Sealing resin composition and semiconductor device

Abstract

Provided is a resin composition for sealing, which is capable of obtaining good continuous moldability at a higher level. This sealing resin composition contains (A) an epoxy resin, (B) a phenol-based curing agent, (C) an inorganic filler, and (D) a butadiene-acrylonitrile copolymer, and is configured so as to satisfy the following condition i. Condition i: A transfer molding machine is used to inject the resin composition for sealing at a mold temperature of 175 DEG C into a mold in which a copper plate having a chromium-plated surface is disposed, and the resin composition is heated at 175 DEG C for 300 seconds and cured. The obtained cured product of the sealing resin composition has a mold shear strength (speed of 300 [mu] m / sec, temperature of 25 DEG C) of 7.0 N / mm2 or less with respect to the copper plate.

Description

Technical Field

[0001] The present invention relates to a sealing resin composition and a semiconductor device. Background Art

[0002] In the recent market trend of miniaturization, lightness and high performance of electronic equipment, the high integration of semiconductor elements has been developed year by year, and the surface mounting of semiconductor devices has also been promoted. In addition, new area mounting type semiconductor devices have been developed, and the shift from existing semiconductor devices is also developing. As a result, the requirements for the performance of the sealing resin composition used in the manufacturing process of semiconductor devices are diversified and advanced, and various corresponding sealing resin compositions are being researched and developed.

[0003] For example, Patent Document 1 discloses that from the viewpoint of improving the adhesion of a sealing resin composition for semiconductor elements to metal and the high-temperature reflow resistance during installation, the sealing resin composition preferably comprises an epoxy resin containing an epoxy compound of a predetermined structure, a phenolic curing agent, an inorganic filler, a hollow structure composed of at least one selected from an organic material and a silicone material, and a curing accelerator as essential components, and further comprises a butadiene-acrylonitrile copolymer and a triazine phenolic resin.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2020-33514 Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] The present inventors have focused on the occurrence of defects in the sealing process of semiconductor devices, which reduces productivity. Furthermore, it has been found that when continuous molding is performed using the conventional sealing resin composition disclosed in Patent Document 1, cracks are generated in a part of the mold of the sealing resin composition, or unfilled parts are generated in the mold, etc., which reduces continuous molding performance.

[0009] Technical solutions for solving technical problems

[0010] The present inventors have conducted intensive research to solve the technical problems of cracks and unfilled parts generated during continuous molding, and have found that even a sealing resin composition comprising an epoxy resin, a phenolic curing agent, an inorganic filler and a butadiene-acrylonitrile copolymer has a composition with good continuous moldability and a composition with poor continuous moldability. Therefore, as a main condition for distinguishing the two, it was recognized that it is effective to control the die shear strength of the cured product of the sealing resin composition with respect to chrome, and this condition was embodied as condition i, thereby completing the present invention.

[0011] According to the present invention, the following sealing resin composition and related techniques can be provided.

[0012] [1] A sealing resin composition comprising:

[0013] (A) Epoxy resin;

[0014] (B) phenolic curing agent;

[0015] (C) inorganic filler materials; and

[0016] (D) butadiene-acrylonitrile copolymer,

[0017] The sealing resin composition is configured to satisfy the following condition i.

[0018] Condition i: Using a transfer molding machine, the sealing resin composition was injected into a mold with a copper plate whose surface was chrome-plated at a mold temperature of 175°C, and heated at 175°C for 300 seconds to cure. The die shear strength (speed 300 μm / sec, temperature 25°C) between the cured product of the sealing resin composition and the chrome-plated surface of the copper plate was 7.0 N / mm 2 the following.

[0019] [2] The sealing resin composition according to [1], wherein

[0020] The content of the (D) butadiene-acrylonitrile copolymer is 0.01 to 2% by mass based on the total amount of the sealing resin composition.

[0021] [3] The sealing resin composition according to [1] or [2], wherein

[0022] (D) The butadiene-acrylonitrile copolymer is represented by the following formula (1).

[0023]

[0024] (In formula (1), x and y are both positive numbers less than 1, and satisfy x+y=1.)

[0025] [4] The sealing resin composition according to [3], wherein

[0026] In the formula (1), y is 0.05 or more and 0.24 or less.

[0027] [5] The sealing resin composition according to any one of [1] to [4], wherein

[0028] The (A) epoxy resin comprises one or more selected from crystalline epoxy resins, novolac epoxy resins, multifunctional epoxy resins, phenol aralkyl epoxy resins, naphthol epoxy resins, triazine core-containing epoxy resins and bridged cyclic hydrocarbon compound-modified phenolic epoxy resins.

