JP2019056041A - Thermosetting resin composition - Google Patents

Abstract

To provide a thermosetting resin composition having sufficient tolerance in a heat cycle test and/or a power cycle test, a sealant made of the thermosetting resin composition, and a semiconductor device using the sealant.SOLUTION: A resin composition includes an epoxy resin (A), a hardening agent (B), and an inorganic filler (C), and satisfies the following condition: the resin composition has a lowest modulus of 10MPa or less evaluated at 200°C after the resin composition is heated from 23°C to 200°C at the rate of 50°C/min and a final modulus of 10MPa or more after 10 min. from initiation of heating.SELECTED DRAWING: Figure 1

Description

  The present invention uses a thermosetting resin composition that gives a cured product excellent in heat resistance, heat dissipation, and low thermal expansion, a sealing material using the curable resin composition, an in-vehicle member, and the sealing material. The present invention relates to a semiconductor device and a manufacturing method for sealing the semiconductor device.

  Among thermosetting resin compositions, epoxy resin compositions are used for electrical and electronic parts, structural materials, and automobiles due to workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. Widely used in fields such as materials, adhesives and paints.

  In electronic device products, sealing materials are used to protect electronic components such as semiconductor elements from external environments such as impact, pressure, humidity, and heat. As the sealing material, an epoxy / phenol-based sealing material in which the main agent is an epoxy resin and the curing agent is a phenol resin is widely used.

  Power semiconductors typified by in-vehicle power modules among electronic device products are important technologies that hold the key to energy saving in electrical and electronic equipment. To further increase the power current, size, and efficiency of power semiconductors Along with this, the transition from conventional silicon (Si) semiconductors to silicon carbide (SiC), gallium nitride (GaN), and diamond (C) semiconductors, which are called wide band gap semiconductors that are expected to be highly efficient, is being promoted. . The advantage of the SiC semiconductor is that it can be operated under higher temperature conditions. Therefore, the semiconductor encapsulant is required to have higher heat resistance than ever before.

  In the case of power semiconductors, the working voltage reaches several hundred to several thousand volts when it comes to high breakdown voltage specifications. It has been reported that defects occur due to the phenomenon of partial discharge under such high voltage conditions. Partial discharge refers to a phenomenon in which an insulator is eroded by a local discharge (surface corona) between an electrode and the surface of an insulator, a discharge (void corona) in a gap (void) inside the insulator, or the like.

  In the crosslinkable polymer, it is considered that the higher the crosslink density is, the more the breakdown due to the electrons accelerated by the electric field can be prevented, and the finer vacancies are less likely to be generated. In addition, it is considered that the insulation characteristics are similarly improved if it becomes difficult for microvoids in the cured product to be generated in a resin molding process such as transfer molding.

As materials having excellent heat resistance, heat-resistant resin compositions containing maleimide compounds and polyamines (see Patent Document 1), bismaleimide resins modified with polybenzoxazine (see Patent Document 2), and the like have been reported. . Such a heat resistant resin composition can exhibit excellent heat resistance.
In addition, electrical and electronic resin parts used in automobiles and the like have recently been downsized and increased in output, and the amount of heat generated per unit volume tends to increase. Accordingly, heat resistance, heat dissipation and low thermal expansion of resin parts are important factors. So far, it has been disclosed that heat dissipation is improved by using carbon, alumina, or boron nitride nanofibers as a filler (see Patent Document 3).

JP 2014-177484 A JP 2012-97207 A JP 2010-1000083 A

However, even in the case of using a heat-resistant resin as described above, it is sufficient in a heat cycle test that repeats heating-cooling assuming an actual high-temperature operation device or a power cycle test that simulates the high-temperature operation state of the element. The fact is that we have not been able to gain tolerance.
In addition, it is a fact that a resin having sufficient heat dissipation and low thermal expansion has not been obtained while having heat resistance.

  The present invention has been made in view of such a background, and a curable resin composition capable of obtaining sufficient resistance in a heat cycle test and / or a power cycle test, and a sealing using the curable resin composition It is an object of the present invention to provide a stopper, a semiconductor device using the sealing material, and a method for manufacturing the semiconductor device.

As a result of intensive studies in view of the above circumstances, the present inventor has completed the present invention. That is, the present invention is as follows.
[1]
(A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II) After the temperature was raised from 23 ° C. to 50 ° C./200° C. by rheometer evaluation, the lowest modulus when evaluated at 200 ° C. was 10 ⁴ MPa or less, and reached 10 minutes after the start of temperature rise. The modulus is 10 ⁵ MPa or more;
The said resin composition satisfy | fills.
[2]
The resin composition has the following conditions:
(I-II) The softening point of the epoxy resin (A) is 35 ° C. or higher;
[1] The resin composition according to [1].
[3]
The resin composition has the following conditions:
(I-III) The residual solvent of the resin composition is less than 0.1% by weight;
The resin composition according to [1] or [2], further satisfying
[4]
The resin composition has the following conditions:
(I-IV) The equivalent of the (B) curing agent is 90 g / eq or less, and the softening point is 105 ° C. or more;
The resin composition according to any one of [1] to [3], further satisfying:
[5]
(A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II-I) On the surface of the (C) inorganic filler in the resin composition, the C atom derived from the (A) epoxy resin or the (B) curing agent in the EDX measurement and the (C) inorganic filler The abundance ratio of the derived X atom is C / X = 1 or more, and the X atom is a C atom in the main component (component contained in the range of 1 to 95 mol%) of the (C) inorganic filler, Atoms other than O, H and N atoms, and said X is defined as the molar concentration of said X atoms;
The resin composition further satisfying
[6]
The resin composition has the following conditions:
(II-II) The weight fraction of the (C) inorganic filler in the resin composition is 95% by weight or less;
[5] The resin composition according to [5].
[7]
The resin composition has the following conditions:
(II-III) The inorganic filler (C) contains at least nanofibers;
The resin composition according to [5] or [6], further satisfying
[8]
The resin composition has the following conditions:
(II-IV) The specific surface area of the (C) inorganic filler relative to the entire resin composition is more than 3 mm ² / g and 1000 m ² / g or less;
The resin composition according to any one of [5] to [7].
[9]
The resin composition has the following conditions:
(II-V) The softening point of the epoxy resin (A) is 35 ° C. or higher;
The resin composition according to any one of [5] to [8], further satisfying
[10]
The resin composition has the following conditions:
(II-VI) The residual solvent of the resin composition is less than 0.1% by weight;
The resin composition according to any one of [5] to [9].
[11]
The resin composition has the following conditions:
(II-VII) The equivalent of the (B) curing agent is 90 g / eq or less, and the softening point is 105 ° C. or more;
The resin composition according to any one of [5] to [10], further satisfying:
[12]
(A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II-I) On the surface of the (C) inorganic filler in the resin composition, the C atom derived from the (A) epoxy resin or the (B) curing agent in the EDX measurement and the (C) inorganic filler The abundance ratio of the derived X atom is C / X = 1 or more, and the X atom is a C atom in the main component (component contained in the range of 1 to 95 mol%) of the (C) inorganic filler, Atoms other than O, H and N atoms, and said X is defined as the molar concentration of said X atoms;
(II-II) The weight fraction of the (C) inorganic filler in the resin composition is 95% by weight or less;
(II-III) The (C) inorganic filler contains at least nanofibers;
(II-IV) The specific surface area of the (C) inorganic filler relative to the entire resin composition is more than 3 mm ² / g and 1000 m ² / g or less;
(II-V) The softening point of the epoxy resin (A) is 35 ° C. or higher;
(II-VI) The residual solvent of the resin composition is less than 0.1% by weight; and (II-VII) The equivalent of the (B) curing agent is 90 g / eq or less and the softening point is 105 ° C. Or more;
The said resin composition satisfy | fills.
[13]
The resin composition according to any one of [1] to [12], wherein the (B) curing agent is a compound having an amino group.
[14]
The diameter of the nanofiber contained in the inorganic filler (C) is 1 nm or more and 990 nm or less, and the aspect ratio (the length of the nanofiber / the diameter of the nanofiber) is 10 or more and 1000 or less, [1]- [13] The resin composition according to any one of [13].
[15]
The sealing material or vehicle-mounted member containing the hardened | cured material of the resin composition in any one of [1]-[14].
[16]
A semiconductor device in which a semiconductor element is sealed with a cured product of the resin composition according to any one of [1] to [14].
[17]
The manufacturing method of a semiconductor device including the process of sealing a semiconductor element by compression molding using the hardened | cured material of the resin composition in any one of [1]-[14].

