion to a semiconductor embedded part, and the like. In the present embodiment, conventionally known silane coupling agents, for example, epoxy silanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; aminosilanes such as 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; isocyanate silanes such as 3-isocyanatopropyltriethoxysilane, and the like. From the viewpoint of adhesion, an epoxy silane such as 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, a secondary amino silane, an isocyanate silane, or the like may be used alone or in combination. The silane coupling agent may be used by simply mixing it with the filler (C), or may be used by subjecting a part or all of the filler to surface treatment in advance. In addition, an aluminate coupling agent or a titanate coupling agent may be contained within a range not departing from the gist of the present embodiment.

The content of the silane coupling agent may be 0.01 to 1% by mass, 0.03 to 0.7% by mass, or 0.05 to 0.5% by mass, based on the total amount of the molding material composition for sealing. By setting the content of the silane coupling agent to 0.01 mass% or more, the adhesion to the semiconductor embedded part can be improved, and by setting the content to 1 mass% or less, the decrease in curability at the time of molding can be reduced.

In order to achieve good productivity of the molding material composition for sealing of the present embodiment, a release agent may be further contained. Examples of the release agent that can be added include natural waxes such as carnauba wax, fatty acid ester waxes, fatty acid amide waxes, non-oxidized polyethylene release agents, and silicone release agents. A release agent other than these may be added. The release agent may be used alone or in combination of two or more.

The molding material composition for sealing of the present embodiment can contain, in addition to the above components, a flame retardant, carbon black, an organic dye, a coloring agent such as titanium oxide or red iron oxide, a thermoplastic resin, an ion trapping agent, an antifoaming agent, and the like, which are generally blended in such a composition, as needed.

In the molding material composition for sealing of the present embodiment, the contents of the thermosetting resin (a), the curing accelerator (B), and the filler (C) may be 80 mass% or more, 90 mass% or more, and 95 mass% or more.

The molding material composition for sealing of the present embodiment can be prepared by uniformly dispersing and mixing a predetermined amount of the complex in which the respective components are mixed. The production method is not particularly limited, and a general method includes, for example, a method in which a mixture in which the above components are mixed in predetermined amounts is sufficiently mixed by using a mixer or the like, followed by melt-mixing by a kneading roll, an extruder or the like, followed by cooling and pulverization.

The molding material composition for sealing thus obtained can provide a cured product that has a high glass transition temperature (Tg) and a high thermal decomposition initiation temperature, has excellent heat resistance, has excellent adhesion to a semiconductor insert, and is less likely to peel off from the semiconductor insert even after a temperature cycle test.

The thermal decomposition starting temperature of the cured product of the molding material composition for sealing may be higher than 350 ℃ and may be 355 ℃ or higher.

The adhesive strength of the cured product of the molding material composition for sealing may be 5MPa or more, and may be 6MPa or more.

The thermal decomposition initiation temperature and the adhesive strength of the cured product can be measured by the methods described in examples.

(electronic parts device)

The electronic component device of the present embodiment includes an element sealed with a cured product of the molding material composition for sealing. The electronic component device is used for a group of lead frames, monocrystalline silicon semiconductor elements or SiC and Ga₂O₃And supporting members such as GaN and diamond elements, and electronic component devices for electrically connecting these members such as wires and bumps and other constituent members and sealing the necessary portions with a cured product of the molding material composition for sealing. In particular SiC, Ga₂O₃And GaN and a diamond element as a support member, an electronic component device sealed with a cured product of the molding material composition for sealing can obtain excellent characteristics.

Fig. 1 is a diagram showing an example of an electronic component device according to the present embodiment. The adhesive layer 3 may be sandwiched between the lead frame 1 such as a copper frame and the semiconductor element 2. The electrodes 4 on the semiconductor element 2 and the lead portions 5 of the lead frame 1 are connected by bonding wires 6, and these are sealed with a cured product (sealing resin) 7 of the molding material composition for sealing of the present embodiment.

As a method for sealing using the sealing molding material composition of the present embodiment, a transfer molding method is most general, and an injection molding method, a compression molding method, or the like may be used.