[0029] [6] The sealing resin composition according to any one of [1] to [5], wherein

[0030] (B) The phenolic curing agent contains one or more selected from the group consisting of novolac-type phenolic resins, multifunctional phenolic resins, modified phenolic resins, aralkyl-type phenolic resins and bisphenol compounds.

[0031] [7] The sealing resin composition according to any one of [1] to [6], further comprising (E) a curing accelerator.

[0032] [8] The sealing resin composition according to any one of [1] to [7], further comprising (F) silicone oil.

[0033] [9] The sealing resin composition according to any one of [1] to [8], which is used for sealing a semiconductor element.

[0034]

[10] A semiconductor device comprising a semiconductor element sealed with the sealing resin composition according to any one of [1] to [9].

[0035] Effects of the Invention

[0036] The sealing resin composition of the present invention can obtain a higher level of good continuous moldability. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is a cross-sectional view showing the structure of the semiconductor device according to this embodiment.

[0038] Figure 2 It is a cross-sectional view showing the structure of a modification example of the semiconductor device according to the present embodiment.

[0039] Description of Reference Numerals

[0040] 20: semiconductor element; 30: substrate; 32: chip pad; 34: external lead; 40: wire; 50: sealing material; 60: solder ball; 100: semiconductor device. DETAILED DESCRIPTION

[0041] In this specification, the expression "a to b" in the description of a numerical range means a or more and b or less unless otherwise specified. For example, "1 to 5 mass %" means "1 mass % or more and 5 mass % or less". In addition, the lower limit and upper limit of a numerical range can be arbitrarily combined with the lower limit and upper limit of another numerical range.

[0042] Each component and material exemplified in the present specification may be used alone or in combination of two or more unless otherwise specified.

[0043] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[0044] In order to avoid cumbersomeness, when there are multiple identical components in the same figure, sometimes only one of them is marked with a symbol, and not all of them are marked with symbols. All drawings are only for illustration. The shapes and size ratios of the components in the drawings do not necessarily correspond to the actual items.

[0045] <Sealing resin composition>

[0046] The sealing resin composition of the present embodiment includes (A) an epoxy resin, (B) a phenolic curing agent, (C) an inorganic filler, and (D) a butadiene-acrylonitrile copolymer, and is configured to satisfy the following condition i, thereby further improving continuous moldability.

[0047] Condition i: Using a transfer molding machine, the sealing resin composition was injected into a mold with a copper plate whose surface was chrome-plated at a mold temperature of 175°C, and heated at 175°C for 300 seconds to cure. The die shear strength (speed 300 μm / sec, temperature 25°C) between the cured product of the sealing resin composition and the chrome-plated surface of the copper plate was 7.0 N / mm 2 the following.

[0048] The details of the mechanism by which the sealing resin composition of the present embodiment obtains the above-mentioned effect by satisfying condition i are not clear, but it is presumed as follows.

[0049] The die shear strength of condition i refers to the bonding strength of the cured product of sealing resin composition and mold.Therefore, by controlling the die shear strength, it is possible to maintain good demoulding properties relative to mold, therefore, even if it is considered that continuous molding, it is also possible to suppress the generation of cracks on the cured product of sealing resin composition, or to produce unfilled parts in mold.And then, at present, as one of the technologies related to the demoulding properties of mold with respect to improvement, it is known that the plating processing of chromium etc. is implemented on the surface of mold to improve demoulding properties.Therefore, in the sealing resin composition of the present embodiment, by controlling the die shear strength relative to chrome plating, it is possible to control demoulding properties with a higher level, it is possible to effectively improve continuous molding properties.

[0050] In condition i, the copper plate whose surface is plated with chromium is a test piece for a close contact test in which chromium is plated to a depth of 0.5 μm on a flat copper substrate.

[0051] By controlling the die shear strength with the copper plate to 7.0N / mm 2 The following can improve the mold release property of the cured product of the sealing resin composition from the mold and improve the continuous molding property. The mold shear strength is preferably 6.5 N / mm 2 Below, more preferably 6.0 N / mm 2 Below, more preferably 5.0 N / mm 2 Below, more preferably 4.5 N / mm 2 the following.

[0052] On the other hand, the lower limit of the die shear strength is not particularly limited, and the lower the better, but from the viewpoint of maintaining good handleability of the sealing resin composition, it is preferably 0.01 N / mm 2 above.

[0053] The sealing resin composition satisfying condition i can be realized by combining known methods, such as controlling the combination of various materials constituting the sealing resin composition, the blending amount of various materials, or controlling the manufacturing conditions of the sealing resin composition, etc. For example, the combination of (A) epoxy resin, (B) phenolic curing agent and (D) butadiene-acrylonitrile copolymer in the sealing resin composition can be adjusted, or the content of (D) butadiene-acrylonitrile copolymer, the content of structural units derived from butadiene and acrylonitrile in the copolymer, etc. can be controlled.