In the resin composition of the present invention, the cured product has sufficient chemical heat resistance and crosslinking density, and maintains sufficient moldability. For this reason, when applying to a transfer mold process, it becomes difficult to apply an excessive pressure to the element and wiring to seal, and the sealed element becomes difficult to produce a defect. Further, the cured product itself has heat resistance, and it becomes difficult to generate microscopic voids that cause defects in the transfer molding process, and exhibits excellent performance in heat cycle tests and / or power cycle tests.
Moreover, the resin composition of the present invention exhibits excellent heat dissipation and low thermal expansibility after having heat resistance by containing nanofibers.

The sealing material which consists of the hardened | cured material of the resin composition of this invention can exhibit the outstanding heat resistance. Therefore, it is suitable as a sealing material for electronic device products using a SiC substrate, for example.
The vehicle-mounted member made of the cured product of the resin composition of the present invention can exhibit excellent heat dissipation and low thermal expansion while having heat resistance. Therefore, for example, it is suitable for electric / electronic resin parts for vehicles.

In addition, in the electronic device product using the sealing material of the present invention, the sealing material can sufficiently exhibit its function even in a high temperature environment where the use temperature is 200 ° C., for example. Therefore, it can be used as an electronic device product having excellent reliability at high temperatures.
In addition, the electric / electronic resin product using the vehicle-mounted member of the present invention has a large heat generation amount from, for example, an electronic component, has high heat dissipation even in a high temperature environment, and has low thermal expansion. This function can be fully demonstrated. Therefore, it can be used as an electrical / electronic resin product having excellent reliability at high temperatures.

FIG. 1 is a graph showing the relationship between temperature and loss modulus for the resin composition tablets obtained in Example 1 and Comparative Example 1. Fig. 2 (2-a) is a surface observation image of the tablet of the resin composition obtained in Example 1 by a scanning electron microscope (SEM), and Fig. 2 (2-b) is an inorganic filler of the tablet. The element distribution by energy dispersive X-ray (EDX) analysis of the surface (Pt2-1) is shown, and FIG. 2 (2-c) is by EDX analysis of the desorption part (Pt2-2) of the inorganic filler of the tablet Element distribution is shown. Fig. 3 (3-a) is a surface observation image by SEM of the tablet of the resin composition obtained in Comparative Example 1, and Fig. 3 (3-b) and Fig. 3 (3-c) are respectively the tablets. The element distribution by EDX of the inorganic filler surface (Pt3-1) and (Pt3-2) is shown. FIG. 4 is a schematic diagram of a power semiconductor device used in this embodiment.

In the present invention, the following resin composition can be shown as one embodiment of the present invention. That is,
(A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II) After the temperature was raised from 23 ° C. to 50 ° C./200° C. by rheometer evaluation, the lowest modulus when evaluated at 200 ° C. was 10 ⁴ MPa or less, and reached 10 minutes after the start of temperature rise. The modulus is 10 ⁵ MPa or more;
A resin composition satisfying

Since the resin composition of the present invention has sufficient fluidity at the time of molding in the transfer molding process by setting the minimum modulus value to 10 ⁴ MPa or less, it does not apply excessive pressure to the elements and wirings to be sealed and is cured. Since the product also has heat resistance due to the composition and sufficient crosslinking density, sufficient resistance can be obtained in the heat cycle test and / or power cycle test. Specifically, by setting the minimum modulus value to 10 ⁴ MPa or less, it becomes difficult to apply excessive pressure to the elements and wirings to be sealed at the time of molding in the transfer molding process, and the cured product after sealing has a fine void. Since the resin can be filled into the mold in a state in which holes are not easily generated, heat cycle test and / or power cycle test resistance can be improved. If the minimum modulus is higher than this, it is difficult to fill the material well, and defects are likely to occur in the heat cycle test and / or the power cycle test. When the reaching modulus is 10 ⁵ MPa or less, the curing becomes insufficient and problems such as deformation of the molded body occur.

Such a resin composition preferably further satisfies the following conditions.
(I-II) (A) The softening point of the epoxy resin is 35 ° C. or higher;
(A) When the softening point of an epoxy resin is 35 degreeC or more, the heat resistance of hardened | cured material can be ensured and a heat cycle test and / or a power cycle test tolerance can be improved.

(I-III) The residual solvent of the resin composition is less than 0.1% by weight;
By reducing the residual solvent in the resin composition to less than 0.1% by mass, defects such as swelling caused by the residual solvent at the time of molding are suppressed, and heat cycle test and / or power cycle test resistance is improved. I can do it.

(I-IV) (B) The equivalent of the curing agent is 90 g / eq or less, and the softening point is 105 ° C. or more;
(B) By setting the equivalent of the curing agent to 90 g / eq or less, the crosslinking density of the cured product can be ensured and the heat resistance of the cured product can be ensured, so that the heat cycle test and / or power cycle test resistance can be achieved. Can be improved. Similarly, when the softening point of (B) the curing agent is 105 ° C. or higher, the heat resistance of the cured product can be secured, and the heat cycle test and / or power cycle test resistance can be improved.

In the present invention, the following resin composition can also be shown as one embodiment of the present invention. That is,
(A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II-I) On the surface of the (C) inorganic filler in the resin composition, (A) epoxy resin or (B) curing agent-derived C atom and (C) inorganic filler-derived X atom in EDX measurement A resin composition having an abundance ratio of C / X = 1 or more.
{In the formula, X atom is an atom other than C atom, O atom, H atom and N atom in the main component (component contained in the range of 1 to 95 mol%) of (C) inorganic filler component, And X is defined as the molar concentration of X atoms};
A resin composition satisfying
(A) When the abundance ratio of C atom derived from epoxy resin or (B) curing agent and X atom derived from (C) inorganic filler is C / X = 1 or more, at the time of molding, (C) inorganic filler Since the sliding is good, it is difficult to apply excessive pressure to the elements and wirings to be sealed, and the resin can be filled into the mold in a state where fine voids are hardly generated in the cured product after sealing. Test and / or power cycle test resistance can be improved.

Such a resin composition preferably further satisfies the following conditions.
(II-II) The weight fraction of (C) inorganic filler in the resin composition is 95% by weight or less;
(C) By making the weight fraction of the inorganic filler 95% by weight or less, the fluidity of the composition at the time of molding is improved, the moldability is improved, and the heat cycle test and / or power cycle test resistance is improved. It can be made. (C) When there is too much inorganic filler amount, the fluidity | liquidity of a composition will worsen at the time of shaping | molding, a shaping | molding defect will generate | occur | produce, and it will become easy to produce a defect in a heat cycle test and / or a power cycle test.