The molding temperature can be 150-250 ℃, 160-220 ℃ or 170-200 ℃. The molding time may be 30 seconds to 600 seconds, 45 seconds to 300 seconds, or 60 seconds to 250 seconds. When the post-curing is performed, the heating temperature is not particularly limited, and may be, for example, 150 to 250 ℃ or 180 to 220 ℃. The heating time is not particularly limited, and may be, for example, 0.5 to 10 hours, or 1 to 8 hours.

[ examples ] A method for producing a compound

The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples at all.

Examples 1 to 14 and comparative examples 1 to 6

The respective components of the types and amounts shown in tables 1 and 2 were kneaded by a biaxial mixing roll to prepare a molding material composition for sealing. The kneading temperature in each of the examples and comparative examples was set to 80 ℃ to 100 ℃. The blank column in tables 1 and 2 indicates no matching.

The components listed in tables 1 and 2 used for the preparation of the molding material composition for sealing are described in detail below.

< (A) thermosetting resin

[ Maleimide resin ]

BMI-2300: polyphenylmethaneimide (mainly containing z 0-2 in the general formula (I)), produced by Dahe chemical industry Co., Ltd., trade name

BMI-80: 2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane, manufactured by KI CHEMICAL Co., Ltd. (ケイ & アイ CHEMICAL Co., Ltd.) and having a trade name

[ phenol resin ]

SN-485: a naphthalene-based phenol resin (mainly composed of a phenol resin having y1 of 0 to 3 in the general formula (III)), available from Nippon iron-based chemical Co., Ltd., trade name, hydroxyl equivalent 215, softening point 87 DEG C

MEH-7500: a triphenylmethane type phenol resin (mainly comprising a phenol resin having x of 1 to 4 in the general formula (II)), trade name of Kogyo Kabushiki Kaisha, hydroxyl equivalent 97, softening point 110 DEG C

MEH-7851: biphenyl type phenol resin, product name of Minghe chemical Co., Ltd., hydroxyl equivalent 204, softening point 70 ℃ C

[ epoxy resin ]

EPPN-502H: a triphenylmethane type epoxy resin (mainly composed of an epoxy resin having n1 of 0 to 3 in the general formula (IV)), manufactured by Nippon Kasei K.K., trade name of epoxy equivalent 168, softening point of 67 DEG C

NC-3000: biphenyl Novolac epoxy resin (trade name, manufactured by Nippon Kabushiki Kaisha, epoxy equivalent 276, softening point 58 ℃ C.)

[ benzoxazine resin ]

Benzoxazine P-d: benzoxazine resin [ benzoxazine resin represented by the formula (VII-1) ] manufactured by Sizhou Kasei Kogyo K.K., trade name

[ cyanate ester resin ]

Cytetester (registered trademark) TA: cyanate ester compound containing 2, 2-bis (4-cyanate phenyl) propane as a main component (99% or more), product name of Mitsubishi gas chemical corporation

(B) curing Accelerator

[ phosphorus-based curing accelerators ]

TPP: triphenylphosphine, manufactured by Beixinghu chemical Co., Ltd., trade name

TPP-BQ: addition product of triphenylphosphine and p-benzoquinone

TPP-BQ was synthesized as follows.

A separable flask equipped with a cooling tube and a stirring device was charged with 4.25g of benzoquinone, 10g of triphenylphosphine, and 30g of acetone, and the reaction was carried out at room temperature (25 ℃ C.) with stirring. The precipitated crystals were washed with acetone, and then filtered and dried to obtain 14g of tan-colored TPP-BQ crystals.

[ imidazole-based curing accelerator ]

2P4 MHZ-PW: 2-phenyl-4-methyl-5-hydroxymethylimidazole, product name of Siguo Kasei Kogyo (reaction initiation temperature with bisphenol A epoxy resin: 129 ℃ C.)

2 MZ-A: 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine, product name of Sizhou chemical industry Co., Ltd. (reaction initiation temperature with bisphenol A epoxy resin: 120 ℃ C.)