[0054] In addition, when the sealing resin composition of the present embodiment is injection molded under the conditions of a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 120 seconds, and further heat-treated at 175°C for 4 hours and post-cured to produce a test piece, it is preferred that the flexural strength and flexural modulus (based on JIS K 6911) of the test piece at 260°C respectively satisfy the following.

[0055] The bending strength is preferably 5 to 100 MPa, more preferably 10 to 80 MPa, and even more preferably 15 to 50 MPa.

[0056] The flexural modulus is preferably 100 to 1000 MPa, more preferably 200 to 900 MPa, and even more preferably 300 to 800 MPa.

[0057] Hereinafter, each component contained in the sealing resin composition of this embodiment is demonstrated.

[0058] [(A) Epoxy resin]

[0059] (A) The epoxy resin is a compound having two or more epoxy groups in one molecule, and may be any of a monomer, an oligomer, and a polymer.

[0060] Specifically, (A) epoxy resin is selected from crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin and other novolac type epoxy resins; triphenylmethane type epoxy resin, alkyl modified trisphenol methane type epoxy resin and other multifunctional epoxy resins; phenol aralkyl type epoxy resin containing phenylene skeleton, phenol aralkyl type epoxy resin containing biphenylene skeleton and other phenol aralkyl type epoxy resin; dihydroxynaphthalene type epoxy resin, dihydroxynaphthalene dimer epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene and other naphthol type epoxy resin; triazine core-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene modified phenol type epoxy resin and other bridged cyclic hydrocarbon compound modified phenol type epoxy resin one or more, more preferably two or more.

[0061] From the viewpoint of obtaining good demolding properties and continuous molding properties, the epoxy resin (A) is preferably one or more selected from triphenylmethane type epoxy resins, biphenyl aralkyl type multifunctional epoxy resins, o-cresol type difunctional epoxy resins, biphenyl type difunctional epoxy resins and bisphenol type difunctional epoxy resins.

[0062] From the same viewpoint, the epoxy resin (A) is preferably one or more selected from tris(hydroxyphenyl)methane epoxy resins, phenol aralkyl epoxy resins containing a biphenylene skeleton, o-cresol novolac epoxy resins, 3,3,5,5'-tetramethylbiphenyl glycidyl ether epoxy resins and multifunctional solid epoxy resins containing a dicyclopentadiene skeleton, more preferably one or more selected from phenol aralkyl epoxy resins containing a biphenylene skeleton, 3,3',5,5'-tetramethylbiphenyl glycidyl ether epoxy resins and multifunctional solid epoxy resins containing a dicyclopentadiene skeleton, and further preferably a phenol aralkyl epoxy resin containing a biphenylene skeleton.

[0063] From the viewpoint of obtaining appropriate fluidity during molding and improving filling properties and continuous moldability, the content of the epoxy resin (A) is preferably 2 mass % or more, more preferably 3 mass % or more, and even more preferably 4 mass % or more based on the entire sealing resin composition.

[0064] In addition, from the viewpoint of improving the reliability of a semiconductor device obtained using the sealing resin composition, the content of the epoxy resin (A) is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further preferably 10% by mass or less, relative to the entire sealing resin composition.

[0065] [(B) Phenolic curing agent]

[0066] As the (B) phenolic curing agent, any monomer, oligomer, or polymer having two or more phenolic hydroxyl groups in one molecule can be used, and the molecular weight and molecular structure thereof are not limited.

[0067] (B) Phenolic curing agent, for example, can be cited phenol novolac type phenolic resins such as phenol novolac resin, cresol novolac resin, bisphenol novolac; polyvinylphenol; phenol-hydroxybenzaldehyde resin, trisphenol methane type phenolic resin and other multifunctional phenolic resins; terpene modified phenolic resin, dicyclopentadiene modified phenolic resin and other modified phenolic resins; aralkyl type phenolic resins such as phenol aralkyl resin having at least one of phenylene skeleton and biphenylene skeleton, naphthol aralkyl resin having at least one of phenylene and biphenylene skeleton; bisphenol compounds such as bisphenol A, bisphenol F, etc., these can be used alone or in combination of two or more.

[0068] Among these compounds, from the viewpoint of obtaining good continuous moldability and improving the insulating properties of a semiconductor device obtained using the sealing resin composition, it is more preferable to use one or more selected from trisphenol methane type phenolic resins, biphenyl aralkyl type phenolic resins, novolac type phenolic resins, phenol aralkyl type resins containing a biphenylene skeleton, and phenol aralkyl type-formaldehyde condensates containing a biphenylene skeleton.

