JP2020145424A - Silicon carbide, gallium oxide, gallium nitride, and molding material composition for sealing diamond element, and electronic component device - Google Patents

Abstract

To provide a molding material composition for sealing that is excellent in heat resistance and is not likely to be separated from a semiconductor insert component during a temperature cycle test, and an electronic component device using the molding material composition for sealing.SOLUTION: A molding material composition for sealing contains a thermosetting resin, a hardening accelerator, and filler. A stress σ generated during curing of the molding material composition for sealing in a mold at 180°C, a stress σ generated when a temperature cycle test at -40 to 250°C is carried out 1000 cycles by using a cured product, and a generated stress σ generated due to irreversible expansion and contraction of the cured product when the temperature cycle test is carried out by using the cured product, satisfy the following formula (1).SELECTED DRAWING: None

Description

The present invention relates to SiC, Ga ₂ O ₃ , GaN, molding material compositions for encapsulating diamond devices, and electronic component devices.

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

In recent years, the momentum for energy conservation has been increasing worldwide against the background of anxiety about future depletion of resource energy or the so-called global warming problem. Power devices (power semiconductors), which control or convert electric power and are called "key devices for energy-saving technology," are attracting attention.
For power semiconductors, power conversion efficiency is one of the items that determine their performance. Here, we have been researching and developing power devices using new semiconductor materials such as silicon carbide (SiC), gallium nitride (GaN), gallium oxide (Ga ₂ O ₃ ), and diamond, which have higher conversion efficiency than conventional Si devices. Distribution in the market is booming.

Among them, SiC and GaN can operate at a high temperature as compared with conventional Si elements, and in particular, SiC has higher withstand voltage than Si elements, so that smaller elements and packages can be used more than ever. It is expected to achieve pressure resistance.

Further, especially in automobile applications, there is a demand for a sealing material that can be used in a harsh environment subject to large temperature changes.
For example, Patent Document 1 describes a sealing resin composition containing a thermosetting resin, a low stress agent, and a filler, and the glass transition temperature of the cured product of the sealing resin composition is determined. Along with satisfying specific conditions, the linear expansion coefficient α2 [ppm / ° C.] of the cured product above the glass transition temperature and the bending elasticity E ₂₅ [GPa] of the cured product at 25 ° C. satisfy the specific conditions. A sealing resin composition is disclosed.

JP-A-2018-150456

However, the sealing resin composition described in Patent Document 1 described above is not sufficiently durable for use in harsh environments in automobile applications in terms of temperature cycle resistance, and there is still room for improvement. ing.

The present invention has been made in view of such circumstances, and has high glass transition temperature and thermal decomposition start temperature, excellent heat resistance, excellent adhesion to semiconductor insert components, and even if a temperature cycle test is performed. It is an object of the present invention to provide a sealing molding material composition capable of obtaining a cured product which is less likely to be peeled from a semiconductor insert component, and an electronic component device using the sealing molding material composition.

As a result of diligent studies to solve the above problems, the present inventors cured the sealing molding material composition in the mold at 180 ° C. for 180 seconds, and then cured it outside the mold at 200 ° C., 8 Based on the generated stress σ (1) generated when post-curing under time conditions to obtain a cured product, and the heat history generated when 1000 cycles of temperature cycle tests at 40 to 250 ° C. were performed using the cured product. Sealing in which the generated stress σ (2) and the generated stress σ (3) generated by the irreversible shrinkage of the cured product when the temperature cycle test is performed 1000 cycles using the cured product satisfy specific conditions. It has been found that the molding material composition for use can solve the above-mentioned problems.
The present invention has been completed based on such findings.

That is, the disclosure of the present application relates to the following.
[1] A sealing molding material composition containing (A) a thermosetting resin, (B) a curing accelerator, and (C) a filler.
Occurrence that occurs when the sealing molding material composition is cured in a mold at 180 ° C. for 180 seconds and then post-cured outside the mold at 200 ° C. for 8 hours to obtain a cured product. The stress σ (1), the stress σ (2) generated by the heat history generated when the temperature cycle test at -40 to 250 ° C. is performed 1000 cycles using the cured product, and the temperature cycle using the cured product. Composition of SiC, Ga ₂ O ₃ , GaN and molding material for encapsulating diamond elements in which the stress σ (3) generated by the irreversible shrinkage of the cured product when the test is carried out for 1000 cycles satisfies the following formula (1). object.

(In the formula, α is the molding shrinkage rate (%) at 25 ° C. with respect to the mold size of the cured product, and β is 25 ° C. with respect to the mold size of the cured product after the cured product is left at 250 ° C. for 500 hours. The shrinkage rate (%), E ₂₅ is the storage elasticity (GPa) of the cured product at 25 ° C., E ₂₅₀ is the storage elasticity (GPa) of the cured product at 250 ° C., and CTEt is the linear expansion coefficient of the lead frame (GPa). (ppm / ° C.), CTE1 is the linear expansion coefficient (ppm / ° C.) below the glass transition temperature of the cured product, CTE2 is the linear expansion coefficient (ppm / ° C.) above the glass transition temperature of the cured product, and Tg is the above. Represents the glass transition temperature (° C) of the cured product.)
[2] The SiC, Ga ₂ O ₃ , GaN and molding material composition for encapsulating a diamond element according to the above [1], wherein the value of σ (3) is 0.00 to 50.0 MPa.
[3] The SiC, Ga ₂ O ₃ , GaN and diamond device encapsulating molding material composition according to the above [1] or [2], wherein the value of σ (1) is 0.00 to 30.0 MPa.
[4] The above-mentioned [1] to [3], wherein the value of α is 0.00 to 0.20% and the value of β-α is 0.00 to 0.40%. Molding material composition for encapsulating SiC, Ga ₂ O ₃ , GaN and diamond devices.
[5] The SiC, Ga ₂ O ₃ , GaN and diamond element seal according to any one of the above [1] to [4], wherein the thermal decomposition start temperature of the cured product of the sealing molding material composition is higher than 350 ° C. Molding material composition for stop.
[6] For encapsulating SiC, Ga ₂ O ₃ , GaN and diamond elements according to any one of [1] to [5] above, wherein the cured product of the molding material composition for encapsulation has an adhesive strength of 5 MPa or more. Molding material composition.
[7] Molding for SiC, Ga ₂ O ₃ , GaN and diamond element encapsulation according to any one of [1] to [6] above, wherein the (C) filler contains the (c-2) hollow structure filler. Material composition.
[8] The molding material composition for encapsulating SiC, Ga ₂ O ₃ , GaN and a diamond device according to any one of the above [1] to [7], which further contains (D) a low stress agent.
[9] The SiC according to any one of [1] to [8] above, wherein the (C) filler contains (c-3) an organic filler, and the (c-3) organic filler contains cellulose. Ga ₂ O ₃ , GaN and diamond device encapsulation molding material composition.
[10] An electronic component device including an element sealed by a cured product of the molding material composition for sealing according to any one of the above [1] to [9].

According to the present invention, a cured product having a high glass transition temperature and a thermal decomposition start temperature, excellent heat resistance, excellent adhesion to semiconductor insert parts, and less likely to peel off from semiconductor insert parts even when a temperature cycle test is performed. It is possible to provide a sealing molding material composition capable of obtaining the above, and an electronic component device using the sealing molding material composition.

Hereinafter, the present invention will be described in detail with reference to one embodiment.

<Molding material composition for sealing SiC, Ga ₂ O ₃ , GaN and diamond elements>
The SiC, Ga ₂ O ₃ , GaN and diamond element encapsulating molding material composition of the present embodiment (hereinafter, also simply referred to as encapsulating molding material composition) are (A) thermosetting resin and (B) cured. A sealing molding material composition containing an accelerator and (C) filler, wherein the sealing molding material composition is cured in a mold at 180 ° C. for 180 seconds, and then outside the mold. The generated stress σ (1) generated when the cured product is obtained by post-curing under the conditions of 200 ° C. for 8 hours, and when a temperature cycle test at 40 to 250 ° C. is performed for 1000 cycles using the cured product. The generated stress σ (2) due to the generated heat history and the generated stress σ (3) generated by the irreversible shrinkage of the cured product when the temperature cycle test is performed 1000 cycles using the cured product are as follows. It is characterized by satisfying (1).

(In the formula, α is the molding shrinkage rate (%) at 25 ° C. with respect to the mold size of the cured product, and β is 25 ° C. with respect to the mold size of the cured product after the cured product is left at 250 ° C. for 500 hours. The shrinkage rate (%), E ₂₅ is the storage elasticity (GPa) of the cured product at 25 ° C., E ₂₅₀ is the storage elasticity (GPa) of the cured product at 250 ° C., and CTEt is the linear expansion coefficient of the lead frame (GPa). (ppm / ° C.), CTE1 is the linear expansion coefficient (ppm / ° C.) below the glass transition temperature of the cured product, CTE2 is the linear expansion coefficient (ppm / ° C.) above the glass transition temperature of the cured product, and Tg is the above. Represents the glass transition temperature (° C) of the cured product.)