(II-III) (C) the inorganic filler contains at least nanofibers;
(C) Since the inorganic filler contains at least nanofibers, the molded body maintains heat resistance, has high heat dissipation, and can exhibit low thermal expansion. (C) When the inorganic filler does not contain nanofibers or contains microfibers instead of nanofibers, the heat dissipation becomes low or the thermal expansibility increases, Unable to fully perform functions and lack reliability.

(II-IV) (C) The specific surface area of the inorganic filler relative to the entire resin composition is more than 3 mm ² / g and not more than 1000 m ² / g;
Similarly, (C) the specific surface area of the inorganic filler with respect to the entire resin composition is more than 3 mm ² / g and 1000 m ² / g or less, so that the molded body maintains heat resistance and has high heat dissipation and low thermal expansion. Can demonstrate its sexuality. (C) If the specific surface area of the inorganic filler relative to the entire resin composition is less than 3 mm ² / g, the heat dissipation will be low, the thermal expansion will be large, and the function as an in-vehicle member will not be fully exerted and reliable. Lack of sex. (C) When the specific surface area with respect to the whole resin composition of an inorganic filler is larger than 1000 m < ² > / g, fluidity | liquidity will deteriorate at the time of shaping | molding and it will become easy to generate | occur | produce a molding defect.

(II-V) (A) The softening point of the epoxy resin is 35 ° C. or higher;
(A) When the softening point of an epoxy resin is 35 degreeC or more, the heat resistance of hardened | cured material can be ensured and a heat cycle test and / or a power cycle test tolerance can be improved.

(II-VI) the residual solvent of the resin composition is less than 0.1% by weight;
By reducing the residual solvent in the resin composition to less than 0.1% by mass, defects such as swelling caused by the residual solvent at the time of molding are suppressed, and heat cycle test and / or power cycle test resistance is improved. I can do it.

(II-VII) (B) The equivalent of the curing agent is 90 g / eq or less, and the softening point is 105 ° C. or more;
(B) By setting the equivalent of the curing agent to 90 g / eq or less, the crosslinking density of the cured product can be ensured and the heat resistance of the cured product can be ensured, so that the heat cycle test and / or power cycle test resistance can be achieved. Can be improved. Similarly, when the softening point of (B) the curing agent is 105 ° C. or higher, the heat resistance of the cured product can be secured, and the heat cycle test and / or power cycle test resistance can be improved.

In the present invention, the following resin composition can also be shown as one embodiment of the present invention. That is,
(A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II-I) On the surface of the (C) inorganic filler in the resin composition, (A) epoxy resin or (B) curing agent-derived C atom and (C) inorganic filler-derived X atom in EDX measurement The abundance ratio is C / X = 1 or more, and the X atom is a C atom, an O atom, an H atom and an N atom among the main components (components contained in the range of 1 to 95 mol%) of the (C) inorganic filler. An atom other than an atom, and X is defined as the molar concentration of the X atom;
(II-II) The weight fraction of (C) inorganic filler in the resin composition is 95% by weight or less;
(II-III) (C) the inorganic filler contains at least nanofibers;
(II-IV) (C) The specific surface area of the inorganic filler relative to the entire resin composition is more than 3 mm ² / g and not more than 1000 m ² / g;
(II-V) (A) The softening point of the epoxy resin is 35 ° C. or higher;
(II-VI) The residual solvent of the resin composition is less than 0.1% by weight; and (II-VII) (B) The equivalent of the curing agent is 90 g / eq or less and the softening point is 105 ° C. or more. is there;
A resin composition satisfying

  The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler as essential components, but may further contain other components.

In the resin composition of the present invention, the minimum modulus at 23 to 200 ° C. before the thermosetting treatment is preferably 10 ⁴ MPa or less, more preferably 10 ³ MPa or less, and further preferably 10 ² MPa or less. By setting the modulus value within the above range, it is possible to prevent the occurrence of damage due to pressure on the semiconductor element and the wiring in the element, and the generation of voids in the cured product due to insufficient fluidity in the transfer molding process. can do.

Further, the modulus after 10 minutes has elapsed since the start of temperature rise under the above conditions is preferably 10 ⁵ MPa or more, more preferably 10 ⁶ MPa or more, and even more preferably 10 ⁷ MPa or more. By setting the modulus value within the above range, the resin can be sufficiently cured at the time of molding in the transfer molding process.

  In addition, the measurement of the said modulus is the value of the loss elastic modulus measured by the parallel plate method using the rheometer (TA Instruments company make, DHR-2). More specifically, the gap is 2000 μm, the diameter of the rotating plate is 8 mm, the frequency is 1.0 HZ, the strain is 0.1%, the temperature is raised from 23 ° C. to 200 ° C. at a heating rate of 50 ° C./min, and held at 200 ° C. The minimum modulus and the modulus after 10 minutes can be obtained.

  Hereinafter, each component of the resin composition of this invention is demonstrated concretely.

[(A) Epoxy resin]
Examples of (A) epoxy resins are monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. For example, bisphenol A type epoxy resin Bisphenol type epoxy resin such as bisphenol F type epoxy resin and tetramethyl bisphenol F type epoxy resin, biphenyl type epoxy resin such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, etc. Crystalline epoxy resins; cresol novolac type epoxy resins, phenol novolac type epoxy resins, naphthol novolac type epoxy resins and other novolak type epoxy resins; phenylene skeleton-containing phenol aralkyl type epoxy resins, Phenolic aralkyl type epoxy resins such as phenolic aralkyl type epoxy resins containing eneylene skeletons, naphthol aralkyl type epoxy resins containing phenylene skeletons, phenol aralkyl epoxy resins containing alkoxynaphthalene skeletons; triphenolmethane type epoxy resins, alkyl-modified triphenolmethane type epoxy resins Trifunctional epoxy resins; modified phenolic epoxy resins such as dicyclopentadiene-modified phenolic epoxy resins and terpene-modified phenolic epoxy resins; heterocyclic-containing epoxy resins such as triazine nucleus-containing epoxy resins; phosphorus atom-containing epoxy resins These may be used alone or in combination of two or more.
Among these compounds, triphenolmethane type epoxy resins such as EPPN501H, EPPN501, EPPN501HY, EPPN502, EPPN502H (manufactured by Nippon Kayaku Co., Ltd.) and the like are dicyclopentadiene types, such as XD-1000 2L. XD-1000 (manufactured by Nippon Kayaku Co., Ltd.), HP-7200, HP-7200H (manufactured by DIC Corporation) and the like are preferable.

  Here, as the phosphorus atom-containing epoxy resin, epoxidized product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”), HCA and quinones Epoxy product of phenol resin obtained by reacting phenolic resin, epoxy resin obtained by modifying phenol novolac type epoxy resin with HCA, epoxy resin obtained by modifying cresol novolac type epoxy resin with HCA, and bisphenol A type epoxy resin using HCA and quinone An epoxy resin obtained by modification with a phenol resin obtained by reacting with a resin.

  The softening point of the epoxy resin (A) is preferably a resin having a temperature of 35 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher from the viewpoint of the heat resistance of the cured product. The upper limit of the softening point of the epoxy resin is not particularly limited, but is preferably 130 ° C. or lower from the viewpoint of ensuring the reactivity of the epoxy resin.

  The softening point mentioned here can be measured, for example, by the ring and ball method based on JISK2351.

