Thermosetting resin composition and electronic component device

Abstract

To provide a thermosetting resin composition which is excellent in fillability and enabling suppression of the occurrence of poor appearance.SOLUTION: A thermosetting resin composition contains a thermosetting resin, a curing agent and an inorganic filler, wherein a particle diameter of the inorganic filler when accumulation from a small diameter side in volume-based particle size distribution measured by a laser scattering diffraction method particle size distribution measurement device is 90% is 25 μm or less, and a disk flow at 180°C exceeds 110 mm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a thermosetting resin composition and an electronic component device. [Background technology]

[0002] In recent years, in order to reduce the cost, size, thickness, weight, performance, and functionality of electronic device devices, there has been a trend toward finer wiring, multi-layering, and more pins for elements, as well as smaller and thinner packages, resulting in higher density packaging. As a result, electronic device devices that are roughly the same size as elements such as ICs (Integrated Circuits), i.e., CSPs (Chip Size Packages), have come into widespread use. Furthermore, SiPs (System in Packages) that incorporate multiple elements in a single package have been developed.

[0003] As a sealing material for sealing elements of electronic component devices, a thermosetting resin composition containing a thermosetting resin, a curing agent, and an inorganic filler is widely used in terms of productivity, cost, etc. As the density and functionality of elements mounted on electronic component devices become higher, the bump-chip distance in CSPs or the distance between elements in SiPs becomes narrower. Therefore, there is a demand for the use of inorganic fillers with smaller particle sizes. However, the use of inorganic fillers with smaller particle sizes may deteriorate the fluidity and filling properties of the sealing material. In order to develop a resin composition having excellent fluidity and filling property, a method of adjusting the particle size distribution of a filler has been proposed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO 13 / 145608 Summary of the Invention [Problem to be solved by the invention]

[0005] It is expected that gaps in elements and the like will become even narrower in the future, and it is predicted that the method described in Patent Document 1 will make it difficult to obtain a resin composition that exhibits suitable fluidity and filling properties for elements and the like with increasingly narrow gaps. Furthermore, when an inorganic filler with a small particle size is used, aggregates of the inorganic filler are likely to occur in the encapsulating resin layer, and as a result, as the encapsulating resin layer that encapsulates the elements becomes thinner, the encapsulated elements become more easily visible, and the elements are not sufficiently concealed by the encapsulating resin layer, which may lead to defects in the appearance of the electronic component device.

[0006] The present disclosure has been made in consideration of the above-described conventional circumstances, and an object of one aspect of the present disclosure is to provide a thermosetting resin composition that has excellent filling properties and suppresses the occurrence of defective appearance, and an electronic component device using the thermosetting resin composition. [Means for solving the problem]

[0007] Specific means for achieving the above object are as follows. <1> Contains a thermosetting resin, a curing agent, and an inorganic filler; The inorganic filler has a particle size of 25 μm or less when the cumulative amount from the small diameter side in a volume-based particle size distribution measured by a laser scattering diffraction method particle size distribution measuring device is 90%; A thermosetting resin composition having a disk flow of more than 110 mm at 180°C. <2> The content of the inorganic filler is 60% by volume or more of the total solid content of the thermosetting resin composition. <1> The thermosetting resin composition according to claim 1. <3> The thermosetting resin contains an epoxy resin, the curing agent contains a phenol-based curing agent, and further contains a curing accelerator. <1> or <2> The thermosetting resin composition according to claim 1. <4> The thermosetting resin composition further contains a solvent, and the content of the solvent is 0.1% by mass to 2% by mass of the entire thermosetting resin composition. <1> ~ <3> 13. The thermosetting resin composition according to claim 12. <5> <1> ~ <4> 13. An electronic component device comprising an element encapsulated with the thermosetting resin composition according to claim 12. Effect of the Invention

[0008] According to one aspect of the present disclosure, it is possible to provide a thermosetting resin composition that has excellent filling properties and suppresses the occurrence of defective appearance, and an electronic component device using this thermosetting resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to the numerical values ​​and their ranges, and do not limit the present disclosure.