The present inventors have conducted a temperature cycle test at -40 to 250 ° C. (hereinafter, also simply referred to as a temperature cycle test), and then the semiconductor insert component and the sealing resin (cured product) are separated from each other by the semiconductor insert. The adhesive force between the part and the cured product is the stress generated when the sealing molding material composition is molded (cured) (generated stress σ (1)), and the temperature cycle test is performed using the cured product. The stress σ (2) generated by the thermal history generated when 1000 cycles are performed, and the stress σ generated by the irreversible shrinkage of the cured product when the temperature cycle test is performed 1000 cycles using the cured product. It was found that it occurs when it is smaller than the sum of (3), and that the generated stress is within a specific range.

The sum of the absolute values of the generated stress σ (1) and the absolute values of σ (2) and σ (3) is 0.00 MPa or more and 100.0 MPa or less. If the sum of the absolute values of σ (1) and σ (2) and σ (3) exceeds 100.0 MPa, the cured product may peel off from the semiconductor insert component after the temperature cycle test. From this point of view, the sum of the absolute values of σ (1) and the absolute values of σ (2) and σ (3) is preferably 80.0 MPa or less, more preferably 70.0 MPa or less.

The generated stress σ (1) is generated when the molding material composition for sealing of the present embodiment is molded, and the composition that was in a liquid state at the time of molding changes to a solid (cured product). It is the total value of the "curing shrinkage" generated by the above and the stress generated due to the "dimensional change due to the post-curing" generated by the post-curing under the conditions of 200 ° C. for 8 hours. σ (1) is an irreversible residual stress. From the viewpoint of preventing peeling between the semiconductor insert component and the cured product even when a temperature cycle test is performed using the cured product of the molding material composition for sealing, the σ (1) is “0 or positive”. It is preferable to take a "value of", and when it takes a "positive value", the value is preferably as small as possible. When σ (1) takes a "positive value", it means that α is a "positive value", that is, "the size is reduced as compared with the time of molding", which means "molding material composition". It means that stress in the direction of being pressed against the semiconductor insert member (compression direction) acts on the object. " On the other hand, when σ (1) takes a “negative value”, from the same argument, “stress in the direction of peeling from the insert member (tensile direction) acts” on the molding material composition, and the compression direction Compared with the stress of, the peeling is significantly promoted. Therefore, σ (1) is preferably “0 or a positive value”. Specifically, the preferable range of σ (1) is preferably 30.0 MPa or less, more preferably 28.0 MPa or less, still more preferably 25.0 MPa or less, and particularly preferably 0.00 MPa. When the value of σ (1) is 30.0 MPa or less, the internal stress in the direction of compressing the cured product does not become too large, the adhesion between the semiconductor insert component and the cured product is improved, and initial peeling is less likely to occur. be able to.
Here, the initial peeling in the present specification means the peelability of the cured product immediately after the semiconductor insert component is sealed with the cured product of the molding material composition for sealing.

Further, from the viewpoint of making it difficult for peeling between the semiconductor insert component and the cured product after the temperature cycle test, the value of α may be "0 (zero) or a positive value" from the above discussion. Preferably, when taking a "positive value", the value is preferably as small as possible. Specifically, the value of α is preferably 0.00 to 0.20%, more preferably 0.00 to 0.15%. When the value of α is 0.00% or more, stress in the compression direction acts inside the package, the adhesion between the semiconductor insert component and the cured product is improved, and initial peeling can be prevented from occurring. On the other hand, when the value of α is 0.20% or less, the internal stress in the direction of compressing the cured product does not become too large, the adhesion between the semiconductor insert component and the cured product is improved, and initial peeling is less likely to occur. Can be done.
By setting the value of α within the range, the value of σ (1) can be set within the range. The value of α is adjusted so that the linear expansion coefficient CTE1 of the sealing molding material composition is 8 to 15 ppm / ° C., more preferably 9 to 14 ppm / ° C., and then 200 ° C. for 8 hours. This can be achieved by selecting a thermosetting resin system in which the glass transition point after curing is 200 ° C. or higher, more preferably 210 ° C. or higher.
The α can be obtained by the method described in Examples.

The cured product repeats reversible expansion and contraction for a while from the start of the temperature cycle test, but gradually thermal decomposition of the cured product begins and irreversible contraction of the cured product begins.
The generated stress σ (2) is a thermal stress generated during the cycle in which the cured product repeats reversible expansion and contraction from the start of the temperature cycle test, and is a reversible stress. Further, the generated stress σ (3) is a stress generated by the irreversible shrinkage of the cured product during 1000 cycles from the cycle in which the thermal decomposition of the cured product starts.
The guideline for the cycle in which the cured product repeats reversible expansion and contraction is about 50 to 400 cycles from the start of the temperature cycle test, although there are differences depending on the type of thermosetting resin.

When the glass transition temperature (Tg) of the cured product of the sealing molding material composition is 200 ° C. or higher and lower than 250 ° C., the Tg is within the temperature range of the temperature cycle test, and the value of 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 CTE2. On the other hand, when the Tg is 250 ° C. or higher, the Tg is equal to or higher than the temperature range of the temperature cycle test, so that the value of σ (2) is the thermal stress generated in the region having the coefficient of linear expansion CTE1.
The value of σ (2) is preferably 35.0 MPa or less, more preferably 30.0 MPa or less, from the viewpoint of preventing peeling between the semiconductor insert component and the cured product even when the temperature cycle test is performed. is there.

The glass transition temperature (Tg) of the cured product is preferably 200 ° C. or higher, more preferably 210 ° C. or higher, from the viewpoint of reducing the generated stress σ (3) due to thermal decomposition of the resin or the like. The upper limit of the glass transition temperature may be, for example, 320 ° C. or lower, or 310 ° C. or lower.
The glass transition temperature (Tg) can be measured by thermomechanical analysis (TMA), and specifically, can be measured by the method described in Examples.

The coefficient of linear expansion CTE1 of the cured product is preferably 8 to 15 ppm / ° C., more preferably 9 to 14 ppm / ° C. Further, the coefficient of linear expansion CTE2 of the cured product preferably has a value as close as possible to the above-mentioned CTE1 from the viewpoint of the difference in coefficient of linear expansion from the semiconductor insert component, but preferably 75 ppm / ° C. or less, and 70 ppm / ° C. More preferably, it is below ° C.
By setting the linear expansion coefficients CTE1 and CTE2 of the cured product within the above range, the value of σ (2) can be within the above range. The linear expansion coefficients CTE1 and CTE2 of the cured product are made of molten silica and / or synthetic silica as the filler, and the content thereof is about 65 to 85% by mass of the entire molding material composition for sealing. This can be within the above range.

In the present embodiment, the coefficient of linear expansion CTE1 of the cured product can be obtained from the slope of the tangent line at 50 to 60 ° C. in the TMA chart obtained by measurement by thermomechanical analysis (TMA). The coefficient of linear expansion CTE2 of the cured product can be obtained from the slope of the tangent line at 290 to 300 ° C. in the TMA chart. Specifically, it can be measured by the method described in Examples.

The σ (3) is preferably 0 (zero) or a positive value from the viewpoint of preventing peeling between the semiconductor insert component and the cured product even when the temperature cycle test is performed. Specifically, it is preferably 50.0 MPa or less, more preferably 40.0 MPa or less, and 0.00 MPa. Is particularly preferable. When the value of σ (3) is 50.0 MPa or less, the internal stress in the direction of compressing the cured product does not become too large, and it is possible to prevent the semiconductor insert component and the cured product from peeling off after the temperature cycle test. ..

Further, from the viewpoint of preventing peeling between the semiconductor insert component and the cured product after the temperature cycle test, it is preferable to set σ (3) to the above value, and for that purpose, the above (β-). The value of α) is preferably 0.00 to 0.40%, more preferably 0.00 to 0.30%. When the value of (β-α) is 0.00% or more, the stress inside the package acts in the compression direction compared to the initial state (before the temperature cycle test), and the semiconductor insert component and the cured product The adhesion is improved, and peeling between the semiconductor insert component and the cured product can be prevented from occurring after the temperature cycle test.
On the other hand, when the value of (β-α) is 0.40% or less, the internal stress in the direction of compressing the cured product does not become too large, the adhesion between the semiconductor insert component and the cured product is improved, and the temperature cycle It is possible to prevent peeling between the semiconductor insert component and the cured product after the test.
By setting the value of (β-α) within the above range, the value of σ (3) can be within the above range. The value of (β-α) can be within the above range by setting the thermal decomposition start temperature of the cured product to preferably 350 ° C. or higher, more preferably 360 ° C. or higher, but a part of the filler. For example, it is particularly effective to use 0.5 to 20% by mass of the filler as a hollow structure filler having an average particle diameter of about 3 to 100 μm.