[0069] In the present embodiment, from the viewpoint of achieving excellent fluidity during molding and improving filling properties and continuous moldability, the content of the (B) phenolic curing agent is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and further preferably 3% by mass or more, relative to the entire sealing resin composition.

[0070] In addition, with respect to a semiconductor device obtained using a sealing resin composition, from the viewpoint of improving moisture-resistant reliability and reflow resistance, the content of the (B) phenolic curing agent is preferably 25% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the entire sealing resin composition.

[0071] From the viewpoint of suppressing the decrease in moisture resistance, curability, etc., the equivalent ratio (EP / OH) of all epoxy groups (EP) and all phenolic hydroxyl groups (OH) used in the sealing resin composition of the present embodiment is preferably 0.5 to 2, and more preferably 0.8 to 1.7.

[0072] [(C) Inorganic filler]

[0073] As the inorganic filler (C), materials generally used in semiconductor sealing resin compositions can be used. In addition, the inorganic filler (C) may be a surface-treated material.

[0074] Specific examples of the (C) inorganic filler include silica such as fused silica, crystalline silica, and amorphous silica; alumina; talc; titanium oxide; silicon nitride; and aluminum nitride. These inorganic fillers may be used alone or in combination of two or more.

[0075] From the viewpoint of excellent versatility, (C) inorganic filler preferably comprises silica. As the shape of silica, molten spherical silica, molten crushed silica, crystalline silica, etc. can be cited. For example, from the viewpoint of suppressing the increase in melt viscosity of the sealing resin composition, spherical silica is preferred.

[0076] From the viewpoint of improving continuous moldability and adhesion, the average diameter (D50) of the inorganic filler (C) is preferably 0.1 μm or more, more preferably 0.3 μm or more, and is preferably 80 μm or less, more preferably 50 μm or less, and further preferably 40 μm or less.

[0077] (C) The particle size distribution of the inorganic filler can be obtained by measuring the particle size distribution of particles on a volume basis using a commercially available laser diffraction particle size distribution measuring apparatus (for example, SALD-7000 manufactured by Shimadzu Corporation).

[0078] From the viewpoint of improving continuous moldability and adhesion, the (C) inorganic filler preferably has a plurality of peaks in the particle size distribution by laser diffraction particle size distribution measurement, and more preferably has at least one peak each between 0.1 and 5 μm and 10 and 30 μm.

[0079] Furthermore, from the viewpoint of increasing the content of the (C) inorganic filler, a material adjusted so as to make the particle size distribution of the (C) inorganic filler wider may be used.

[0080] From the viewpoint of obtaining the releasability of the cured product and improving the low hygroscopicity and low thermal expansion of the sealing material formed using the sealing resin composition, thereby more effectively improving the moisture resistance reliability and reflow resistance of the obtained semiconductor device, the content of the (C) inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, relative to the entire sealing resin composition.

[0081] In addition, from the viewpoint of more effectively improving the fluidity and filling properties when molding the sealing resin composition, the content of the (C) inorganic filler is preferably 97% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, relative to the entire sealing resin composition.

[0082] [(D) Butadiene-acrylonitrile copolymer]

[0083] The (D) butadiene-acrylonitrile copolymer functions as a material that imparts mold release properties to the cured product and bonds the (A) epoxy resin and the (C) inorganic filler to a semiconductor element or an organic substrate that is a component of a semiconductor device.

[0084] In addition, since the (D) butadiene-acrylonitrile copolymer is compatible with the mixture of the (A) epoxy resin and the (B) phenolic curing agent, and the (D) butadiene-acrylonitrile copolymer can be uniformly dispersed, it is estimated that the mold release property is maintained over the entire outer surface of the cured product, and the continuous moldability can be improved.

[0085] As the (D) butadiene-acrylonitrile copolymer, a copolymer having a structure represented by the following formula (1) is preferred.

[0086]

[0087] In the above formula (1), x and y are both positive numbers less than 1, and satisfy x + y = 1. Among them, y is preferably 0.05 to 0.24, and more preferably 0.07 to 0.20.

[0088] By setting the content y of the structural unit derived from acrylonitrile to the above numerical range, compatibility with the (A) epoxy resin is appropriately achieved, and continuous moldability is easily improved.

[0089] The number average molecular weight of the butadiene-acrylonitrile copolymer (D) is preferably 2,000 to 5,000, and more preferably 3,000 to 4,000.

[0090] The number average molecular weight can be calculated in terms of polystyrene using a GPC apparatus such as HLC-8120 manufactured by TOSOH. By setting the number average molecular weight within the above range, the occurrence of filling defects during molding due to reduced fluidity can be suppressed.