[0010] In the present disclosure, the term "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple types of corresponding substances. When multiple types of substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the particles corresponding to each component may include multiple types of particles. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified. In the present disclosure, the term "solid content" refers to the remaining components remaining after removing volatile components such as solvents from a mixture or a thermosetting resin composition.

[0011] <Thermosetting resin composition> The thermosetting resin composition of the present disclosure contains a thermosetting resin, a curing agent, and an inorganic filler, and the inorganic filler has a particle size (hereinafter sometimes referred to as D90) at which the cumulative percentage from the small diameter side in a volume-based particle size distribution measured by a laser scattering diffraction particle size distribution measuring device is 90% of 25 μm or less, and a disk flow at 180° C. of more than 110 mm. The thermosetting resin composition of the present disclosure has excellent filling properties and suppresses the occurrence of defective appearance. The present inventors have found that the above-mentioned problems can be solved by using an inorganic filler having a D90 of 25 μm or less and a disk flow at 180° C. exceeding 110 mm, and have completed the present invention.

[0012] The thermosetting resin composition of the present disclosure contains a thermosetting resin, a curing agent, and an inorganic filler, and optionally contains other components such as a curing accelerator, a colorant, an ion exchanger, a release agent, a flame retardant, a stress relaxation agent, a coupling agent, and a solvent. Hereinafter, each component contained in the thermosetting resin composition of the present disclosure will be described in detail.

[0013] (thermosetting resin) The thermosetting resin composition of the present disclosure contains a thermosetting resin. The type of thermosetting resin is not particularly limited, and examples thereof include epoxy resin, phenol resin, thiol resin, urea resin, melamine resin, urethane resin, silicone resin, maleimide resin, and unsaturated polyester resin. In the present disclosure, a resin that exhibits both thermoplastic and thermosetting properties, such as an acrylic resin containing an epoxy group, is included in the "thermosetting resin". The thermosetting resin may be solid or liquid at room temperature and normal pressure (e.g., 25°C and atmospheric pressure), and is preferably solid. The thermosetting resin may be used alone or in combination of two or more types.

[0014] The thermosetting resin preferably includes an epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, the novolac type epoxy resins are obtained by epoxidizing a novolac resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst (phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, etc.); the triphenylmethane type epoxy resins are obtained by epoxidizing a triphenylmethane type phenolic resin obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst; and the novolac resins are obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst (triphenylmethane type epoxy resins). diphenylmethane type epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl type epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene type epoxy resins which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing type epoxy resins which are diglycidyl ethers of bisphenol S, etc.; epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester type epoxy resins which are glycidyl esters of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine type epoxy resins in which active hydrogen bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is substituted with a glycidyl group; dicyclopentadiene type epoxy resins which are epoxidized co-condensation resins of dicyclopentadiene and phenolic compounds;Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which are epoxy-modified epoxy resins in which the olefin bonds in the molecule have been epoxidized; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenolic resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenolic resins; and dicyclopentadiene-modified phenolic resins, which are glycidyl ethers of dicyclopentadiene-modified phenolic resins. Examples of the epoxy resin include pentadiene-modified epoxy resins; cyclopentadiene-modified epoxy resins which are glycidyl ethers of cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified epoxy resins which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins; and the like. Further examples of the epoxy resin include epoxidized silicone resins and aminophenol-type epoxy resins which are glycidyl ethers of aminophenol. These epoxy resins may be used alone or in combination of two or more.

[0015] Among the above epoxy resins, from the viewpoint of the balance between heat resistance and fluidity, epoxy resins selected from the group consisting of biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, sulfur atom-containing type epoxy resins, novolac type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, copolymer type epoxy resins and aralkyl type epoxy resins (these are referred to as "specific epoxy resins"). The specific epoxy resins may be used alone or in combination of two or more.

[0016] When the epoxy resin contains a specific epoxy resin, from the viewpoint of exhibiting the performance of the specific epoxy resin, the content thereof is preferably 30% by mass or more, and more preferably 50% by mass or more, of the entire epoxy resin.