The value of β is preferably 0.50% or less, more preferably 0.40% or less. By setting the value of β within the range, the value of (β-α) can be set within the range.
The β can be obtained by the method described in Examples.

The storage elastic modulus E ₂₅ of the cured product at 25 ° C. is preferably 8 to 15 GPa, more preferably 9 to 14 GPa. When the value of E ₂₅ is within the above range, the values of σ (1), σ (2), and σ (3) can be set within the above range, respectively.

The storage elastic modulus E ₂₅₀ of the cured product at 250 ° C. is preferably 2 to 10 GPa, more preferably 2 to 9 GPa. When the value of E ₂₅₀ is within the above range, the value of σ (2) can be within the above range.
The storage elastic modulus can be measured by Dynamic Mechanical Analysis (DMA), and specifically, can be measured by the method described in Examples.

The encapsulating molding material composition of the present embodiment contains (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 at least two or more selected from the group consisting of maleimide resin, phenol resin, epoxy resin, benzoxazine resin, and cyanate resin are heat resistant. It is preferable from the viewpoint of property, 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 a compound represented by the following general formula (I) is preferable. Maleimide resin is a resin that forms a three-dimensional network structure and is cured by reacting maleimide groups with heating. In addition, the maleimide resin imparts a high glass transition temperature (Tg) to the cured product by a cross-linking reaction to improve heat resistance and heat-decomposability.

In the general formula (I), R ¹ is independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom. p is an integer of 0 to 4 independently, and q is an integer of 0 to 3.
Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group; a chloromethyl group, a 3-chloropropyl group and the like. Substituent alkyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; aryl group such as phenyl group, tolyl group, xsilyl group; monovalent such as aralkyl group such as benzyl group and phenethyl group The hydrocarbon group of.
Also, if the R ¹ there are a plurality, the plurality of R ¹ may be the same or different from each other.
z is an integer of 0 to 10, preferably an integer of 0 to 4.

The maleimide resin represented by the general formula (I) is compared with at least one selected from the group consisting of a phenol resin and a benzoxazine resin at a temperature of 170 ° C. or higher in the presence of a curing accelerator (B) described later. The addition reaction is easily carried out to give high heat resistance to the cured product of the molding material composition for sealing.

Specific examples of the maleimide resin represented by the general formula (I) include N, N'-(4,4'-diphenylmethane) bismaleimide and bis (3-ethyl-5-methyl-4-maleimidephenyl). ) Methane, polyphenylmethane maleimide and the like.
Further, the maleimide resin is, for example, N, N'-(4,4'-diphenylmethane) bismaleimide having z = 0 as a main component, BMI, BMI-70 (all manufactured by Keiai Kasei Co., Ltd.). , BMI-1000 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), which is a polyphenylmethane maleimide containing z = 0 to 2 as a main component, can be obtained as commercial products. it can.

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 that can be used in combination include m-phenylene bismaleimide, 2,2-bis [4- (4-maleimide phenoxine) phenyl] propane, and 1,6-bismaleimide- (2,2,4-trimethyl). ) Hexane and the like can be mentioned. Other conventionally known maleimide resins may be used in combination. When a maleimide resin other than the maleimide resin represented by the general formula (I) is blended, the blending amount thereof is preferably 30 parts by mass with respect to 100 parts by mass of the maleimide resin represented by the general formula (I). Parts or less, more preferably 20 parts by mass or less.

As long as the phenol resin has two or more phenolic hydroxyl groups per molecule, those generally used as a sealing material for electronic parts are widely used without being limited by the molecular structure, molecular weight, etc. Can be done. Examples of the phenol resin include phenol novolac resin, phenol xylene resin, cresol novolac resin, aralkyl type phenol resin, cyclopentadiene type phenol resin, triphenol alkane type phenol resin, triphenylmethane type phenol resin, naphthalene type phenol resin, and biphenyl. Examples include type phenolic resin. Of these, triphenylmethane-type phenolic resin and naphthalene-type phenolic resin are preferable from the viewpoint of glass transition temperature (Tg), and biphenyl-type phenolic resin is preferable from the viewpoint of thermal decomposition. These may be used alone or in combination of two or more.

The softening point of the phenolic resin is preferably 55 to 120 ° C., more preferably 60 to 110 ° C. from the viewpoint of productivity, flow characteristics and the like of the sealing molding material composition.
The softening point in the present specification refers to a "ring-ball type softening point" and means a value measured in accordance with ASTM D36.

The triphenylmethane-type phenol resin is preferably a phenol resin having a triphenylmethane skeleton represented by the following general formula (II), and the naphthalene-type phenol resin is a naphthalene represented by the following general formula (III). A phenolic resin having a skeleton is preferable.

(In the formula, x is 0 to 10.)

(In the formula, y1 is 0 to 10.)

In the general formula (II), x is 0 to 10, preferably 1 to 4. Further, in the general formula (III), y1 is 0 to 10, preferably 0 to 3.

The phenol resin represented by the general formula (II) is MEH-7500 (manufactured by Meiwa Kasei Co., Ltd.), and the phenol resin represented by the general formula (III) is SN-485 (Nippon Steel & Sumitomo Metal Chemical Co., Ltd.). ), And the biphenyl-type phenol resin can be obtained as a commercially available product as MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.).

As long as the epoxy resin has two or more epoxy groups in one molecule, it is widely used that is generally used as a sealing material for electronic parts without being limited by the molecular structure, molecular weight, etc. Can be done. Examples of the epoxy resin include biphenyl type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dicyclopentadiene type epoxy resin, and bird. Heterocyclic epoxy resin such as phenylmethane type epoxy resin, triphenol methane type epoxy resin, triazine nucleus containing epoxy resin, stillben type bifunctional epoxy resin, naphthalene type epoxy resin, dihydroxynaphthalene novolac type epoxy resin, condensed ring aromatic carbonization Examples thereof include hydrogen-modified epoxy resin and alicyclic epoxy resin. Of these, a triphenylmethane type epoxy resin and a naphthalene type epoxy resin are preferable from the viewpoint of glass transition temperature (Tg), and a biphenyl type epoxy resin is preferable from the viewpoint of thermal decomposition.
One type of these epoxy resins may be used, or two or more types may be mixed and used.

The softening point of the epoxy resin is preferably 40 to 130 ° C., more preferably 50 to 110 ° C. from the viewpoint of improving productivity and fluidity of the molding material composition for sealing.

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

(In the formula, n1 is 0 to 10.)

(In the formula, n2 is 0 to 10.)

In the general formula (IV), n1 is 0 to 10, preferably 0 to 3. Further, in the general formula (V), n2 is 0 to 10, preferably 0 to 3.

The epoxy resin represented by the general formula (IV) is EPPN-502H (manufactured by Nippon Steel Corporation), and the epoxy resin represented by the general formula (V) is ESN-375 (Nippon Steel & Sumikin Chemical Co., Ltd.). The epoxy resin represented by the general formula (VI) is HP-4710 (manufactured by DIC Corporation), and the biphenyl type epoxy resin is NC-3000 (Nippon Steel & Sumikin Co., Ltd.). (Manufactured), each of which can be obtained as a commercially available product.

The benzoxazine resin may be a compound having two or more benzoxazine rings in one molecule and can be polymerized, and is not particularly limited. However, from the viewpoint of the glass transition temperature (Tg), the following general formula (VII) is used. The compound represented is preferred.

In the general formula (VII), X1 is an alkylene group having 1 to 10 carbon atoms, an oxygen atom, or a direct bond. R ² and R ³ are each independently a hydrocarbon group having 1 to 10 carbon atoms.

The alkylene group of X1 has 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. 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, an octylene group and the like. Of these, a methylene group, an ethylene group and a propylene group are preferable, and a methylene group is particularly preferable.

Examples of the hydrocarbon group having 1 to 10 carbon atoms of R ² and R ³ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group; a vinyl group and an allyl group. , Alkenyl groups such as butenyl group, pentenyl group and hexenyl group; aryl groups such as phenyl group, tolyl group and xsilyl group; monovalent hydrocarbon groups such as aralkyl groups such as benzyl group and phenethyl group.
Further, when a plurality of R ² and R ³ exist, the plurality of R ² and the plurality of R ³ may be the same or different from each other.

m1 is independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0. m2 is independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 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). One type of these resins may be used, or two or more types may be used in combination.