  Although it does not specifically limit about the lower limit of the compounding ratio of the whole epoxy resin, It is preferable that it is 5 mass% or more in all the resin compositions, It is more preferable that it is 10 mass% or more, 17 mass% or more More preferably it is. When the lower limit of the blending ratio is within the above range, there is little possibility of causing a decrease in fluidity. In addition, the upper limit of the blending ratio of the entire epoxy resin is not particularly limited, but is preferably 50% by mass or less, and more preferably 40% by mass or less in the total resin composition. When the upper limit value of the blending ratio is within the above range, it is easy to match the thermal expansion coefficient with the surrounding members. Moreover, in order to improve the meltability of the resin, it is desirable to appropriately adjust the blending ratio according to the type of epoxy resin used.

[(B) Curing agent]
(B) The curing agent is not particularly limited as long as it is cured by reacting with an epoxy resin. For example, a straight chain having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine and the like. Aliphatic diamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis (4-aminophenyl) cyclohexane, dicyanodiamide, etc. Amines; Anili Resol type phenol resins such as modified resole resins and dimethyl ether resole resins; Novolak type phenol resins such as phenol novolac resins, cresol novolac resins, tert-butylphenol novolac resins, nonylphenol novolac resins; phenylene skeleton-containing phenol aralkyl resins, biphenylene skeleton-containing phenol aralkyls Phenol aralkyl resins such as resins; phenol resins having a condensed polycyclic structure such as naphthalene skeleton and anthracene skeleton; polyoxystyrenes such as polyparaoxystyrene; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), etc. Alicyclic acid anhydride, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic Acid anhydrides including aromatic acid anhydrides such as acids (BTDA); Polymercaptan compounds such as polysulfides, thioesters and thioethers; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; Organics such as carboxylic acid-containing polyester resins Acids are exemplified. These may be used alone or in combination of two or more.

  The equivalent of the above curing agent is preferably 90 g / eq or less, more preferably 80 g / eq, and further preferably 70 g / eq or less from the viewpoint of the heat resistance of the cured product. When the equivalent of the cured product is within the above range, a sufficient crosslinking density is ensured in the cured product, and physical heat resistance can be obtained.

  The equivalent of the curing agent here is defined as the number of grams including 1 equivalent of active hydrogen in the curing agent.

Among the above curing agents, the softening point is preferably 105 ° C. or higher, more preferably 140 ° C. or higher, and further preferably 170 ° C. or higher from the viewpoint of the heat resistance of the cured product. When the softening point of the curing agent is in the above range, the cured product can obtain sufficient heat resistance.
(B) The curing agent is preferably a compound having an amino group. Preferred curing agents include 4,4′-diaminodiphenyl sulfone (DDS), 3,3′-diaminodiphenyl sulfone, 1,3-bis (3-aminophenoxy) benzene, 4,4,4′-diaminodiphenyl ether, Examples include 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, and paraphenylenediamine.

  Of these, the curing agent used for the semiconductor encapsulating material is preferably an amine-based or amino-based compound from the viewpoint of ensuring the crosslinking density, reliability, etc., and is preferably an aromatic diamine compound or aromatic bisaminophenol compound. More preferred is at least one diamine compound selected from the group consisting of alicyclic diamine, linear aliphatic diamine or siloxane diamine.

  Aromatic bisaminophenol compounds include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminodiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) Propane, 3,3′-dihydroxy-4,4′-diaminobenzophenone, 3,3′-dihydroxy-4,4′-di Minodiphenyl ether, 4,4′-dihydroxy-3,3′-diaminodiphenyl ether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis (3-amino-4- Hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) -bis (2-aminophenol) and the like.

  Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 1,5 -Diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2 , 5-diethylcyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2- (3-aminocyclopentyl) -2-propylamine, mensendiamine, isophoronediamine, norbornane Diamine, 1-cycloheptene-3,7-diamine, , 4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2 4,8,10-tetraoxaspiro- [5,5] -undecane and the like.

  Examples of linear aliphatic diamine compounds include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. Hydrocarbon type diamines such as, or alkylene oxide type diamines such as 2- (2-aminoethoxy) ethylamine, 2,2 ′-(ethylenedioxy) diethylamine, bis [2- (2-aminoethoxy) ethyl] ether, etc. Is mentioned.

  Examples of the siloxane diamine compound include dimethyl (poly) siloxane diamine, for example, trade names PAM-E, KF-8010, and X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.

  In the case where a curing agent is used, the mixing ratio of the entire epoxy resin and the entire curing agent is such that the equivalent ratio of the total number of epoxy groups (EP) of the entire epoxy resin to the equivalent of the entire curing agent is 0.8 or more, 1.3 The following is preferable. When the equivalent ratio is within this range, sufficient curability can be obtained during molding of the resin composition. Moreover, when the equivalent ratio is within this range, good physical properties in the cured resin can be obtained. In consideration of the heat resistance of the resin composition, the equivalent ratio is brought close to 1.0 so that the curability of the resin composition and the glass transition temperature or the thermal elastic modulus of the resin cured product can be increased. Is desirable.

[(C) inorganic filler]
(C) The inorganic filler is characterized by containing at least a nanofiller. The nanofiler as the inorganic filler of the present invention can be applied to any of organic materials, inorganic materials, or mixed materials of inorganic materials and organic materials, and can be appropriately selected from the viewpoints of heat dissipation and thermal expansion. it can.
Organic materials include polysaccharides such as cellulose, bacterial cellulose, starch, glycogen, and chitosan, proteins such as collagen and keratin, thermoplastic resins such as polyolefin, polystyrene, polyester, polycarbonate, ABS resin, polyvinyl chloride, and poly (meth). Acrylic acid, polyamide, polyacrylonitrile, polyether sulfone, polyvinyl alcohol, polyacetal, polyethylene oxide, polyvinylidene fluoride, polyurethane as thermosetting resin, polyimide, phenol resin, melamine resin, polybenzimidazole, carbon nanofiber as carbon material , Carbon nanotube (single wall), carbon nanotube (multilayer), carbon nanohorn, carbon nanocone, car N'nanokoiru, carbon nano-twist, carbon nano-balloon, carbon nano-wall, carbon nano-chapters toilet, graphene, nanographene, include the graphene nanoribbons.

As the inorganic material, oxides, nitrides, and carbides are preferable. Specifically, SiC, AlN, Al ₂ O ₃ , Si ₃ N ₄ , TiN, ZrO ₂ , Y ₂ O ₃ , MgO, BN, SiO ₂ , _{al 2 O 3 · SiO 2,} MgO · SiO 2, ZrN, NbN, TaN, TaC , and the like. In particular, carbon materials and inorganic materials are preferable from the viewpoints of high heat dissipation and low thermal expansion, and specifically, carbon nanofibers, carbon nanotubes, SiC, AlN, Al ₂ O ₃ , and Si ₃ N ₄ , and more preferably SiC, AlN, Al ₂ O ₃ , and Si ₃ N _{4 made} of an inorganic material from the viewpoint of high heat dissipation.

  The method for producing the nanofiber is not particularly limited, but in the case of organic materials, melt spinning, electrospinning, melt blowing, centrifugal spinning, flash spinning, self-organization, physical defibration, chemical defibration, etc. are suitable. For the carbon nanofiber, chemical vapor deposition, self-organization, supercritical, spinning, and for the carbon nanotube, chemical vapor deposition, arc discharge, laser deposition, plasma deposition and the like can be used. In the case of an inorganic material, electrospinning, self-assembly, and the like are preferable, and it is preferable to use an alkoxide metal, a metal with a complex, or the like. In addition, the surface of the nanofiber made of organic material is coated with an organic material or inorganic material different from the nanofiber, and the surface of the nanofiber made of inorganic material is coated with an organic material or inorganic material different from the nanofiber. Are also included in the nanofibers of the present invention.