(C) Filler

[ (c-1) inorganic Filler ]

FB-105: fused spherical silica, trade name of trade name, average particle diameter 18 μm, specific surface area 4.5m, manufactured by ECO²/g

[ (c-2) hollow structured packing ]

E-SPHERES SL 75: an inorganic hollow filler mainly composed of amorphous aluminum (65 to 85%) and mullite (20 to 30%), having an average particle diameter of 55 μm, manufactured by Pacific Cement Co., Ltd., trade name, and having an elastic modulus of 10GPa

(D) Low-stress agent

EP-5518: silicone powder mainly composed of polymethylsilsesquioxane, manufactured by Torreken corporation (Tokyo レ & ダウコーニング Co., Ltd.), having a trade name and an average particle diameter of 3 μm

< other ingredients >

KBM-403: silane coupling agent, 3-glycidoxypropyltrimethoxysilane, available under the trade name of shin-Etsu chemical Co., Ltd

HW-4252E: release agent (oxidized polyethylene-based release agent having a number average molecular weight of 1,000) manufactured by Mitsui chemical Co., Ltd., trade name

Baxipalm wax No. 1: a mold release agent, carnauba wax, manufactured by Toyo ADL K.K. (Toyo アドレ Co., Ltd.), trade name

The characteristics of the molding material compositions for sealing prepared in examples 1 to 14 and comparative examples 1 to 6 were measured and evaluated under the following measurement conditions. The evaluation results are shown in tables 1 and 2.

The molding of the molding material is carried out by a transfer molding machine under conditions of a mold temperature of 185 ℃, a molding pressure of 10MPa, and a curing time of 180 seconds, unless otherwise specified. In addition, post-curing was carried out at 200 ℃ for 8 hours.

< evaluation item >

(1) Molding shrinkage factor α, shrinkage factor β, (β - α)

The molding material composition for sealing was molded under the above conditions using a mold having a diameter of 100mm × 10mmt, and post-cured under the above conditions to prepare a molded article (diameter of 100mm × 10 mmt). The molded article thus obtained was measured for four predetermined dimensions at room temperature (25 ℃) using a micrometer (DIGIMATIC MICROMETER, made by sanfeng (ltd. ミツトヨ), hereinafter the same) and the average value thereof was defined as the dimension of the molded article. From the dimensions of the obtained molded article, the amount of change with respect to the internal dimensions of the mold at room temperature was obtained, and the molding shrinkage α was calculated.

Further, after the molded article obtained under the above conditions was left at 250 ℃ for 500 hours, the dimensions of the molded article were measured at four predetermined positions at room temperature (25 ℃) by using a micrometer, and the average value thereof was recorded as the dimension of the molded article. From the dimensions of the obtained molded article, the amount of change with respect to the internal dimensions of the mold was obtained, and the shrinkage rate β was calculated.

(2) Storage modulus of elasticity

The molding material composition for sealing was molded under the above-mentioned conditions using a mold of 4.3mm × 3.0mm × 35mm, and further post-cured under the above-mentioned conditions to prepare a molded article (4.3mm × 3.0mm × 35 mm). The thickness of a sample obtained by cutting the molded article into a desired size was measured with a micrometer, and the dynamic viscoelasticity modulus at 25 ℃ and the dynamic viscoelasticity modulus at 250 ℃ were measured in a tensile mode of 10Hz and at a temperature increase rate of 10 ℃/min from room temperature (25 ℃) to 300 ℃ using a dynamic viscoelasticity apparatus (product name: Q800, manufactured by TAInstructions) to calculate the respective storage elastic moduli.

(3) Glass transition temperature (Tg) and coefficients of linear expansion CTE1, CTE2

The glass transition temperature (Tg) was measured as a criterion for the heat resistance of a cured product of the molding material composition for sealing. First, the molding material composition for sealing was molded under the above-mentioned conditions using a mold of 4mm × 4mm × 20mm, and further post-cured under the above-mentioned conditions to prepare a molded article (4mm × 4mm × 20 mm). The molded article was cut into a desired size to obtain a sample, and the sample was subjected to temperature rise from room temperature (25 ℃) to 320 ℃ at a temperature rise rate of 10 ℃ per minute by using a thermal analyzer (product name: SSC/5200, manufactured by Seiko instruments Co., Ltd. (セイコーインスツル) according to TMA method to measure the glass transition temperature (Tg). From the obtained TMA chart, the coefficient of linear expansion CTE1 was defined as the slope of the tangent line at 50 ℃ to 60 ℃ and the coefficient of linear expansion CTE2 was defined as the slope of the tangent line at 290 ℃ to 300 ℃.