As the benzoxazine resin, a benzoxazine resin represented by the above formula (VII-1) is preferable. Further, in the benzoxazine resin represented by the general formula (VII), the content of the benzoxazine resin represented by the formula (VII-1) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass. %, More preferably 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 Pd (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

Examples of the cyanate resin include a cyanate ester monomer having at least two cyanate groups in one molecule (hereinafter, also simply referred to as a cyanate ester monomer). The cyanate ester monomer is particularly advantageous in adhesion.
In addition, in this embodiment, a "cyanate ester monomer" refers to a cyanate ester compound which does not contain a 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. For example, bis (4-cyanatephenyl) methane, 1,1-bis (4-cyanatephenyl) ethane, 2,2-bis (4-cyanatephenyl) propane, bis (3-methyl-4-cyanatephenyl) methane, A compound having two cyanate groups in one molecule, such as bis (3,5-dimethyl-4-cyanatephenyl) methane, bis (3,5-dimethyl-4-cyanatephenyl) -4-cyanatephenyl-1,1 , 1-ethane, etc., compounds having three cyanate groups in one molecule, and the like can be mentioned. Conventionally known compounds other than these may be used.

Specific examples of the cyanate ester monomer include Primacet LECY (manufactured by Lonza Japan Co., Ltd.) containing 1,1-bis (4-cyanatephenyl) ethane as a main component and 2,2-bis (4-cyanatephenyl). ) CYTESTER (registered trademark) TA (manufactured by Mitsubishi Gas Chemical Company, Inc.) containing propane as a main component can be obtained as a commercially available product.

As the thermosetting resin (A), a thermosetting resin other than the above-mentioned maleimide resin, phenol resin, epoxy resin, benzoxazine resin, and cyanate resin may be used in combination as long as the effect of the present invention is not impaired. .. For example, when a cyanate ester monomer is used as the thermosetting resin (A), a cyanate ester resin having a repeating structure in the molecule, such as a novolak type cyanate ester, can be used in combination.
When the maleimide resin, phenol resin, epoxy resin, benzoxazine resin, and cyanate resin are used in combination as the (A) thermosetting resin, and a thermosetting resin other than these resins is used in combination, the (A) thermosetting resin The content of the maleimide resin, the phenol resin, the epoxy resin, the benzoxazine resin, and the cyanate resin with respect to the total amount is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.

The content of the thermosetting resin (A) is preferably 10 to 30% by mass, more preferably 15 to 25% by mass, based on the total amount of the molding material composition for sealing. (A) When the content of the thermosetting resin is 10% by mass or more, moldability such as flow characteristics can be ensured, and when it is 30% by mass or less, insulation properties such as flame retardancy and tracking resistance are obtained. Can be secured.

[(B) Curing accelerator]
As the curing accelerator (B) used in the present embodiment, those generally used as a sealing material for electronic components can be widely used without particular limitation. Examples of the (B) curing accelerator include (b-1) phosphorus-based curing accelerator, (b-2) imidazole-based curing accelerator, and the like, from the viewpoint of the balance between adhesion and moldability. It is preferable to use in combination.
In the present embodiment, the "imidazole-based curing accelerator" is synonymous with an imidazole compound containing a nitrogen atom at the 1st and 3rd positions on the 5-membered ring.

The phosphorus-based curing accelerator (b-1) mainly comprises a cross-linking reaction between the maleimide resin and the phenol resin and / or the benzoxazine resin, and cross-linking between the phenol resin and / or the benzoxazine resin and the epoxy resin. It has a function of promoting the reaction and the tripartization reaction of the cyanate resin. The phosphorus-based curing accelerator (b-1) indirectly reduces the self-polymerization reaction between the maleimide resins by accelerating these reactions, and suppresses the generation of peel stress with the semiconductor insert component. Have.

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

The imidazole-based curing accelerator (b-2) mainly has a function of promoting the self-polymerization reaction of the maleimide resin and enhancing the moldability of the molding material composition for sealing. Further, the action of the (b-2) imidazole-based curing accelerator is promoted by the presence of the epoxy resin, and it is possible to impart good curability and moldability to the sealing molding material composition of the present embodiment. It becomes.

Examples of the (b-2) imidazole-based curing accelerator include 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl. -4-Methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2-phenyl-4 -Methyl-5-hydroxymethylimidazole and the like can be exemplified, and these may be used alone or in combination of two or more. Further, a conventionally known imidazole-based curing accelerator other than the above may be applied.

The imidazole-based curing accelerator (b-2) can be appropriately selected and used as necessary. From the viewpoint of the balance between the moldability of the molding material composition for encapsulation and the adhesion between the cured product of the composition and the semiconductor insert component, 2,4-diamino-6- [2'-methylimidazolyl- (1'). )] It is preferable to use a compound having a relatively high activity temperature, such as -ethyl-s-triazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole, alone, or in combination of two or more. Specifically, the reaction start temperature when the (b-2) imidazole-based curing accelerator is reacted with a bisphenol A type epoxy resin (liquid) at a mass ratio of 1/20 is preferably 5 ° C. It is more than 175 ° C., more preferably 100 ° C. or more and less than 160 ° C., still more preferably 100 ° C. or more and 150 ° C. or less. The above-mentioned (b-2) imidazole-based hardening accelerator may be used alone or in combination of two or more.
Here, the reaction start temperature is defined as when the composition containing (b-2) imidazole-based curing accelerator and bisphenol A type epoxy resin is heated at a heating rate of 10 ° C./min using DSC. It refers to the temperature at the intersection of the tangent line and the temperature axis of the steepest peak on the rising curve of the exothermic or heat absorption peak.
When the reaction start temperature of the imidazole-based curing accelerator (b-2) is 85 ° C. or higher, peeling from the semiconductor insert component can be reduced, and when it is lower than 175 ° C., a molding material composition for sealing. The moldability of the product can be improved.

The content of the curing accelerator (B) is preferably 0.1 to 1.0% by mass, more preferably 0.1 to 0.5% by mass, based on the total amount of the molding material composition for sealing. (B) When the content of the curing accelerator is 0.1% by mass or more, the moldability of the molding material composition for sealing can be ensured, and when it is 1.0% by mass or less, the fluidity can be ensured. It will be possible.

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

[(C) Filler]
The filler (C) used in the present embodiment is not particularly limited, and conventionally known fillers can be used. Examples of the (C) filler include (c-1) an inorganic filler, (c-2) a hollow structure filler, and (c-3) an organic filler, and particularly due to a dimensional change during a temperature cycle test. From the viewpoint of reducing the generated stress σ (3), (c-1) inorganic filler and (c-2) hollow structure filler are used together, or (c-1) inorganic filler and (c-3) organic filler are used together. It is preferable to use it together with the material. All of (c-1) inorganic filler, (c-2) hollow structure filler, and (c-3) organic filler may be filled.
In the present embodiment, the “hollow structure filler” refers to a filler having one or more hollow structures inside the filler.

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

The average particle size of the inorganic filler (c-1) is preferably 5 to 30 μm, more preferably 6 to 25 μm, and even more preferably 8 to 20 μm. When the average particle size is 5 μm or more, the moldability can be improved, and when it is 30 μm or less, the mechanical strength can be improved.
In the present specification, the average particle size refers to the median value (D50) measured by a laser diffraction / scattering method (for example, manufactured by Shimadzu Corporation, apparatus name: SALD-3100).

The content of the (c-1) inorganic filler is preferably 70 to 100% by mass, more preferably 80 to 99% by mass, based on the total amount of the (C) filler from the viewpoint of linear expansion coefficient, mechanical strength and the like. More preferably, it is 90 to 99% by mass.

The hollow structure filler (c-2) reduces the (initial) generated stress σ (1) generated due to the dimensional change (molding shrinkage rate) accompanying the curing of the sealing molding material composition, and at 250 ° C. By reducing the shrinkage rate β after being left for 500 hours, it is also effective in suppressing the generated stress σ (3).

The hollow structure filler (c-2) is not particularly limited, and is an inorganic hollow structure such as so-called hollow glass containing soda lime glass, borosilicate glass, aluminum silicate, mullite, quartz and the like as main components and hollow silica. Use a silicone-based hollow structure filler containing a silicone compound as a main component, such as a silsesquioxane compound having a structure in which the siloxane bond is represented by (CH ₃ SiO _3/2 ) _n in a three-dimensional network. be able to.
The "silsesquioxane compound" in the present specification has a structure in which the siloxane bond is cross-linked in a three-dimensional network represented by (CH ₃ SiO _3/2 ) _n , and has a methyl group and phenyl in the side chain. It refers to a compound having an organic functional group such as a group in which the side chain is a methyl group in an amount of 80% or more.
Among the "hollow structure fillers", the inorganic hollow structure filler and the silicone-based hollow structure filler have high heat resistance of the hollow structure filler itself, so that the composition of the molding material for sealing has higher heat resistance. It can be used for things.

The elastic modulus of the hollow structure filler (c-2) is preferably 0.1 to 15 GPa, more preferably 0.2 to 12 GPa. Among them, the inorganic hollow structure fillers such as hollow glass and hollow silica having a relatively high elastic modulus have a relatively high effect of suppressing shrinkage of the sealing resin during curing, and a high effect of suppressing stress generated during curing. Therefore, it is preferable. Further, a silicone-based hollow structure filler having a relatively low elastic modulus is preferable because the elastic modulus of the encapsulant can be lowered by adding a small amount and the stress relaxation effect during heat shrinkage is high. When an inorganic hollow structure filler such as hollow glass or hollow silica is used in combination with a silicone-based hollow structure filler, even if a relatively small amount is added, the effect of suppressing peeling from the semiconductor insert component is high, and high heat resistance is required. It is also applicable to the sealing resin to be used, and is uniform in the present embodiment.
The elastic modulus of the hollow structure filler (c-2) in the present embodiment can be measured by, for example, a dynamic ultrafine hardness tester.