  The average diameter of such nanofibers is not particularly limited, but is preferably 1 nm or more and 990 nm or less, more preferably 500 nm or less, further preferably 300 nm or less, particularly preferably 200 nm or less, and most preferably 100 nm or less. When the average diameter of the nanofibers exceeds the upper limit, the heat dissipation and thermal expansion tend to be difficult to improve sufficiently.

  Further, the aspect ratio (length / diameter) of the nanofiber is not particularly limited, but is preferably 10 or more and 1000 or less, and preferably 30 or more and 800 or less from the viewpoint of heat dissipation, thermal expansibility, and viscosity when mixed with a resin. Is more preferably 50 or more and 500 or less, particularly preferably 80 or more and 500 or less, and most preferably 100 or more and 400 or less.

By selecting the inorganic filler under the above conditions, the inorganic filler can easily form a percolation structure in the resin, and an excellent epoxy resin composition exhibiting high heat dissipation and low thermal expansion can be obtained.
In the inorganic filler of the present invention, the inorganic filler other than the nanofiler is not particularly limited as long as the resin composition has good meltability. For example, fused crushed silica, fused spherical silica, crystalline silica, Silica such as secondary agglomerated silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium white, talc, clay, mica, glass fiber and the like. Among these, fused spherical silica is particularly preferable. Further, the shape of the particles is preferably infinitely spherical, and the amount of filling can be increased by mixing particles having different particle sizes. Moreover, in order to improve the meltability of the resin composition, it is preferable to use fused spherical silica.

Although there is no restriction | limiting in particular as thermal conductivity of the inorganic filler of this invention, 0.5 W / m * K or more is preferable, 1 W / m * K or more is more preferable, 5 W / m * K or more is more preferable, 20 W / M · K or more is particularly preferable, and 30 W / m · K or more is most preferable. From the viewpoint of a thermal conductivity of 30 W / m · K or more, SiC, AlN, Al ₂ O ₃ , Si ₃ N _{4 and the} like are mentioned as suitable materials. The resin composition of the present invention thus obtained maintains high heat resistance, and has a high level of heat dissipation and thermal expansion in a well-balanced manner.
It is preferable that the heat conductivity of the molded object of this embodiment is 0.5-70 W / mK, More preferably, it is 5-70 W / mK. Thereby, a heat dissipation characteristic can be improved more. The thermal conductivity is a sample (1 mm thick part) at 40 ° C. using a resin composition having a size of 25 mm × 25 mm × 1 mm using a steady-state thermal conductivity measuring device (“GH-1” manufactured by ULVAC-RIKO Co., Ltd.). ) Was measured in the thickness direction (W / mK).

  (C) As an upper limit of the content rate of an inorganic filler, it is preferable that it is 95 mass% or less on the basis of the whole resin composition of this invention, It is more preferable that it is 90 mass% or less, 83 mass% or less More preferably. When the upper limit value of the content ratio of the inorganic filler is within the above range, the fluidity of the resin composition does not decrease, and good results can be obtained in the heat cycle testability after curing. Moreover, it does not specifically limit as a lower limit of the content rate of an inorganic filler, However, It is preferable that it is 50 mass% or more in all the resin compositions, and it is more preferable that it is 60 mass% or more. When the upper limit value of the blending ratio is within the above range, it is easy to match the thermal expansion coefficient with the surrounding members.

  (C) The lower limit of the average particle diameter (D50) of the inorganic filler is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 4 μm or more. The upper limit of the average particle size of the inorganic filler is not particularly defined, but is preferably 50 μm or less, and more preferably 40 μm or less. The maximum particle size is preferably 105 μm or less. When the average particle size is less than 0.5 μm, the fluidity of the resin composition is lowered and the moldability may be impaired. On the other hand, if the average particle diameter exceeds 40 μm, the molded product may be warped or the dimensional accuracy may be reduced. On the other hand, if the maximum particle size exceeds 105 μm, the moldability may be reduced.

  Here, the average particle diameter (D50) of the inorganic filler (C) can be determined by, for example, a laser diffraction particle size distribution measuring device (Helos & Rodos manufactured by Sympatec), and the average particle size is measured by the same device. The particle size distribution (D50) at which the integrated volume is 50% in the obtained particle size distribution.

  As the inorganic filler, two or more inorganic fillers having different specific surface areas (SSA) and / or average particle diameters (D50) can be used.

(C) One or two or more inorganic fillers may be mixed, and the specific surface area (SSA) relative to the entire composition is preferably more than 3 mm ² / g and 1000 m ² / g or less. When the specific surface area (SSA) with respect to the entire composition is within the above range, the fluidity of the resin composition is easily secured. Preferably the upper limit of the specific surface area is less than 1000 m ² / g, more preferably not more than 800 m ² / g, more preferably 700 meters ² / g or less.

  The specific surface area (SSA: specific surface area) of (C) inorganic filler mentioned here can be determined by the BET method using a specific surface area measuring device, for example.

Here, the specific surface area (SSA) of (C) inorganic filler to (D) the entire composition is, for example, an inorganic filler having a specific surface area Am ² / g and an addition amount X wt%, and a specific surface area Bm ² / g. In the case where two types of inorganic fillers are mixed with an inorganic filler having an addition amount of Y wt%, the following formula:
Specific surface area (SSA) of the entire composition = A × X + B × Y
Can be obtained.

  In addition to the above components, the resin composition of the present invention may contain a curing accelerator as necessary. As a hardening accelerator, what is necessary is just to accelerate | stimulate the hardening reaction of an epoxy group and a hardening | curing agent, and what is generally used for a sealing material can be used. Specific examples include phosphorus-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; 1,8-diazabicyclo (5 , 4,0) Undecene-7, amidine compounds such as imidazole; tertiary amines such as benzyldimethylamine and quaternary onium salts of the above compounds, such as amidinium salts, ammonium salts, and amine complexes containing nitrogen atoms Compounds; boron compounds, organic acid metal salts, Lewis acids and the like.

  Although the lower limit of the mixture ratio of the whole hardening accelerator is not specifically limited, It is preferable that it is 0.1 mass% or more in all the resin compositions. Sufficient curability can be obtained when the lower limit of the blending ratio of the entire curing accelerator is within the above range. Moreover, although the upper limit of the mixture ratio of the whole hardening accelerator is not specifically limited, It is preferable that it is 1 mass% or less in all the resin compositions. Sufficient fluidity can be obtained when the upper limit of the blending ratio of the entire curing accelerator is within the above range. In order to improve the meltability, it is desirable to adjust the blending ratio as appropriate according to the type of curing accelerator used.

  In addition to the above components, a coupling agent can be blended in the resin composition of the present invention as necessary. As the coupling agent, various known silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane and vinyl silane, titanium based compounds, aluminum chelates, aluminum / zirconium based compounds and the like are used. be able to. Examples of these include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane Vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ [Bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N -Β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) Ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloro Propyl trimeth Sisilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-triethoxylyl-N- (1,3-dimethyl) Silane coupling agents such as hydrolyzate of rubylidene) propylamine, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxy Siacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tric Examples include titanate coupling agents such as milphenyl titanate and tetraisopropyl bis (dioctyl phosphite) titanate, and these may be used alone or in combination of two or more.