[0091] The (D) butadiene-acrylonitrile copolymer is preferably liquid at 25° C. and has a viscosity of 50 to 160 Pa·s. It is more preferably liquid at 40° C. and has a viscosity of 5 to 50 Pa·s. This can provide appropriate fluidity, and can improve mold release and continuous molding properties.

[0092] From the viewpoint of obtaining mold release properties of the cured product and obtaining fluidity and adhesion, the content of the (D) butadiene-acrylonitrile copolymer is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass % or more based on the entire sealing resin composition.

[0093] From the viewpoint of suppressing high viscosity and obtaining good continuous moldability, the content of the (D) butadiene-acrylonitrile copolymer is preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the entire sealing resin composition.

[0094] The sealing resin composition of the present embodiment may further contain the following components.

[0095] [(E) Curing accelerator]

[0096] The (E) curing accelerator is used to accelerate the curing reaction between the epoxy groups in the (A) epoxy resin and the phenolic hydroxyl groups in the (B) phenolic curing agent.

[0097] (E) The curing accelerator may include, for example, a phosphorus atom-containing compound selected from organic phosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds, etc.; a nitrogen atom-containing compound such as amidine or tertiary amines of 1,8-diazabicyclo[5.4.0]undecene-7, benzyldimethylamine, 2-methylimidazole, etc., and a quaternary salt of the above amidine or amine; or one or more polyhydroxynaphthalene compounds such as 2,3-dihydroxynaphthalene.

[0098] Among them, from the viewpoint of improving curability, it is more preferred to include a compound containing a phosphorus atom. As a compound containing a phosphorus atom, for example, 4-hydroxy-2-(triphenylphosphonium)phenolate can be cited. In addition, from the viewpoint of improving the balance between continuous formability and curability, it is more preferred to include a compound with latency such as a tetrasubstituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, an adduct of a phosphonium compound and a silane compound.

[0099] From the viewpoint of improving the curing characteristics of the sealing resin composition, the content of the curing accelerator (E) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on the entire sealing resin composition.

[0100] In addition, from the viewpoint of obtaining the releasability of the cured product and obtaining preferred fluidity when the sealing resin composition is molded, the content of the (E) curing accelerator is preferably 2.0 mass % or less, more preferably 1.0 mass % or less, and further preferably 0.5 mass % or less, relative to the entire sealing resin composition.

[0101] [(F) Silicone oil]

[0102] (F) Silicone oil is partially miscible in the resin component when the resin component is molten, and partially becomes incompatible, thus exhibiting a surface active effect. Thus, for example, as (A) epoxy resin, even if a crystalline epoxy resin is used, its recrystallization can be suppressed, and the uneven curability of the sealing resin composition can be reduced. In addition, when a release agent is used, the release agent is separated during molding, and the release agent can be suppressed from precipitating on the surface of the cured product to prevent mold contamination.

[0103] (F) As silicone oil, epoxy-modified organopolysiloxane, amino-modified organopolysiloxane, hydrocarbon-modified organopolysiloxane, polycaprolactone-modified organopolysiloxane etc. are mentioned, for example.

[0104] From the viewpoint of improving the curing characteristics of the sealing resin composition, the content of the silicone oil (F) is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass % or more, based on the entire sealing resin composition.

[0105] In addition, from the viewpoint of obtaining the releasability of the cured product and obtaining preferred fluidity when the sealing resin composition is molded, the content of the (F) silicone oil is preferably 2.0 mass % or less, more preferably 1.0 mass % or less, and further preferably 0.5 mass % or less, relative to the entire sealing resin composition.

[0106] [Other ingredients]

[0107] The sealing resin composition of this embodiment may contain components other than the above components, for example, one or more of various additives such as coupling agents, fluidity imparting agents, release agents, ion scavengers, low stress components, flame retardants, colorants, antioxidants, etc. may be appropriately blended.

[0108] As the coupling agent, for example, various silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane and vinylsilane; titanium compounds; aluminum chelates, aluminum / zirconium compounds and other known coupling agents can be used.

[0109] The aminosilane is not particularly limited, and examples thereof include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl γ-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6-(aminohexyl) 3-aminopropyltrimethoxysilane, and N-(3-(trimethoxysilylpropyl)-1,3-phenylenediamine.

[0110] The content of the coupling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the inorganic filler (C).

[0111] The release agent may include, for example, one or more selected from natural waxes such as carnauba wax; synthetic waxes such as montanate wax and oxidized polyethylene wax; higher fatty acids such as zinc stearate and metal salts thereof; paraffin wax; and carboxylic acid amides such as erucic acid amide.