(C-2) The hollow structure filler contains at least one selected from silica, alumina, and a silica-alumina compound, particularly from the viewpoint of the effect of suppressing the generated stress σ (3) due to the dimensional change during the temperature cycle test. An inorganic hollow structure filler and / or a silicone-based hollow structure filler containing a silsesquioxane compound is preferable, and among them, an inorganic hollow structure containing at least one selected from silica-alumina compound and alumina. It is more preferably a structural filler.

The hollow structure filler (c-2) that can be suitably used in the present embodiment preferably does not contain an alkali metal and / or an alkaline earth metal from the viewpoint of reducing corrosion of the semiconductor insert due to ionic impurities. If contamination cannot be prevented, it should be reduced as much as possible.

(C-2) A hollow structure filler containing at least one selected from silica, alumina, and a silica-alumina compound and having a low content of alkali metal, alkaline earth metal, and the like is, for example, silicic acid. It is available on the market as Kinospheres (manufactured by Kansai Matek Co., Ltd., trade name) and Espheres (manufactured by Pacific Cement Co., Ltd., trade name) whose main components are aluminum and mullite (compound of silica and alumina). is there. Further, as a silicone-based hollow structure filler containing a silsesquioxane compound (silsesquioxane compound-based filler), for example, NH-SBN04 (Nikko Rica Co., Ltd.) containing polymethylsilsesquioxane as a main component. It is available on the market as a product (trade name).

(C-2) The hollow structure filler has an average particle diameter of 3 to 100 μm from the viewpoint of reducing peeling from the semiconductor insert component and achieving both productivity and moldability of the molding material composition for encapsulation. It is preferably 3 to 60 μm, and more preferably 3 to 60 μm. When the average particle size is 3 μm or more, peeling is reduced, and when the average particle size is 100 μm or less, the productivity and moldability of the sealing molding material composition are good.

As the hollow structure filler having an average particle size of 3 to 100 μm, the Kinospheres (manufactured by Kansai Matek Co., Ltd., trade name) series such as Kinospheres 75 (average particle size 35 μm) is used, and Easefields (Pacific Cement Co., Ltd.) (Product, trade name) series, such as Easefields SL75 (average particle size 55 μm) and Easefear's SL125 (average particle size 80 μm) are available on the market. In addition, Glass Bubbles K37 (average particle size 45 μm), Glass Bubbles iM30K (average particle size 16 μm) (above, manufactured by 3M Japan Ltd.), NH-SBN04 (average particle size 4 μm, manufactured by Nikko Rika Co., Ltd.), etc. Is also available on the market.

When the molding material composition for sealing of the present embodiment contains (c-2) a hollow structure filler, the content thereof is preferably 0.5 to 30% by mass with respect to the total amount of the (C) filler. It is more preferably 1 to 20% by mass, still more preferably 1 to 10% by mass. (C-2) When the content of the hollow structure filler is 0.5% by mass or more, the peeling from the semiconductor insert component is reduced due to the effect of reducing the generated stress σ (3), and it should be 20% by mass or less. For example, the moldability and the insulating property are improved, and it is possible to prevent a decrease in thermal conductivity. In particular, when the (c-2) hollow structure filler contains a silsesquioxane compound, the content thereof is preferably 0.5 to 10% by mass, more preferably 1 to 6 with respect to the total amount of the (C) filler. It is by mass, more preferably 1.2 to 5% by mass.

Examples of the (c-3) organic filler include resin fillers and fibrous fillers. Examples of the resin filler include those made of cellulose, nylon, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, tetrafluoroethylene resin and the like. The resin filler may have a core-shell structure. Examples of the fibrous filler include polyester fibers, aramid fibers, cellulose fibers and the like. Above all, from the viewpoint of reducing thermal stress, it is preferable that the (c-3) organic filler has high crystallinity and does not have a melting point or a softening point in a temperature range up to 250 ° C. Specifically, the (c-3) organic filler preferably contains a cellulose component.

When the molding material composition for sealing of the present embodiment contains (c-3) an organic filler, the content thereof is preferably 0.03 to 1.5% by mass with respect to the total amount of the molding material composition. It is more preferably 0.05 to 1.0% by mass, and even more preferably 0.1 to 0.5% by mass. When it is 0.03% by mass or more, the effect of reducing thermal stress can be sufficiently obtained, and when it is 1.5% by mass or less, the fluidity of the molding material composition for sealing can be enhanced.

The average particle size of the (c-3) organic filler is preferably 0.1 to 150 μm, more preferably 0.5 to 100 μm, and even more preferably 1 to 75 μm. (C-3) The shape of the organic filler may be fibrous or irregular. In the case of fibrous or amorphous, it is preferable that the average value of the length (major axis) of the longest portion of each particle is in the above range. When the average particle size is 0.1 μm or more, the fluidity of the molding material composition for sealing can be enhanced, and when it is 150 μm or less, the effect of reducing thermal stress can be sufficiently obtained.

(C-3) From the viewpoint of electrical reliability, the organic filler preferably contains as little ionic impurities as possible.
The (c-3) organic filler may be added as it is, or may be added after premixing with a part or all of the (A) thermosetting resin in advance. (C-3) The organic filler is available on the market as KC Flock (registered trademark) W-50GK (manufactured by Nippon Paper Industries, Ltd., trade name, average particle size 45 μm) and the like.

In the present invention, it is more effective to add the (c-3) organic filler with the silane coupling agent by stirring and mixing it, and then premixing it with a part or all of the (A) thermosetting resin. ..
Examples of silane coupling agents include epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-. Aminosilanes such as aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; 3-mercaptopropyl Examples thereof include mercaptosilane such as trimethoxysilane; isocyanate silane such as 3-isocyanoxide propyltriethoxysisilane, and conventionally known silane coupling agents can be appropriately used.
From the viewpoint of (c-3) dispersibility of the organic filler in (A) thermosetting resin, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and N-phenyl-3-aminopropyltri A silane coupling agent having an alicyclic or aromatic ring in the molecule, such as methoxysilane, is preferable.

As a method of premixing a part / or all of the silane coupling agent with (c-3) an organic filler and a part / or all of (A) a thermosetting resin, for example, (c-3) organic filling The mixing ratio of the material and a part of the silane coupling agent was set to 50/1 to 2/1 in terms of mass ratio, and the mixture was stirred and mixed at room temperature (25 ° C.) for 1 to 30 minutes, and then (A) heat. (A) The thermosetting resin is mixed so that the ratio of a part of the curable resin to (c-3) the organic filler is 100/1 to 10/1 in terms of mass ratio, and (A) the thermosetting resin It is possible to exemplify mixing at a temperature equal to or higher than the melting point or the softening point, for example, 70 to 180 ° C. for 10 minutes to 1 hour.
A conventionally known mixing device or the like may be used. The silane coupling agent and the thermosetting resin (A) may be used alone or in combination of two or more.

The content of the filler (C) is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, still more preferably 70 to 80% by mass, based on the total amount of the molding material composition for sealing. Is. (C) When the content of the filler is 60% by mass or more, it is possible to secure the difference in linear expansion coefficient necessary for securing the mechanical strength and suppressing the peeling from the semiconductor insert component, and it is 90% by mass or less. Then, it becomes possible to secure moldability such as flow characteristics.

It is preferable that the sealing molding material composition of the present embodiment further contains (D) a low stress agent from the viewpoint of reducing peeling from the semiconductor insert component. Examples of the low stress agent include silicone compounds such as silicone powder, silicone oil and silicone rubber; polybutadiene compounds; acrylonitrile-butadiene copolymer compounds such as acrylonitrile-carboxyl group-terminated butadiene copolymer compounds. Of these, a silicone powder containing polymethylsilsesquioxane or the like, which has relatively high heat resistance, as a main component is preferable. These may be used alone or in combination of two or more.

The average particle size of the silicone powder is preferably 0.5 μm or more and less than 5 μm, and more preferably 1 μm or more and 4 μm or less.

The silicone oil has a viscosity at 25 ° C. of preferably 500 mm ² / s or less, more preferably 400 mm ² / s or less, and even more preferably 200 mm ² / s or less. When the viscosity at 25 ° C. is 500 mm ² / s or less, (c-3) the dispersibility in the organic filler is good. The lower limit of the viscosity at 25 ° C. is not particularly limited, but may be 10 mm ² / s or more.
The silicone oil may or may not have a functional group, but when it has a functional group, it is preferably a functional group that does not have reactivity with a silane coupling agent. If the functional group of the silicone oil is reactive with the silane coupling agent, the molecular weight may increase due to the cross-linking reaction and the fluidity of the viscosity may deteriorate.