  Although the compounding quantity of a coupling agent is not specifically limited, It is preferable that it is 0.05 to 3 mass% with respect to (C) inorganic filler, and 0.1 to 2.5 mass% is preferable. More preferred. By setting it as 0.05 mass% or more, a flame | frame can be adhere | attached favorably, and a moldability can be improved by setting it as 3 mass% or less.

  In addition to the above components, the resin composition of the present invention may contain known additives as necessary. Specific examples of additives that can be used include colorants such as carbon black and titanium oxide; mold release agents such as natural wax, synthetic wax, higher fatty acids or metal salts thereof, paraffin, aliphatic esters, and oxidized polyethylene; silicone oil, Low stress agent such as silicone rubber and olefin rubber; ion scavenger such as hydrotalcite; inorganic flame retardant such as aluminum hydroxide and antimony trioxide, phosphorus flame retardant, nitrogen flame retardant, silicone flame retardant, organic Flame retardants such as metal salt flame retardants; various additives such as antioxidants, curing aids, and emulsifiers can be blended.

  The resin composition of the present invention is usually in the form of a powder or a tablet obtained by compressing it as necessary, and can be produced using any conventionally known technique capable of uniformly dispersing and mixing each component. it can. For example, all the components are pulverized and pulverized, mixed with a Henschel mixer, etc., then melt kneaded with a heating roll, melt kneaded with a kneader, mixed with a special mixer, or an appropriate combination of these methods. The semiconductor device of the present invention can be manufactured by resin-sealing a semiconductor element mounted on a lead frame or the like by transfer molding or the like using the resin composition of the present invention.

  Although a solvent can be used in the adjustment of the resin composition, voids resulting from the solvent are generated in the cured product, and there is a concern that appearance defects and reliability deterioration may occur. Often done.

  The residual solvent of the resin composition is preferably 0.1 wt% or less, more preferably 0.05 wt% or less, and further preferably 0.01 wt% or less. The quantification of the residual solvent can be performed, for example, using gas chromatography.

  In the resin composition of the present invention, the surface of the (C) inorganic filler is sufficiently covered with (A) an epoxy resin, (B) a curing agent, etc. in a powdered or tableted state, Higher fluidity can be shown.

The abundance ratio of (A) epoxy resin component or (B) curing agent component-derived C atom and (C) inorganic filler component-derived X atom in EDX measurement on the surface of (C) inorganic filler component before thermosetting treatment Is preferably C / X = 1 or more, more preferably C / X = 1.5 or more, and further preferably C / X = 2 or more. By setting the value of C / X within the above range, the resin composition can exhibit higher fluidity. X atom is an atom other than C atom, O atom, H atom and N atom in the main component of (C) inorganic filler component (defined as a component contained in the range of 1 to 95 mol%), X is defined by the molar concentration of X atoms constituting the main component. Although the kind of X atom is not specifically limited, It is preferable that they are a light element, a light metal, and a metal. X atoms vary depending on the type of inorganic filler, and examples include Al atoms in the case of alumina, B atoms in the case of boron nitride, Mg atoms in the case of magnesium hydroxide, and Si atoms in the case of silica.
In addition, said C is the molar concentration of the carbon atom contained in this (A) epoxy resin component or (B) hardening | curing agent component, The main component of said (C) inorganic filler component is this inorganic filler. The component contained in 1-95 mol% inside.

  The C / X can be measured by, for example, elemental quantification by SEM-EDX and calculating a correction according to the element from the peak integral value by the “standardless method (simple quantification method)”.

The present invention provides a sealing material or a vehicle-mounted member containing a cured product of the resin composition of the above-described embodiment; a semiconductor device in which a semiconductor element is sealed with a cured product of the resin composition of the above-described embodiment; and The present invention is also applicable to a method for manufacturing a semiconductor device, which includes a step of sealing a semiconductor element by compression molding using a cured product of the resin composition of the above-described embodiment.
The sealing material using the resin composition of the present invention can be widely used in the electrical and electronic fields such as semiconductor sealing materials and printed wiring board insulating materials. Realize highly reliable electronic device products when used under the higher temperature conditions in the electrical / electronic field, for example, as a sealing material for power semiconductors represented by in-vehicle power modules. I can do it.

Below, this invention is demonstrated in detail based on an Example and a comparative example. However, the present invention is not limited by these.
It shows below about the component used by the Example and the comparative example.

(Epoxy resin (A))
Epoxy resin 1: Trisphenol methane type epoxy resin having a softening point of 67 ° C. (EPPN-502H manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 2: Trisphenol methane type epoxy resin having a softening point of 52 ° C. (EPPN-501H manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 3: dicyclopentadiene-modified epoxy resin having a softening point of 73 ° C. (XD-1000 manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 4: Triglycidylaminophenol which is liquid at room temperature (about 23 ° C.) (JER630 manufactured by Mitsubishi Chemical Corporation)

(Curing agent (B))
Curing agent 1: 4,4′-diaminodiphenylsulfone (DDS) with a softening point of 175 to 180 ° C. and an equivalent weight of 62.1 g / eq (Wako Pure Chemical Industries, Ltd.)
Curing agent 2: Novolac type phenolic resin having a softening point of 100 ° C. and an equivalent of 105 g / eq (Resist Top PSM-4324 manufactured by Gunei Chemical Co., Ltd.)
Curing agent 3: 1,3-bis (3-aminophenoxy) benzene (Wako Pure Chemical Industries) with a softening point of 106.5-110 ° C. and an equivalent weight of 73 g / eq
Curing agent 4: 4,4′-diaminodiphenyl ether having a softening point of 186 to 187 ° C. and an equivalent weight of 50.6 g / eq (Wako Pure Chemical Industries, Ltd.)
Curing agent 5: 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene (Tokyo Kasei) having a softening point of 115 ° C. and an equivalent weight of 86.1 g / eq.
Curing agent 6: α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene (Tokyo Kasei) having a softening point of 165 ° C. and an equivalent weight of 86.1 g / eq.

(Inorganic filler (C))
Spherical inorganic filler 1: Spherical fused silica (average particle size 32 μm, specific surface area 1.3 m ² / g)
Spherical inorganic filler 2: spherical fused silica (average particle size 4.2 μm, specific surface area 1.5 m ² / g)
Spherical inorganic filler 3: spherical fused silica (average particle size 4.2 μm, specific surface area 3.5 m ² / g)
Spherical inorganic filler 4: Spherical fused silica (average particle size 4.2 μm, specific surface area 4.5 m ² / g)
Spherical inorganic filler 5: Spherical fused silica (average particle size 2.7 μm, specific surface area 2.1 m ² / g)
Spherical inorganic filler 6: spherical fused silica (average particle size 0.4 μm, specific surface area 7.3 m ² / g)
Inorganic filler 7: nanofiber SiC (average diameter 230 nm, aspect ratio 110, specific surface area 150 m ² / g)
Inorganic filler 8: nanofiber AlN (average diameter 400 nm, aspect ratio 150, specific surface area 50 m ² / g)
Inorganic filler 9: nanofiber Al ₂ O ₃ (average diameter 50 nm, aspect ratio 200, specific area 500 m ² / g)

(Other ingredients)
Curing accelerator: Triphenylphosphine (Tokyo Kasei)
MEK (Wako Pure Chemical Industries)

<Examples 1-7 and Comparative Examples 2-3, 5>
After the raw materials of the resin composition having the composition shown in Table 1 were pulverized and mixed for 5 minutes with a super mixer, they were uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing of the present invention and comparison. . This resin composition was pulverized with a mixer and further tableted with a tablet machine. The residual solvent of the composition was quantified using gas chromatography (SHIMADZU, GC-2014).