[0017] Among the specific epoxy resins, from the viewpoint of fluidity, biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, or sulfur atom-containing type epoxy resins are more preferable, and from the viewpoint of heat resistance, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, or aralkyl type epoxy resins are preferable. Specific examples of preferable epoxy resins are shown below.

[0018] The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferred. Among the epoxy resins represented by the following general formula (II), R 8 In the above, the oxygen atoms are substituted at the 4 and 4' positions, and the 3, 3', 5 and 5' positions are methyl groups. 8 YX-4000H (Mitsubishi Chemical Corporation, product name) where R is a hydrogen atom, 8 4,4'-bis(2,3-epoxypropoxy)biphenyl, where R is a hydrogen atom; 8 When is a hydrogen atom and R 8 The oxygen atom is substituted at the 4 and 4' positions, and the 3, 3', 5, and 5' positions are methyl groups. 8is a hydrogen atom, YL-6121H (product name, Mitsubishi Chemical Corporation) and the like are commercially available.

[0019] [ka]

[0020] In formula (II), R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

[0021] The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferred. Among the epoxy resins represented by the following general formula (III), R 9 In the above, the oxygen atoms are substituted at the 4 and 4' positions, and the 3, 3', 5 and 5' positions are methyl groups. 9 is a hydrogen atom, and R 10 are all hydrogen atoms, and R 9 Three of the 3, 3', 5, and 5' positions are methyl groups, one is a t-butyl group, and the remaining R 9 is a hydrogen atom, and R 10 and mixtures of those in which all of the above are hydrogen atoms.

[0022] [ka]

[0023] In formula (III), R 9 and R 10 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

[0024] The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), R 11 are all hydrogen atoms, and R 12 In the above, the oxygen atoms are substituted at the 4 and 4' positions, and the 3, 3', 5 and 5' positions are methyl groups. 12 YSLV-80XY (product name, Nippon Steel Chemical & Material Co., Ltd.), in which R is a hydrogen atom, is commercially available.

[0025] [ka]

[0026] In formula (IV), R 11 and R 12 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

[0027] The sulfur-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, an epoxy resin represented by the following general formula (V) is included. Among the epoxy resins represented by the following general formula (V), R 13 In the above, when the oxygen atom is substituted at the 4 and 4' positions, the 3 and 3' positions are t-butyl groups, the 6 and 6' positions are methyl groups, and the remaining R 13 YSLV-120TE (product name, Nippon Steel Chemical & Material Co., Ltd.), in which R is a hydrogen atom, is commercially available.

[0028] [ka]

[0029] In formula (V), R 13represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

[0030] The novolac type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac type phenolic resin. For example, a novolac type phenolic resin such as a phenol novolac resin, a cresol novolac resin, or a naphthol novolac resin may be used as the novolac type phenolic resin. Rishi Epoxy resins obtained by epoxidation using a method such as diethyl etherification are preferred, and epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), R 14 are all hydrogen atoms, and R 15 is a methyl group, and i=1; ESCN-190 and ESCN-195 (product names, Sumitomo Chemical Co., Ltd.); 14 N-770 and N-775 (trade names, DIC Corporation) in which all of R 14 are all hydrogen atoms, the part where i = 0 and the part where i = 1, R 15 YDAN-1000-10C (product name, Nippon Steel Chemical & Material Co., Ltd.), a styrene-modified phenol novolac type epoxy resin having a portion where R is -CH(CH3)-Ph; 14 are all hydrogen atoms, i=1, and R 15 is a methyl group and i=2, R 15 Benzyl group-modified cresol novolac epoxy resins, which have one methyl group and one benzyl group, are commercially available.

[0031] [ka]

[0032] In formula (VI), R 14 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 15represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0033] The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferable. Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) where i=0 is available as a commercially available product.

[0034] [ka]

[0035] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0036] The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane type phenolic resin obtained from an aromatic aldehyde compound and a phenolic compound is preferred, and an epoxy resin represented by the following general formula (VIII) is more preferred. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, product name) and EPPN-502H (Nippon Kayaku Co., Ltd., product name), in which i is 0 and k is 0, are commercially available.