In the present invention, (c-3) an organic filler is added by stirring and mixing with a mixture of a silane coupling agent and silicone oil, and then premixing with a part or all of (A) a thermosetting resin. Then, it is even more effective.
The silane coupling agent and the silicone oil are particularly effective when a combination that forms an emulsifying dispersion (emulsion) with each other is selected while satisfying the above requirements. As a combination of a silane coupling agent and a silicone oil that form an emulsifying dispersion while satisfying the above requirements, for example, an epoxy silane such as 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane and It is possible to exemplify a combination with a double-ended epoxy-modified dimethyl silicone or the like. These are KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name), KF-105 (both-terminal epoxy-modified dimethyl silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name). , 15 mm ² / s) in viscosity at 25 ° C., etc. are available on the market.
The mixing ratio of the silane coupling agent and the silicone oil is not particularly limited, but can be, for example, 10/1 to 1/10 in terms of mass ratio. Stirring of the mixture of the silane coupling agent and the silicone oil and (c-3) the organic filler, and the premixing of (A) the thermosetting resin after mixing are performed by (A) the thermosetting resin and the silane coupling. The mixing ratio with the agent may be as described above.

When the (D) low stress agent is used, the content of the (D) low stress agent is preferably 0.5 to 10% by mass, more preferably 1 to 6 with respect to the total amount of the molding material composition for encapsulation. It is mass%. (D) When the content of the low stress agent is 0.5% by mass or more, it is effective in suppressing peeling from the viewpoint of reducing the elastic modulus and improving the adhesion, and when it is 10% by mass or less, molding such as flow characteristics It is possible to prevent deterioration of sexuality.

The sealing molding material composition of the present embodiment preferably contains a silane coupling agent from the viewpoints of moisture resistance, mechanical strength, adhesion to semiconductor insert parts, and the like. In this embodiment, epoxy silanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N. Aminosilanes such as -2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; isocyanates such as 3-isocyanuspropyltriethoxysisilane Conventionally known silane coupling agents such as silane can be appropriately used. From the viewpoint of adhesion, it is preferable to use epoxysilanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, secondary aminosilanes, and isocyanatesilanes alone or in combination. .. The silane coupling agent may be used by simply mixing it with the filler (C), or may be used by surface-treating a part or all of the silane coupling agent in advance. Further, an aluminate-based coupling agent or a titanate-based coupling agent may be contained as long as the effect of the present embodiment is not impaired.

The content of the silane coupling agent is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.7% by mass, still more preferably 0.05, based on the total amount of the molding material composition for sealing. ~ 0.5% by mass. By setting the content of the silane coupling agent to 0.01% by mass or more, the adhesion to the semiconductor insert component can be improved, and by setting the content to 1% by mass or less, the curability during molding can be reduced. It can be reduced.

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

In addition to the above components, the encapsulating molding material composition of the present embodiment includes flame retardants, carbon blacks, organic dyes, titanium oxide, colorants such as red iron oxide, etc., which are generally blended in this type of composition. A thermoplastic resin, an ion trap agent, a defoaming agent and the like can be blended as needed.

The content of the (A) thermosetting resin, (B) curing accelerator, and (C) filler in the sealing molding material composition of the present embodiment is preferably 80% by mass or more, more preferably. It is 90% by mass or more, more preferably 95% by 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 each of the above-mentioned components. The preparation method is not particularly limited, but as a general method, for example, a predetermined amount of each of the above components is sufficiently mixed with a mixer or the like, then melt-mixed with a mixing roll, an extruder or the like, and then cooled. , A method of crushing can be mentioned.

The sealing molding material composition thus obtained has a high glass transition temperature (Tg) and a thermal decomposition start temperature, and is excellent in heat resistance, and also has excellent adhesion to semiconductor insert parts, even after a temperature cycle test. A cured product that does not easily peel off from the semiconductor insert component can be obtained.
The thermal decomposition start temperature of the cured product of the molding material composition for sealing is preferably higher than 350 ° C., more preferably 355 ° C. or higher.
The adhesive strength of the cured product of the sealing molding material composition is preferably 5 MPa or more, more preferably 6 MPa or more.
The thermal decomposition start temperature and the adhesive strength of the cured product can both be measured by the methods described in Examples.

(Electronic component equipment)
The electronic component device of the present embodiment includes an element sealed with a cured product of the sealing molding material composition. The electronic component device includes a lead frame, a single crystal silicon semiconductor element or a support member such as SiC, Ga ₂ O ₃ , GaN and a diamond element, a wire for electrically connecting these, a member such as a bump, and the like. This is an electronic component device in which a necessary portion is sealed with a cured product of the sealing molding material composition with respect to a set of constituent members of the above. In particular, when SiC, Ga ₂ O ₃ , GaN and a diamond element are used as support members, an electronic component device sealed with a cured product of the sealing molding material composition can obtain good characteristics.

The transfer molding method is the most common method for sealing using the sealing molding material composition of the present embodiment, but an injection molding method, a compression molding method, or the like may also be used.
The molding temperature may be 150 to 250 ° C., 160 to 220 ° C., or 170 to 200 ° C. The molding time may be 30 to 600 seconds, 45 to 300 seconds, or 60 to 250 seconds. Further, in the case of post-curing, the heating temperature is not particularly limited, but may be, for example, 150 to 250 ° C. or 180 to 220 ° C. The heating time is not particularly limited, but may be, for example, 0.5 to 10 hours or 1 to 8 hours.

Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these examples.

(Examples 1 to 14 and Comparative Examples 1 to 6)
Each component of the type and the blending amount shown in Tables 1 and 2 was kneaded with a mixing biaxial roll to prepare a molding material composition for sealing. The kneading temperature in each Example and Comparative Example was set to 80 to 100 ° C. The blanks in Tables 1 and 2 indicate no compounding.

(Example 15)
(C-3) KC Flock (registered trademark) W-50GK (manufactured by Nippon Paper Co., Ltd.) 2.5 parts by mass as an organic filler, KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent 0 .25 parts by mass and KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.) as silicone oil 0.5 parts by mass (mass ratio 10/1/2), and further stirred and mixed at room temperature (25 ° C) for 5 minutes. Then, it was used as the component (E-1). Next, as the component (E-1), (A) thermosetting resin BMI-80 (manufactured by KI Kasei Co., Ltd.) and EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.) were added to BMI-. Mix at 80 / EPPN-502H / (component (c-3) in component (E-1)) = 20/70 / 2.5 (mass ratio), and further stir and mix at 150 ° C. for 30 minutes. It was used as a premix. In the obtained premix, (A) thermosetting resin BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), SN-485 (manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.), (B) 2P4MHZ- as a curing accelerator. PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.), (c-1) FB-105 (manufactured by Electrochemical Industry Co., Ltd.) as an inorganic filler, (c-2) Espheres SL75 (Pacific cement (Pacific cement) as a hollow structure filler (Manufactured by Co., Ltd.), (D) Silicone powder (EP-5518, manufactured by Toray Dow Corning Co., Ltd.) as a low stress agent, KBM-403 as a silane coupling agent, and HW-4252E (Mitsui Chemicals, Inc.) as a release agent. ) Was mixed so as to have the blending amount shown in Table 1, and kneaded with a mixing biaxial roll to prepare a molding material composition for sealing according to Example 15.

(Example 16)
(C-3) KC Flock (registered trademark) W-50GK (manufactured by Nippon Paper Co., Ltd.) 5 parts by mass as an organic filler, KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 as a silane coupling agent KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.) as 1 part by mass (mass ratio 10/1/2) of KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed as a part by mass and silicone oil, and further stirred and mixed at room temperature (25 ° C.) for 5 minutes (E -2) Used as an ingredient. Next, as the component (E-2), (A) thermosetting resin BMI-80 (manufactured by KI Kasei Co., Ltd.) and EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.) were added to BMI-. Mix at 80 / EPPN-502H / (component (c-3) in component (E-2)) = 20/70/5 (mass ratio), and further stir and mix at 150 ° C. for 30 minutes to prepare a premix. And said. In the obtained premix, (A) thermosetting resin BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), SN-485 (manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.), (B) 2P4MHZ- as a curing accelerator. PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.), (c-1) FB-105 (manufactured by Electrochemical Industry Co., Ltd.) as an inorganic filler, (c-2) Espheres SL75 (Pacific cement (Pacific cement) as a hollow structure filler (Manufactured by Co., Ltd.), (D) Silicone powder (EP-5518, manufactured by Toray Dow Corning Co., Ltd.) as a low stress agent, KBM-403 as a silane coupling agent, and HW-4252E (Mitsui Chemicals, Inc.) as a release agent. ) Was mixed so as to have the blending amount shown in Table 1 and kneaded with a mixing biaxial roll to prepare a molding material composition for sealing according to Example 16.