The modulus was measured based on the following method. The resin composition tableted so as to have a diameter of 1 cmφ and a thickness of 2 mm under a pressure of 20 MPa was measured by a parallel plate method using a rheometer (TA Instruments, DHR-2). Under the conditions of a gap of 2000 μm, a rotating plate diameter of 8 mm, a frequency of 1.0 HZ, and a strain of 0.1%, the temperature of the measurement part was stabilized at 23 ° C., and then increased from 23 ° C. to 200 ° C. at a heating rate of 50 ° C./min. The sample was heated and held at 200 ° C., and the modulus in the range was measured, and the minimum modulus in loss elastic modulus and the modulus after 10 minutes from the start of temperature increase were obtained. As an example, the rheometer results of Example 1 and Comparative Example 1 are shown in FIG. From FIG. 1, the value of the lowest modulus is 1.0 × 10 ² MPa in Example 1 and 2.0 × 10 ⁴ MPa in Comparative Example 1, and the modulus after 10 minutes is 1.0 × 10 ^{7 in} Example 1. MPa and Comparative Example 1 are determined to be 2.0 × 10 ⁷ MPa.

  C / Si was measured based on the following method. The resin composition tableted so as to have a diameter of 1 cmφ and a thickness of 1 cm under a pressure of 20 MPa was cleaved at room temperature to prepare a cut section inside the sample. Next, after fixing to the SEM sample stage, a conductive treatment was performed, and this was used as a speculum sample. Using an ultra-high resolution field emission scanning electron microscope (SU8220 manufactured by Hitachi High-Technologies) as the SEM body, an energy dispersive X-ray analyzer (NORAN System Seven manufactured by Thermo Fisher) as the EDX apparatus, acceleration voltage condition 5 kV, probe current condition High, WD (working distance) 15 mm, EDX measurement mode, in the condition of area analysis of about 10 μm region, a target was set on the surface of the inorganic filler in the active section, and the measurement time was 60 seconds. The elemental quantitative value was calculated by calculating a correction according to the element from the peak integral value by the “standardless method (simplified quantitative method)”. An example of the result in Example 1 is shown in FIG. 2 and Table 7, and an example of the result in Comparative Example 1 is shown in FIG. 3 and Table 8. The shadow of the SEM photograph and the result of EDX confirm that Pt2-1 in FIG. 2 and Table 7 is the surface of the inorganic filler, and Pt2-2 is a trace of the inorganic filler being detached. Paying attention to the results of EDX in FIG. 2 and Table 7, the peak of Si derived from the inorganic filler is observed because Pt2-1 is the surface of the inorganic filler, but Pt2-2 is a trace of the desorption of the inorganic filler. There is almost no Si peak derived from the inorganic filler.

  In accordance with a conventional method, a module on which a power semiconductor element was mounted was produced. The tableted resin composition was coated on the entire module by a transfer molding method, and was heat-cured at 250 ° C. for 8 hours, followed by resin sealing to produce a power semiconductor device.

  A schematic diagram of the manufactured power semiconductor device is shown in FIG. In the power semiconductor device 4, the lower surface side electrode of the power semiconductor element 41 is electrically connected to the lead member 43 through the bonding material 42. The main electrode of the power semiconductor element 41 is electrically connected to the lead member 43 via the wire 44. On the lower surface side of the lead member 43, a heat radiating plate 46 for releasing heat generated in the power semiconductor element 41 through the heat transfer sheet 45 to the outside is provided. The periphery of the power semiconductor element 41 is sealed with a sealing member 47 with the lead member 43 and a part of the heat radiating plate 46 exposed. The sealing member 47 contains the resin composition produced by the above procedure.

  Using the produced power semiconductor device, the cycle life of the power semiconductor devices of Example 1-7 and Comparative Example 1-5 was evaluated by a power cycle test (ΔTc = 125 ° C. 75 ° C.-200 ° C.).

<Comparative Example 1>
Comparative Example 1 shown in Table 1 is the same as Example 1 except that after mixing and grinding for 5 minutes with a super mixer, mixing and kneading were not performed uniformly using a mixing roll, but were further ground and mixed for 25 minutes with a super mixer. went.

<Comparative example 4>
Comparative Example 4 shown in Table 1 was performed in the same manner as in Example 1 except that the inorganic filler was treated in advance in accordance with Patent Document WO2015-125760 and MEK was treated as an organic solvent.

  Table 1 shows the results. A clear difference was found in the results of the power cycle test between Example 1-7 and Comparative Example 1-5. In Comparative Example 1, because of the difference in mixing method, in Comparative Example 2, the weight fraction of the inorganic filler is too large. In Comparative Example 3, the specific surface area of the inorganic filler with respect to the entire composition is too large. Since the particle size of the inorganic filler is too small, the inorganic filler is not sufficiently coated with the resin component, and it is considered that defects in the power cycle test are likely to occur. In Comparative Example 5, it is considered that defects in the power cycle test are likely to occur because the composition is not completely cured as indicated by the modulus value after 10 minutes. Moreover, about Example 7, since a composition contains a solvent, it is easy to generate | occur | produce a defect in hardened | cured material and it is thought that the defect in a power cycle test is easy to generate | occur | produce.

<Examples 8, 9, and 10>
Example 1 and Examples 8, 9, and 10 shown in Table 3 are the same as Example 1 except that a heat cycle test at 200 ° C. to −50 ° C. is performed instead of the power cycle test in Example 1. went. Details of the heat cycle test are shown below.

  Using a thermal shock device TSE-11 manufactured by ESPEC Corporation, one cycle is 30 minutes at 200 ° C. and 30 minutes at −50 ° C., and a sample is taken out after 500 times, and the cured product is visually checked for cracks and peeling. confirmed.

  Table 3 shows the results. In Examples 1, 8, and 9, no crack was observed after the heat cycle test, and in Example 10, a crack was observed after the heat cycle test. In Example 10, since the softening point of the epoxy resin is too low, it is considered that defects are likely to occur after the heat cycle test.

<Examples 11 to 15>
Example 1 and Examples 11 to 15 shown in Table 5 were performed in the same manner as in Table 3 except that the temperature condition of the heat cycle test was performed at 180 ° C. to −50 ° C.

  Table 5 shows the results. In Examples 1 and 9-14, no crack was observed after the heat cycle test, and in Example 15, a crack was observed after the heat cycle test. In Example 15, the heat resistance of the cured product is insufficient because the softening point of the curing agent is too low, and the crosslinking density of the cured product is insufficient because the equivalent of the curing agent is too large. It is thought that it is easy to generate.

The element quantitative value is a value obtained by calculating a correction according to the element by the “standardless method (simplified quantitative method)” from the peak integrated values of the EDX charts of FIG. 2 (2-b) and FIG. 2 (2-c). .

The element quantitative value is a value obtained by calculating a correction according to the element by the “standardless method (simple quantitative method)” from the peak integrated values of the EDX charts of FIGS. 3 (3-b) and 3 (3-c). .

  From these results, the power semiconductor device encapsulated by the encapsulant using the resin composition of the present invention exhibited excellent power cycle test resistance and heat cycle test resistance, respectively.

<Examples 16 to 18>
The raw materials of the resin composition having the composition shown in Table 9 were pulverized and mixed for 5 minutes with a super mixer, and then uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing according to the present invention and for comparison. . This resin composition was pulverized with a mixer and further tableted with a tablet machine. The residual solvent of the composition was quantified using gas chromatography (SHIMADZU, GC-2014).