[0037] [ka]

[0038] In formula (VIII), R 17 and R 18represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3, and each k independently represents an integer of 0 to 4. n is an average value and represents a number of 0 to 10.

[0039] The copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. For example, an epoxy resin obtained by glycidyl etherification of a novolac type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferred, and an epoxy resin represented by the following general formula (IX) is more preferred. Among the epoxy resins represented by the following general formula (IX), R 21 is a methyl group, i is 1, j is 0, and k is 0, and NC-7300 (trade name, Nippon Kayaku Co., Ltd.) is available as a commercially available product.

[0040] [ka]

[0041] In formula (IX), R 19 ~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, and each k is independently an integer of 0 to 4. Each l and m is an average value and a number of 0 to 10, and (l+m) is a number of 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either one of the following formulas (IX-1) or (IX-2). In formulas (IX-1) and (IX-2), R 19 ~R 21 The definitions of i, j and k are as follows: 19 ~R 21 The definitions of i, j and k are the same as those of i, j and k. n is 1 (when bonding via a methylene group) or 0 (when bonding not via a methylene group).

[0042] [ka]

[0043] The epoxy resin represented by the above general formula (IX) may be a random copolymer containing l structural units and m structural units randomly, an alternating copolymer containing them alternately, a copolymer containing them regularly, a block copolymer containing them in a block form, etc. Any one of these may be used alone, or two or more may be used in combination.

[0044] Another preferred copolymer epoxy resin is Epiclon HP-5000 (trade name, DIC Corporation), a methoxynaphthalene-cresol formaldehyde co-condensation epoxy resin containing the following two structural units in a random, alternating or block order: In the following general formula, n and m are each an average value and a number from 0 to 10, and (n+m) is a number from 0 to 10, preferably n and m are each an average value and a number from 1 to 9, and (n+m) is a number from 2 to 10.

[0045] [ka]

[0046] The aralkyl type epoxy resin is not particularly limited as long as it is an epoxy resin made from a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol, cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof. For example, an epoxy resin obtained by glycidyl etherification of a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol, cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof is preferred, and an epoxy resin represented by the following general formulas (X) and (XI) is more preferred.

[0047] Among the epoxy resins represented by the following general formula (X), i is 0 and R 38 is a hydrogen atom, i is 0, and R 38 is a hydrogen atom and all R 8 CER-3000 (product name, Nippon Kayaku Co., Ltd.), which is a mixture of epoxy resins in which l is a hydrogen atom and epoxy resins in which j is a hydrogen atom at a mass ratio of 80:20, is commercially available. Furthermore, among the epoxy resins represented by the following general formula (XI), ESN-175 (product name, Nippon Steel Chemical & Material Co., Ltd.), in which l is 0, j is 0, and k is 0, is commercially available.

[0048] [ka]

[0049] In formulae (X) and (XI), R 38 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 37 , R 39 ~R 41 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, each k is independently an integer of 0 to 4, and each 1 is independently an integer of 0 to 4. Each n is an average value and is independently a number of 0 to 10.

[0050] R in the above general formulas (II) to (XI) 8 ~R 21 and R 37 ~R 41 With respect to the above, the term "may all be the same or different" means, for example, that 8 to 88 R 8 This means that all of the R may be the same or different. 9 ~R 21 and R 37 ~R 41In addition, the numbers of each element in the formula may all be the same or different. 8 ~R 21 and R 37 ~R 41 may be the same or different. For example, R 9 and R 10 may be the same or different. In addition, the monovalent organic group having 1 to 18 carbon atoms in the general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

[0051] In the above general formulas (II) to (XI), n is an average value, and each is preferably independently in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the thermosetting resin composition during melt molding decreases, and the occurrence of filling defects, deformation of bonding wires (gold wires connecting elements and leads), etc. tends to be suppressed. It is more preferable to set n in the range of 0 to 4.