(Example 17)
(C-3) 2.5 parts by mass of KC Flock (registered trademark) W-50GK (manufactured by Nippon Paper Co., Ltd.) as an organic filler, and KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent. The mixture was mixed at 0.25 parts by mass (mass ratio 10/1), and further stirred and mixed at room temperature (25 ° C.) for 5 minutes to obtain the component (E-3). Next, as the component (E-3), (A) thermosetting resin BMI-80 (manufactured by KI Kasei Co., Ltd.) and EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.) were added to BMI-. Mix at 80 / EPPN-502H / (component (c-3) in component (E-3)) = 20/70 / 2.5 (mass ratio), and further stir and mix at 150 ° C. for 30 minutes. It was used as a premix. In the obtained premix, (A) thermosetting resin BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), SN-485 (manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.), (B) 2P4MHZ- as a curing accelerator. PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.), (c-1) FB-105 (manufactured by Electrochemical Industry Co., Ltd.) as an inorganic filler, (c-2) Espheres SL75 (Pacific cement (Pacific cement) as a hollow structure filler (Manufactured by Co., Ltd.), (D) Silicone powder (EP-5518, manufactured by Toray Dow Corning Co., Ltd.) as a low stress agent, KBM-573 as a silane coupling agent, and HW-4252E (Mitsui Chemicals, Inc.) as a release agent. ) Was mixed so as to have the blending amount shown in Table 1 and kneaded with a mixing biaxial roll to prepare a molding material composition for sealing according to Example 17.

Details of each component shown in Tables 1 and 2 used for preparing the molding material composition for sealing are as follows.

<(A) Thermosetting resin>
[Maleimide resin]
-BMI-2300: Polyphenylmethanemaleimide (mainly composed of z = 0 to 2 in the general formula (I)), manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name-BMI-80: 2,2-bis [ 4- (4-Maleimidephenoxin) Phenyl] Propane, manufactured by Keiai Kasei Co., Ltd., trade name

[Phenolic resin]
SN-485: Naphthalene-type phenolic resin (mainly composed of phenolic resin having y1 = 0 to 3 in general formula (III)), manufactured by Nippon Steel & Sumitomo Metal Corporation, trade name, hydroxyl group equivalent 215, softening point 87 ° C.
MEH-7500: Triphenylmethane-type phenolic resin (mainly composed of phenolic resin having x = 1 to 4 in general formula (II)), manufactured by Meiwa Kasei Co., Ltd., trade name, hydroxyl group equivalent 97, softening point 110 ℃
-MEH-7851: Biphenyl-type phenolic resin, manufactured by Meiwa Kasei Co., Ltd., trade name, hydroxyl group equivalent 204, softening point 70 ° C.

〔Epoxy resin〕
EPPN-502H: Triphenylmethane type epoxy resin (main component is epoxy resin with n1 = 0 to 3 in general formula (IV)), manufactured by Nippon Kayaku Co., Ltd., trade name, epoxy equivalent 168, softening point 67 ℃
-NC-3000: Biphenyl novolac epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 276, softening 58 ° C)

[Benzooxazine resin]
-Benzooxazine P-d: benzoxazine resin [benzoxazine resin represented by the formula (VII-1)], manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name.

[Cyanate resin]
-CYTESTER (registered trademark) TA: Cyanate ester compound containing 2,2-bis (4-cyanatephenyl) propane as the main component (99% or more), manufactured by Mitsubishi Gas Chemical Company, Inc., trade name

<(B) Hardening accelerator>
[Phosphorus-based hardening accelerator]
-TPP: Triphenylphosphine, manufactured by Hokuko Chemical Co., Ltd., trade name-TPP-BQ: Additive of triphenylphosphine and parabenzoquinone

In addition, TPP-BQ was synthesized by the following.
4.25 g of benzoquinone, 10 g of triphenylphosphine and 30 g of acetone were charged in a separable flask equipped with a cooling tube and a stirrer, and reacted at room temperature (25 ° C.) under stirring. The precipitated crystals were washed with acetone, filtered, and dried to obtain 14 g of TPP-BQ as yellowish brown crystals.

[Imidazole-based hardening accelerator]
2P4MHZ-PW: 2-phenyl-4-methyl-5-hydroxymethylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name (reaction start temperature with bisphenol A type epoxy resin: 129 ° C)
2MZ-A: 2,4-diamino-6- [2'-methylimidazolyl- (1')] -ethyl-s-triazine, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name (with bisphenol A type epoxy resin) Reaction start temperature: 120 ° C)

<(C) Filler>
[(C-1) Inorganic filler]
FB-105: fused spherical silica, manufactured by Denki Kagaku Kogyo Co., Ltd., trade name, average particle diameter 18 μm, specific surface area 4.5 m ² / g

[(C-2) Hollow structure filler]
-Easfears SL75: Inorganic hollow structure filler containing amorphous aluminum (65-85%) and mullite (20-30%) as main components, average particle size 55 μm, manufactured by Taiheiyo Cement Co., Ltd., trade name, Elastic modulus 10GPa

[(C-3) Organic filler]
・ KC Flock (registered trademark) W-50GK (manufactured by Nippon Paper Industries, Ltd., trade name, average particle size 45 μm)

<(D) Low stress agent>
[Silicone powder]
EP-5518: Silicone powder containing polymethylsilsesquioxane as the main component, manufactured by Toray Dow Corning Co., Ltd., trade name, average particle size 3 μm
[Silicone oil]
-KF-105: Epoxy-modified dimethyl silicone at both ends, manufactured by Shin-Etsu Chemical Co., Ltd., trade name, viscosity at 25 ° C. 15 mm ² / s

<Other ingredients>
-KBM-403: Silane coupling agent, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name-KBM-573: Silane coupling agent, N-phenyl-3-aminopropyltrimethoxy Silane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: HW-4252E: Release agent (oxidized polyethylene-based mold release agent with a number average molecular weight of 1,000), manufactured by Mitsui Chemicals Co., Ltd., trade name: Carnauba Wax 1 No .: Release agent, Carnauba wax, manufactured by Toyo Adre Co., Ltd., trade name

The characteristics of the encapsulating molding material composition prepared in Examples 1 to 17 and Comparative Examples 1 to 6 were measured and evaluated under the measurement conditions shown below. The evaluation results are shown in Tables 1 and 2.
Unless otherwise specified, the molding material was molded by a transfer molding machine under the conditions of a mold temperature of 185 ° C., a molding pressure of 10 MPa, and a curing time of 180 seconds. Post-curing was performed at 200 ° C. for 8 hours.

<Evaluation items>
(1) Molding shrinkage rate α, shrinkage rate β, (β-α)
A molding material composition for sealing was molded under the above conditions using a mold having a diameter of 100 mm × 10 mmt, and then post-cured under the above conditions to prepare a molded product (φ100 mm × 10 mmt). The obtained molded product was measured at four predetermined dimensions at room temperature (25 ° C.) using a micrometer (manufactured by Mitutoyo Co., Ltd., DIGIMATIC_MICROMETER; the same applies hereinafter), and the average value was the dimension of the molded product. And said. From the dimensions of the obtained molded product, the amount of change with respect to the inner dimensions of the mold at room temperature was obtained, and the molding shrinkage rate α was calculated.
Further, after the molded product obtained under the above conditions was left at 250 ° C. for 500 hours, the dimensions of the molded product were measured at room temperature (25 ° C.) at room temperature (25 ° C.) using a micrometer, and the average value was measured. The dimensions of the molded product were used. The amount of change with respect to the inner size of the mold was obtained from the size of the obtained molded product, and the shrinkage rate β was calculated.

(2) Storage elastic modulus Using a mold having a storage elastic modulus of 4.3 mm × 3.0 mm × 35 mm, the molding material composition for encapsulation was molded under the above conditions, and further cured under the above conditions to form a molded product (4. 3 mm × 3.0 mm × 35 mm) was produced. A test piece is obtained by cutting the molded product to the required dimensions, the thickness of the test piece is measured with a micrometer, and the product is pulled using a dynamic viscoelastic device (manufactured by TA Instrument, trade name: Q800). The temperature was raised from room temperature (25 ° C) to 300 ° C at a mode of 10 Hz and a temperature rise rate of 10 ° C / min, and the dynamic viscoelasticity at 25 ° C and the dynamic viscoelasticity at 250 ° C were measured, and the respective storage elastic moduli were measured. Was calculated.