[0112] From the viewpoint of improving the releasability of the cured product of the sealing resin composition, the content of the release agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, and is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.5% by mass or less, relative to the entire sealing resin composition.

[0113] A specific example of the ion scavenger is hydrotalcite.

[0114] From the viewpoint of improving the reliability of the sealing material, the content of the ion scavenger is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and is preferably 1.0 mass % or less, more preferably 0.5 mass % or less, based on the entire sealing resin composition.

[0115] Specific examples of the low stress component include silicone rubber, silicone elastomer, silicone resin and other organic silicon, and rubber.

[0116] From the viewpoint of improving the reliability of the sealing material, the content of the low stress component is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably 0.1 mass % or more, and is preferably 5 mass % or less, more preferably 3 mass % or less, further preferably 1 mass % or less, relative to the entire sealing resin composition.

[0117] Specific examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene.

[0118] From the viewpoint of improving the flame retardancy of the sealing material, the content of the flame retardant is preferably 1% by mass or more, more preferably 5% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, based on the entire sealing resin composition.

[0119] Specific examples of the colorant include carbon black and red iron.

[0120] From the viewpoint of obtaining a preferred color tone of the sealing material, the content of the colorant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is preferably 2% by mass or less, more preferably 1% by mass or less, based on the entire sealing resin composition.

[0121] Specific examples of the antioxidant include hindered phenol compounds, hindered amine compounds, and thioether compounds.

[0122] <Sealing resin composition>

[0123] The sealing resin composition of the present embodiment is solid at room temperature (25° C.), and its shape can be selected according to the molding method of the sealing resin composition, and examples thereof include ingots; particle forms such as powder and granules; and sheets.

[0124] In addition, about the manufacture method of sealing resin composition, for example, utilize known device to mix the above-mentioned each component, utilize roller, kneading machine or extruder to carry out melt mixing then, pulverize after cooling, can obtain sealing resin composition by the above method.In addition, also can be shaped after pulverizing, obtain particle-like or sheet-like sealing resin composition.For example, also can ingot molding be ingot-like, obtain particle-like sealing resin composition.In addition, for example, also can utilize vacuum extruder to obtain sheet-like sealing resin composition.In addition, also can appropriately adjust dispersity and fluidity etc. to the obtained sealing resin composition.

[0125] The sealing resin composition obtained in this embodiment has excellent adhesion to metal parts. More specifically, according to this embodiment, the adhesion between the cured product of the sealing resin composition and parts made of Ag, Ni, Cu or alloys containing one or more of these can also be improved.

[0126] The sealing resin composition of the present embodiment can be used for transfer molding, injection molding, or compression molding.

[0127] Furthermore, by using the sealing resin composition obtained in this embodiment, a semiconductor device having excellent reliability can be obtained.

[0128] The sealing resin composition of the present embodiment has a melt viscosity of 30 Pa·s or less, preferably 20 Pa·s or less at 175° C. This provides excellent moldability and excellent processing stability when sealing a semiconductor element with the sealing resin composition.

[0129] <Semiconductor devices>

[0130] The semiconductor device of the present embodiment is a device for sealing semiconductor elements using the cured product of the sealing resin composition of the present embodiment described above. As specific examples of semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, solid-state imaging elements, etc. can be cited. The semiconductor element is preferably a so-called element without the injection and emission of light other than optical semiconductor elements such as light-receiving elements and light-emitting elements (light-emitting diodes, etc.).

[0131] The substrate of the semiconductor device is, for example, a wiring substrate such as an interposer or a lead frame. The semiconductor element may be electrically connected to the substrate by wire bonding or flip chip connection.

[0132] Examples of semiconductor devices obtained by sealing a semiconductor element by sealing molding using a sealing resin composition include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Flame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded Array Process BGA), eWLB (Embedded Wafer-Level BGA), Fan-In eWLB, and Fan-Out eWLB.

[0133] Hereinafter, the invention will be described in more detail with reference to the accompanying drawings.

[0134] Figure 1 and Figure 2 Each of them is a cross-sectional view showing the structure of a semiconductor device. In addition, in this embodiment, the structure of the semiconductor device is not limited to Figure 1 and Figure 2 The structure shown.

[0135] first, Figure 1 The semiconductor device 100 shown includes a semiconductor element 20 mounted on a substrate 30 and a sealing material 50 that seals the semiconductor element 20 .

[0136] The sealing material 50 is composed of a cured product obtained by curing the sealing resin composition according to the present embodiment described above.