The modulus was measured based on the following method. The resin composition tableted so as to have a diameter of 1 cmφ and a thickness of 2 mm under a pressure of 20 MPa was measured by a parallel plate method using a rheometer (TA Instruments, DHR-2). Under the conditions of a gap of 2000 μm, a rotating plate diameter of 8 mm, a frequency of 1.0 HZ, and a strain of 0.1%, the temperature of the measurement part was stabilized at 23 ° C., and then increased from 23 ° C. to 200 ° C. at a heating rate of 50 ° C./min. The sample was heated and held at 200 ° C., and the modulus in the range was measured, and the minimum modulus in loss elastic modulus and the modulus after 10 minutes from the start of temperature increase were obtained. In all the compositions, it was confirmed that the lowest modulus was 10 ⁴ MPa or less and the ultimate modulus after 10 minutes from the start of temperature increase was 10 ⁵ MPa or more. The results are shown in Table 9.

  C / X (X = Si or Al) was measured based on the following method. The resin composition tableted so as to have a diameter of 1 cmφ and a thickness of 1 cm under a pressure of 20 MPa was cleaved at room temperature to prepare a cut section inside the sample. Next, after fixing to the SEM sample stage, a conductive treatment was performed, and this was used as a speculum sample. Using an ultra-high resolution field emission scanning electron microscope (SU8220 manufactured by Hitachi High-Technologies) as the SEM body, an energy dispersive X-ray analyzer (NORAN System Seven manufactured by Thermo Fisher) as the EDX apparatus, acceleration voltage condition 5 kV, probe current condition High, WD (working distance) 15 mm, EDX measurement mode, in the condition of area analysis of about 10 μm region, a target was set on the surface of the inorganic filler in the active section, and the measurement time was 60 seconds. The elemental quantitative value was calculated by calculating a correction according to the element from the peak integral value by the “standardless method (simplified quantitative method)”. It was confirmed that C / (X = Si or Al) = 1 or more in all compositions. The results are shown in Table 9.

  The measurement of thermal conductivity was performed based on the following method. Using a resin composition having a size of 25 mm × 25 mm × 1 mm with a steady-state thermal conductivity measuring device (“GH-1” manufactured by ULVAC-RIKO), heat in the thickness direction of the sample (1 mm thick portion) at 40 ° C. Conductivity (W / mK) was measured. In all compositions, the thermal conductivity ranged from 0.5 to 70 W / mK. The results are shown in Table 9.

  From these results, it was confirmed that the resin composition of the present invention exhibits a good thermoelectric power rate, that is, heat dissipation.

  The sealing material using the resin composition of the present invention can be widely used in the electrical and electronic fields such as semiconductor sealing materials and printed wiring board insulating materials. Realize highly reliable electronic device products when used under the higher temperature conditions in the electrical / electronic field, for example, as a sealing material for power semiconductors represented by in-vehicle power modules. I can do it.

4 Power Semiconductor Device 41 Power Semiconductor Element 42 Bonding Material 43 Lead Member 44 Wire 45 Heat Transfer Sheet 46 Heat Dissipation Plate 47 Sealing Member

Claims (17)

(A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II) After the temperature was raised from 23 ° C. to 50 ° C./200° C. by rheometer evaluation, the lowest modulus when evaluated at 200 ° C. was 10 ⁴ MPa or less, and reached 10 minutes after the start of temperature rise. The modulus is 10 ⁵ MPa or more;
The said resin composition satisfy | fills. The resin composition has the following conditions:
(I-II) The softening point of the epoxy resin (A) is 35 ° C. or higher;
The resin composition according to claim 1, further satisfying The resin composition has the following conditions:
(I-III) The residual solvent of the resin composition is less than 0.1% by weight;
The resin composition according to claim 1 or 2, further satisfying: The resin composition has the following conditions:
(I-IV) The equivalent of the (B) curing agent is 90 g / eq or less, and the softening point is 105 ° C. or more;
The resin composition according to any one of claims 1 to 3, further satisfying: (A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II-I) On the surface of the (C) inorganic filler in the resin composition, the C atom derived from the (A) epoxy resin or the (B) curing agent in the EDX measurement and the (C) inorganic filler The abundance ratio of the derived X atom is C / X = 1 or more, and the X atom is a C atom in the main component (component contained in the range of 1 to 95 mol%) of the (C) inorganic filler, Atoms other than O, H and N atoms, and said X is defined as the molar concentration of said X atoms;
The said resin composition satisfy | fills. The resin composition has the following conditions:
(II-II) The weight fraction of the (C) inorganic filler in the resin composition is 95% by weight or less;
The resin composition according to claim 5, further satisfying The resin composition has the following conditions:
(II-III) The inorganic filler (C) contains at least nanofibers;
The resin composition according to claim 5 or 6, further satisfying The resin composition has the following conditions:
(II-IV) The specific surface area of the (C) inorganic filler with respect to the entire resin composition is more than 3 mm ² / g and 1000 m ² / g or less;
The resin composition according to any one of claims 5 to 7, further satisfying The resin composition has the following conditions:
(II-V) The softening point of the epoxy resin (A) is 35 ° C. or higher;
The resin composition according to any one of claims 5 to 8, further satisfying The resin composition has the following conditions:
(II-VI) The residual solvent of the resin composition is less than 0.1% by weight;
The resin composition according to any one of claims 5 to 9, further satisfying The resin composition has the following conditions:
(II-VII) The equivalent of the (B) curing agent is 90 g / eq or less, and the softening point is 105 ° C. or more;
The resin composition according to any one of claims 5 to 10, further satisfying (A) A resin composition containing an epoxy resin, (B) a curing agent, and (C) an inorganic filler, the following conditions:
(II-I) On the surface of the (C) inorganic filler in the resin composition, the C atom derived from the (A) epoxy resin or the (B) curing agent in the EDX measurement and the (C) inorganic filler The abundance ratio of the derived X atom is C / X = 1 or more, and the X atom is a C atom in the main component (component contained in the range of 1 to 95 mol%) of the (C) inorganic filler, Atoms other than O, H and N atoms, and said X is defined as the molar concentration of said X atoms;
(II-II) The weight fraction of the (C) inorganic filler in the resin composition is 95% by weight or less;
(II-III) The (C) inorganic filler contains at least nanofibers;
(II-IV) The specific surface area of the (C) inorganic filler with respect to the entire resin composition is more than 3 mm ² / g and 1000 m ² / g or less;
(II-V) The softening point of the epoxy resin (A) is 35 ° C. or higher;
(II-VI) The residual solvent of the resin composition is less than 0.1% by weight; and (II-VII) The equivalent of the (B) curing agent is 90 g / eq or less and the softening point is 105 ° C. Or more;
The said resin composition satisfy | fills.   The resin composition according to any one of claims 1 to 12, wherein the (B) curing agent is a compound having an amino group.   The diameter of the nanofiber contained at least in the (C) inorganic filler is 1 nm or more and 990 nm or less, and the aspect ratio (length of nanofiber / diameter of nanofiber) is 10 or more and 1000 or less. 14. The resin composition according to any one of items 13.   The sealing material or vehicle-mounted member containing the hardened | cured material of the resin composition of any one of Claims 1-14.   The semiconductor device with which the semiconductor element is sealed with the hardened | cured material of the resin composition of any one of Claims 1-14.   The manufacturing method of a semiconductor device including the process of sealing a semiconductor element by compression molding using the hardened | cured material of the resin composition of any one of Claims 1-14.