(4) Generating stress

The molding shrinkage factor α, shrinkage factor β, and storage elastic modulus E obtained in the above (1) to (3)₂₅、E₂₅₀The glass transition temperature (Tg) and the coefficients of linear expansion CTE1 and CTE2 were calculated as values of σ (1), σ (2), and σ (3), and the value of the following formula (1) was calculated.

0.00MPa≤|σ(1)|+|σ(2)|+|σ(3)|≤100.0MPa (1)

σ(1)＝α×E₂₅

σ(3)＝(β-a)×E₂₅₀

Wherein α represents a molding shrinkage (%) of the cured product with respect to a mold size at 25 ℃, β represents a shrinkage (%) of the cured product with respect to a mold size at 25 ℃ after the cured product is left at 250 ℃ for 500 hours, and E₂₅Represents a storage elastic modulus (GPa), E at 25 ℃ of the cured product₂₅₀The storage elastic modulus (GPa) of the cured product at 250 ℃, the coefficient of linear expansion (ppm/. degree.C.) of a lead frame by CTEt, the coefficient of linear expansion (ppm/. degree.C.) of the cured product at a temperature lower than the glass transition temperature by CTE1, the coefficient of linear expansion (ppm/. degree.C.) of the cured product at a temperature higher than or equal to the glass transition temperature by CTE2, and the Tg, the glass transition temperature (degree.C.) of the cured product. Here, a lead frame made of copper was used as the lead frame, and the coefficient of linear expansion CTEt of the lead frame was set to 17ppm/℃.

(5) Starting temperature of thermal decomposition

As another criterion for the heat resistance of a cured product of the molding material composition for sealing, the thermal decomposition temperature based on a thermogravimetric differential thermal analyzer (TG-DTA) was measured. The molding material composition for sealing was molded under the above conditions using a mold of 4mm × 4mm × 20mm, and further post-cured under the above conditions to prepare a molded article (4mm × 4mm × 20 mm). The molded article was cut into a sample having the same size as that of the above-mentioned (3), and the sample was sufficiently crushed in a mortar to obtain a powder, which was heated from room temperature (25 ℃) to 600 ℃ at a temperature increase rate of 10 ℃/min. From the obtained weight change chart, the temperature at which 1% weight loss is recognized is referred to as the thermal decomposition temperature. "EXSTAR 6000" manufactured by Seiko instruments K.K. (セイコーインスツル, Ltd.) was used as the measurement apparatus.

(6) Adhesive Strength (cohesion force)

The molding material composition for sealing was molded under the above conditions on an island portion of a Cu lead frame (product name "LQFP-2828 p" manufactured by mitsui corporation, mitsui corporation) under high tech, and a molded article post-cured under the above conditions was further produced. The printed molded article having a diameter of 3.5mm formed on the island portion of the Cu lead frame was peeled off from the lower portion of the molded article at a height of 0.5mm from the lower portion thereof in the shear direction at a speed of 0.08 mm/sec using an adhesion tester (SS-30 WD, manufactured by Western GmbH), and the adhesion strength (adhesion force) between the molded article and the Cu lead frame was measured.

(7) Peelability (initial stage)

SiC chips (6 × 6 × 0.15mmt, no surface protection film) were fixed TO the center of the TO-247-sealed island (8.5 × 11.5mm) of the Cu lead frame using a sintered Ag paste (CT2700R7S) made by kyoto corporation (kyoto セラ), and 10 molded articles were prepared under the above conditions using the molding material composition for sealing. The molded article was observed using an ultrasonic imaging apparatus (FS 300II, manufactured by hitachi corporation), and the presence or absence of separation between islands around the SiC chip and the cured product of the molding material composition for sealing was confirmed. Before and after post-curing, the number of packages from which peeling of the island portion was observed after post-curing was 3 or less out of 10 was regarded as passed. As the Cu lead frame, a Cu lead frame was used which was subjected to argon plasma treatment for 60 seconds by a plasma cleaner AC-300 manufactured by Nordson corporation immediately before molding the molding material composition for sealing.