[0137] And, in Figure 1 In the example, the case where the substrate 30 is a circuit substrate is illustrated. In this case, Figure 1As shown, a plurality of solder balls 60 are formed on the other surface of the substrate 30 opposite to the surface on which the semiconductor element 20 is mounted. The semiconductor element 20 is mounted on the substrate 30 and is electrically connected to the substrate 30 via the wire 40. On the other hand, the semiconductor element 20 may be flip-chip mounted on the substrate 30. Here, the wire 40 is not limited, and for example, Ag wire, Ni wire, Cu wire, Au wire, and Al wire can be cited. Preferably, the wire 40 is composed of Au, Cu, or Ag, or an alloy containing one or more of them.

[0138] The sealing material 50 seals the semiconductor element 20, for example, by covering the other surface of the semiconductor element 20 opposite to the surface facing the substrate 30. Figure 1 In the illustrated example, the sealing material 50 is formed so as to cover the other surface and the side surfaces of the semiconductor element 20 .

[0139] In the present embodiment, the sealing material 50 is formed of a cured product of the above-mentioned sealing resin composition. Therefore, in the semiconductor device 100, the sealing material 50 and the lead 40 have excellent adhesion, and thus the reliability of the semiconductor device 100 is excellent.

[0140] The sealing material 50 can be formed by sealing and molding a sealing resin composition using a known method such as transfer molding or compression molding.

[0141] Figure 2 is a cross-sectional view showing the structure of the semiconductor device 100 according to the present embodiment, and Figure 1 Different examples. Figure 2 In the semiconductor device 100 shown in FIG. 1 , a lead frame is used as the substrate 30. In this case, the semiconductor element 20 is mounted on a die pad 32 on the substrate 30, for example, and is electrically connected to an external lead 34 via a wire 40. In addition, the sealing material 50 is connected to the substrate 30. Figure 1 The example shown is also composed of a cured product of the sealing resin composition of the present embodiment.

[0142] As mentioned above, although embodiment of this invention was demonstrated referring drawings, these are illustrations of this invention, and various structures other than the above-mentioned can also be adopted.

[0143] Example

[0144] (1) Raw materials

[0145] (A) Epoxy resin

[0146] · Epoxy resin 1: o-cresol novolac type epoxy resin "CNE-195LL" manufactured by Changchun Synthetic Resin Co., Ltd.

[0147] Epoxy resin 2: Phenol aralkyl type epoxy resin "NC-3000" manufactured by Nippon Kayaku Co., Ltd.

[0148] Epoxy resin 3: Biphenyl type epoxy resin "YX4000K" manufactured by Mitsubishi Chemical Corporation

[0149] (B) Phenolic curing agent

[0150] Phenol curing agent 1: Phenol aralkyl type phenol resin containing biphenylene skeleton "MEH-7851SS" manufactured by UBE Co., Ltd.

[0151] (C) Inorganic filling materials

[0152] Inorganic filler 1: Spherical silica "FB-940" manufactured by Denka, particle size 15 μm

[0153] Inorganic filler 2: Spherical silica "SO-C5" Admatechs, particle size 1.5μm

[0154] Inorganic filler 3: Spherical silica "SO-C2" Admatechs, particle size 0.5μm

[0155] (D) Butadiene-acrylonitrile copolymer

[0156] ·Butadiene-acrylonitrile copolymer 1: a compound represented by the following formula (d1). Viscosity 39 Pa·s (40° C.)

[0157]

[0158] ·Butadiene-acrylonitrile copolymer 2: a compound represented by the following formula (d2). Viscosity 10 Pa·s (40° C.)

[0159]

[0160] ·Butadiene-acrylonitrile copolymer 3: a compound represented by the following formula (d3). Viscosity 39 Pa·s (40° C.)

[0161]

[0162] (E) Curing accelerator

[0163] Curing accelerator 1: 4-hydroxy-2-(triphenylphosphonium)phenolate

[0164] Curing accelerator 2: 2,3-dihydroxynaphthalene

[0165] (F) Silicone oil

[0166] Silicone oil 1: dimethylsiloxane-alkyl carboxylic acid-4,4'-(1-methylethylidene) bisphenol glycidyl ether copolymer (M69B manufactured by Sumitomo Bakelite Co., Ltd.)

[0167] (other)

[0168] · Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane

[0169] · Coupling agent 2: 3-mercaptopropyltrimethoxysilane

[0170] Release agent 1: Carnauba wax "TOWAX-132" manufactured by Toa Chemical Co., Ltd.

[0171] · Ion scavenger 1: “DHT-4H” manufactured by Kyowa Chemical Industry Co., Ltd.

[0172] Colorant 1: Carbon black, manufactured by Tokai Carbon Co., Ltd.