(3) Glass transition temperature (Tg) and coefficient of linear expansion CTE1, CTE2
The glass transition temperature (Tg) was measured as one of the measures of the heat resistance of the cured product of the molding material composition for sealing. First, a molding material composition for encapsulation was molded under the above conditions using a mold of 4 mm × 4 mm × 20 mm, and then post-cured under the above conditions to prepare a molded product (4 mm × 4 mm × 20 mm). A test piece is obtained by cutting the molded product to the required size, and using the test piece, ascending using a thermal analyzer (manufactured by Seiko Instruments Inc., trade name: SSC / 5200) by the TMA method. The temperature was raised from room temperature (25 ° C.) to 320 ° C. at a temperature rate of 10 ° C./min, and the glass transition temperature (Tg) was measured. Further, from the obtained TMA chart, the slope of the tangent line at 50 to 60 ° C. was defined as the linear expansion coefficient CTE1, and the slope of the tangent line at 290 to 300 ° C. was defined as the linear expansion coefficient CTE2.

(4) Generated stress From the molding shrinkage α, shrinkage β, storage elastic modulus E ₂₅ , E ₂₅₀ , glass transition temperature (Tg) and linear expansion coefficients CTE1 and CTE2 obtained in the above (1) to (3). The values of σ (1), σ (2), and σ (3) were obtained, and the values of the following equation (1) were calculated.

In the formula, α is the molding shrinkage rate (%) at 25 ° C. with respect to the mold size of the cured product, and β is the molding shrinkage rate (%) at 25 ° C. with respect to the mold size of the cured product after the cured product is left at 250 ° C. for 500 hours. Shrinkage rate (%), E ₂₅ is the storage elasticity (GPa) of the cured product at 25 ° C., E ₂₅₀ is the storage elasticity (GPa) of the cured product at 250 ° C., and CTEt is the linear expansion coefficient (ppm) of the lead frame. / ° C.), CTE1 is the linear expansion coefficient (ppm / ° C.) below the glass transition temperature of the cured product, CTE2 is the linear expansion coefficient (ppm / ° C.) above the glass transition temperature of the cured product, and Tg is the curing. Represents the glass transition temperature (° C) of an object. Here, a copper lead frame is used as the lead frame, and the coefficient of linear expansion CTEt of the lead frame is 17 ppm / ° C.

(5) Thermal decomposition start temperature As another measure of the heat resistance of the cured product of the sealing molding material composition, the thermal decomposition temperature was measured by a thermogravimetric differential thermal analyzer (TG-DTA). A molding material composition for encapsulation was molded under the above conditions using a 4 mm × 4 mm × 20 mm mold, and further cured under the above conditions to prepare a molded product (4 mm × 4 mm × 20 mm). A test piece obtained by cutting out the molded product in the same size as in (3) above is used as a test piece, and the powder obtained by sufficiently grinding the test piece in a mortar is used at a room temperature (25 ° C.) at a heating rate of 10 ° C./min. Was heated to 600 ° C. From the obtained weight change chart, the temperature at which a weight loss of 1% was observed was defined as the thermal decomposition temperature. As the measuring device, "EXSTAR6000" manufactured by Seiko Instruments Inc. was used.

(6) Adhesive strength (adhesive strength)
A molded product obtained by molding a molding material composition for sealing on an island portion of a Cu lead frame (manufactured by Mitsui High-Tech Co., Ltd., trade name "LQFP-2828p") under the above conditions, and then post-curing under the above conditions. Was produced. Using a bond tester (manufactured by Seishin Shoji Co., Ltd., SS-30WD), a φ3.5 mm printed molded product molded on the island of the Cu lead frame from a height of 0.5 mm from the bottom of the molded product. It was peeled off in the shearing direction at a speed of 0.08 mm / sec, and the adhesive strength (adhesion force) between the molded product and the Cu lead frame was measured.

(7) Detachability (initial)
A SiC chip (6 x 6 x 0.15 mmt, no surface protective film) is placed in the center of the island (8.5 x 11.5 mm) of the TO-247 package of the Cu lead frame, manufactured by Kyocera Corporation, and sintered Ag paste. (CT2700R7S) was fixed, and 10 molded products were prepared by molding the sealing molding material composition under the above conditions. The molded product was observed using an ultrasonic imaging device (FS300II, manufactured by Hitachi, Ltd.), and it was confirmed whether or not the island around the SiC chip and the cured product of the molding material composition for sealing were peeled off. Observation was performed before and after post-curing, and the number of packages in which peeling of the island portion was observed after post-curing was 3 out of 10 and passed. Further, the Cu lead frame was used by subjecting the sealing molding material composition to an argon plasma treatment for 60 seconds using a plasma cleaner AC-300 manufactured by Nordson immediately before molding.

(8) Detachability (after temperature cycle test)
After the test of (7) above, a total of 10 packages (molded products) in which peeling of the island portion was not observed and molded products manufactured under the conditions shown in (7) above were used, and a temperature cycle test shown below was further performed. Was done. Using a thermal shock test device (TSA-42EL manufactured by ESPEC CORPORATION), the molded product was left at −40 ° C. for 30 minutes, then heated to 250 ° C. at a heating rate of 40 ° C./min, and then. A temperature cycle test of 1000 cycles was performed with a temperature decrease rate of 40 ° C./min and a temperature decrease to −40 ° C. as one cycle after being left at 250 ° C. for 30 minutes. The molded product after the temperature cycle test was observed using an ultrasonic imaging device (FS300II, manufactured by Hitachi, Ltd.), and the presence or absence of peeling between the island around the SiC chip and the cured product of the molding material composition for sealing was observed. After confirmation, the number of packages in which peeling of the island portion was observed was 3 out of 10 or less.

The cured products of the sealing molding material compositions of Examples 1 to 17 satisfying the formula (1) have high glass transition temperature and thermal decomposition start temperature, are excellent in heat resistance, and have excellent adhesion to semiconductor insert parts. It is excellent, and it can be seen that peeling from the semiconductor insert component is unlikely to occur even after the temperature cycle test.

Claims (10)

A molding material composition for sealing, which comprises (A) a thermosetting resin, (B) a curing accelerator, and (C) a filler.
Occurrence that occurs when the sealing molding material composition is cured in a mold at 180 ° C. for 180 seconds and then post-cured outside the mold at 200 ° C. for 8 hours to obtain a cured product. The stress σ (1), the stress σ (2) generated by the heat history generated when the temperature cycle test at -40 to 250 ° C. is performed 1000 cycles using the cured product, and the temperature cycle using the cured product. Composition of SiC, Ga ₂ O ₃ , GaN and molding material for encapsulating diamond elements in which the stress σ (3) generated by the irreversible shrinkage of the cured product when the test is carried out for 1000 cycles satisfies the following formula (1). object.

(In the formula, α is the molding shrinkage rate (%) at 25 ° C. with respect to the mold size of the cured product, and β is 25 ° C. with respect to the mold size of the cured product after the cured product is left at 250 ° C. for 500 hours. The shrinkage rate (%), E ₂₅ is the storage elasticity (GPa) of the cured product at 25 ° C., E ₂₅₀ is the storage elasticity (GPa) of the cured product at 250 ° C., and CTEt is the linear expansion coefficient of the lead frame (GPa). (ppm / ° C.), CTE1 is the linear expansion coefficient (ppm / ° C.) below the glass transition temperature of the cured product, CTE2 is the linear expansion coefficient (ppm / ° C.) above the glass transition temperature of the cured product, and Tg is the above. Represents the glass transition temperature (° C) of the cured product.) The molding material composition for encapsulating SiC, Ga ₂ O ₃ , GaN and a diamond device according to claim 1, wherein the value of σ (3) is 0.00 to 50.0 MPa. The molding material composition for encapsulating SiC, Ga ₂ O ₃ , GaN and a diamond element according to claim 1 or 2, wherein the value of σ (1) is 0.00 to 30.0 MPa. The SiC, Ga _{2 according} to any one of claims 1 to 3, wherein the value of α is 0.00 to 0.20% and the value of β-α is 0.00 to 0.40%. O _3, GaN and diamond element encapsulation molding composition. The molding material for sealing SiC, Ga ₂ O ₃ , GaN and diamond elements according to any one of claims 1 to 4, wherein the thermal decomposition start temperature of the cured product of the molding material composition for sealing is higher than 350 ° C. Composition. The SiC, Ga ₂ O ₃ , GaN and diamond device sealing molding material composition according to any one of claims 1 to 5, wherein the cured product of the sealing molding material composition has an adhesive strength of 5 MPa or more. .. The molding material composition for encapsulating SiC, Ga ₂ O ₃ , GaN and a diamond device according to any one of claims 1 to 6, wherein the (C) filler contains (c-2) a hollow structure filler. (D) The molding material composition for encapsulating SiC, Ga ₂ O ₃ , GaN and a diamond device according to any one of claims 1 to 7, further comprising (D) a low stress agent. The SiC, Ga ₂ O _{3 according} to any one of claims 1 to 8, wherein the (C) filler contains (c-3) an organic filler, and the (c-3) organic filler contains cellulose. , GaN and diamond device encapsulation molding material compositions. An electronic component device comprising an element sealed by a cured product of the sealing molding material composition according to any one of claims 1 to 9.