(8) Peelability (after temperature cycle test)

After the test of (7), a temperature cycle test was further performed as follows using 10 packages (molded articles) in total from which no peeling of island portions was observed and the molded articles produced under the conditions shown in (7). The molded article was left at-40 ℃ for 30 minutes, then heated at a heating rate of 40 ℃ per minute to 250 ℃ and left at 250 ℃ for 30 minutes, and then cooled at a cooling rate of 40 ℃ per minute to-40 ℃ as a single cycle, using TSA-42EL, a thermal shock test apparatus (manufactured by Espeek corporation, エスペック), and a temperature cycle test was performed for 1000 cycles. The molded article after the temperature cycle test was observed using an ultrasonic imaging apparatus (FS 300II, manufactured by hitachi corporation) to confirm whether or not the islands around the SiC chip and the cured product of the molding material composition for sealing were peeled, and it was regarded as acceptable that the number of packages from which island portions were peeled was 3 or less out of 10.

[ Table 1]

TABLE 1

*1: registered trademark

[ Table 2]

TABLE 2

*1: registered trademark

It is found that the sealing molding material compositions of examples 1 to 14 satisfying the formula (1) have high glass transition temperature and thermal decomposition initiation temperature of the cured product, excellent heat resistance, excellent adhesion to the semiconductor insert, and are less likely to cause separation from the semiconductor insert even after a temperature cycle test.

Claims

1. A molding material composition for sealing which comprises (A) a thermosetting resin, (B) a curing accelerator and (C) a filler,

a stress σ (1) generated when the molding material composition for sealing is cured in a mold under the conditions of 180 ℃ and 180 seconds and then post-cured outside the mold under the conditions of 200 ℃ and 8 hours to obtain a cured product, a stress σ (2) generated based on the thermal history generated when a temperature cycle test of-40 ℃ to 250 ℃ is performed for 1000 cycles using the cured product, and a stress σ (3) generated due to irreversible shrinkage of the cured product when the temperature cycle test is performed for 1000 cycles using the cured product satisfy the following formula (1),

o.ooMPa≤|σ(1)|+|σ(2)|+|σ(3)|≤100.0MPa (1)

σ(1)＝α×E₂₅

σ(3)＝(β-α)×E₂₅₀

wherein α represents the molding shrinkage of the cured product at 25 ℃ relative to the mold size, β represents the shrinkage of the cured product at 250 ℃ relative to the mold size after the cured product has been left to stand at 25 ℃ for 500 hours, and E₂₅Represents the storage elastic modulus at 25 ℃ of the cured product, E₂₅₀The storage elastic modulus at 250 ℃ of the cured product, CTEt represents the linear expansion coefficient of a lead frame, CTE1 represents the linear expansion coefficient of the cured product at a temperature lower than the glass transition temperature, CTE2 represents the linear expansion coefficient of the cured product at a temperature higher than or equal to the glass transition temperature, and Tg represents the glass transition temperature of the cured product, wherein the unit of the α and the β is%, and the E is₂₅And said E₂₅₀In GPa, in ppm/deg.C, in Tg in C, in CTEt, CTE1 and CTE 2.

2. The molding material composition for sealing according to claim 1,

the value of sigma (3) is 0.00-50.0 MPa.

3. The molding material composition for sealing according to claim 1 or 2,

the value of sigma (1) is 0.00-30.0 MPa.

4. The molding material composition for sealing according to any one of claims 1 to 3,

the value of alpha is 0.00-0.20%, and the value of beta-alpha is 0.00-0.40%.

5. The molding material composition for sealing according to any one of claims 1 to 4,

6. The molding material composition for sealing according to any one of claims 1 to 5,

7. The molding material composition for sealing according to any one of claims 1 to 6,

the (C) filler comprises (C-2) a hollow structured filler.

8. The molding material composition for sealing according to any one of claims 1 to 7,

9. An electronic component device, wherein,

the electronic component device comprises an element sealed with a cured product of the molding material composition for sealing of any one of claims 1 to 8.