[0173] (2) Preparation of Sealing Resin Composition

[0174] The above raw materials were used to mix the components shown in Table 1 with a stirrer. Then, the obtained mixture was roll-kneaded, cooled, and pulverized to obtain a sealing resin composition in the form of a powder or granular material.

[0175] (3) Evaluation and measurement of sealing resin composition

[0176] <Condition i>

[0177] Using a transfer molding machine ("KTS-15" manufactured by Uetaki Seiki Co., Ltd.), the sealing resin composition was injected into a mold equipped with a copper plate with a chrome-plated surface (manufactured by Asuka-corporation Co., Ltd., chrome-plated copper substrate for close fitting evaluation, 0.5 μm chromium plating treatment) at a mold temperature of 175°C, and heated at 175°C for 300 seconds to cure it. The die shear strength (speed 300 μm / sec, temperature 25°C) (N / mm2) between the cured product of the sealing resin composition obtained and the copper plate was measured using a DAGE4000 manufactured by Nordson Advanced Technology KK. 2 ).

[0178] <Continuous Formability>

[0179] Continuous moldability: Using a low-pressure transfer automatic molding machine (manufactured by Dai-ichi Seiko, GP-ELF), under the conditions of mold temperature 175°C, injection pressure 9.6 MPa, and curing time 90 seconds, the sealing resin composition is used to seal and mold silicon chips, etc., and the 80-pin QFP (Cu lead frame, package external dimensions: 14mm×20mm×2mm thick, pad size: 6.5mm×6.5mm, chip size 6.0mm×6.0mm×0.35mm thick) is continuously molded up to 150 times.

[0180] As for the judgment criteria, the case where continuous molding without problems such as non-filling was possible until 150 pushes was marked as ◎, the case where continuous molding without problems such as non-filling was possible until 100 pushes was marked as ○, and the case where non-filling occurred until 50 pushes was marked as ×.

[0181] <Flexural modulus, flexural strength>

[0182] The sealing resin composition was injection molded using a low-pressure transfer molding machine (KTS-30, manufactured by Uetaki Seiki Co., Ltd.) at a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 120 seconds to obtain a molded product having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. The molded product was then further heated at 175°C for 4 hours and post-cured to produce a test piece.

[0183] Using this test piece, the flexural modulus and flexural strength were measured at an atmospheric temperature of 260°C in accordance with JIS K 6911.

[0184] [Table 1]

[0185]

[0186] This application claims priority based on Japanese patent application No. 2023-175775 filed on October 11, 2023, and all the contents disclosed in it are incorporated into this specification.

Claims

1. A sealing resin composition, characterized in that Include: (A) Epoxy resin; (B) phenolic curing agent; (C) inorganic filler materials; and (D) butadiene-acrylonitrile copolymer, The sealing resin composition is constituted to satisfy the following condition i: Condition i: Using a transfer molding machine, the sealing resin composition is injected into a mold with a copper plate whose surface is chrome-plated at a mold temperature of 175°C, and heated at 175°C for 300 seconds to cure it. The die shear strength of the cured product of the sealing resin composition and the chrome-plated surface of the copper plate measured at a speed of 300 μm / sec and a temperature of 25°C is 7.0 N / mm 2 the following.

2. The sealing resin composition according to claim 1, wherein: The content of the (D) butadiene-acrylonitrile copolymer is 0.01 to 2% by mass based on the total amount of the sealing resin composition.

3. The sealing resin composition according to claim 1 or 2, characterized in that: (D) The butadiene-acrylonitrile copolymer is represented by the following formula (1), In formula (1), x and y are both positive numbers less than 1, and satisfy x+y=1.

4. The sealing resin composition according to claim 3, wherein: In the formula (1), y is 0.05 or more and 0.24 or less.

5. The sealing resin composition according to claim 1 or 2, wherein: The (A) epoxy resin comprises one or more selected from crystalline epoxy resins, novolac epoxy resins, multifunctional epoxy resins, phenol aralkyl epoxy resins, naphthol epoxy resins, triazine core-containing epoxy resins and bridged cyclic hydrocarbon compound-modified phenolic epoxy resins.

6. The sealing resin composition according to claim 1 or 2, wherein: (B) The phenolic curing agent contains one or more selected from the group consisting of novolac-type phenolic resins, multifunctional phenolic resins, modified phenolic resins, aralkyl-type phenolic resins and bisphenol compounds.

7. The sealing resin composition according to claim 1 or 2, wherein: It further contains (E) a curing accelerator.

8. The sealing resin composition according to claim 1 or 2, wherein: Also includes (F) silicone oil.

9. The sealing resin composition according to claim 1 or 2, wherein: Used to seal semiconductor components.

10. A semiconductor device, characterized in that: A semiconductor element is sealed with the sealing resin composition according to claim 1 or 2.

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