[0052] Specific examples of preferred epoxy resins that can be used in the thermosetting resin composition have been described above in accordance with the general formulas (II) to (XI). More specific preferred epoxy resins include 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl from the viewpoint of heat resistance, and 4,4'-bis(2,3-epoxypropoxy)-biphenyl from the viewpoints of moldability and heat resistance.

[0053] The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 60 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0054] The epoxy resin may be liquid or solid. When the epoxy resin is solid, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoints of moldability and heat resistance, it is preferably 40°C to 180°C, and from the viewpoint of handling during preparation of the thermosetting resin composition, it is more preferably 50°C to 130°C. In the present disclosure, the softening point refers to a value measured by the ring and ball method of JIS K 7234:1986. In the present disclosure, the melting point refers to a value measured in accordance with the visual observation method of JIS K 0064:1992.

[0055] From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the content of the epoxy resin in the thermosetting resin composition is preferably 0.5% by mass to 60% by mass, and more preferably 2% by mass to 50% by mass.

[0056] (hardening agent) The thermosetting resin composition of the present disclosure contains a curing agent. The type of the curing agent is not particularly limited, and is not particularly limited as long as it is a compound that undergoes a curing reaction with the thermosetting resin used in combination. For example, curing agents used in combination with an epoxy resin include phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, polymercaptan-based curing agents, polyaminoamide-based curing agents, isocyanate-based curing agents, and blocked isocyanate-based curing agents. The curing agent may be used alone or in combination of two or more types. The curing agent may be solid or liquid at room temperature and normal pressure (for example, 25°C, atmospheric pressure), and is preferably solid. When the thermosetting resin is an epoxy resin, the curing agent is preferably a phenol-based curing agent or an amine-based curing agent from the viewpoint of heat resistance. Examples of the phenol-based curing agent include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specific examples of the phenol-based curing agent include polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; novolac-type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde, under an acid catalyst; and phenolic compounds synthesized from the above-mentioned phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, and the like. Examples of the phenolic curing agent include aralkyl-type phenolic resins such as aryl aralkyl resins and naphthol aralkyl resins; paraxylylene-modified phenolic resins; metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above-mentioned phenolic compounds and dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acid catalyst; and phenolic resins obtained by copolymerizing two or more of these. These phenolic curing agents may be used alone or in combination of two or more.

[0057] Among the phenol-based curing agents, from the viewpoint of heat resistance, at least one selected from the group consisting of aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, triphenylmethane-type phenolic resins, copolymerized phenolic resins of triphenylmethane-type phenolic resins and aralkyl-type phenolic resins, and novolac-type phenolic resins (these are referred to as "specific phenol-based curing agents"). The specific phenol-based curing agents may be used alone or in combination of two or more.

[0058] When the phenol-based curing agent contains a specific phenol-based curing agent, from the viewpoint of fully exerting the performance thereof, the content of the specific phenol-based curing agent is preferably 30 mass% or more, and more preferably 50 mass% or more, of the entire phenol-based curing agent.

[0059] Examples of the aralkyl type phenolic resin include phenol aralkyl resins and naphthol aralkyl resins synthesized from a phenolic compound and dimethoxy-para-xylene, bis(methoxymethyl)biphenyl, etc. The aralkyl type phenolic resin may be further copolymerized with other phenolic resins. Examples of the copolymerized aralkyl type phenolic resin include a copolymerized phenolic resin of a triphenylmethane type phenolic resin and an aralkyl type phenolic resin, a copolymerized phenolic resin of a salicylaldehyde type phenolic resin and an aralkyl type phenolic resin, and a copolymerized phenolic resin of a novolac type phenolic resin and an aralkyl type phenolic resin.

[0060] The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds and naphthol compounds, and dimethoxy-para-xylene, bis(methoxymethyl)biphenyl or a derivative thereof. For example, phenolic resins represented by the following general formulas (XII) to (XIV) are preferred.

[0061] [ka]

[0062] In formulas (XII) to (XIV), R 23 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 22 , R 24 , R 25 and R 28 R represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 26 and R 27 represents a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, each k is independently an integer of 0 to 4, and each p is independently an integer of 0 to 4. Each n is an average value and is independently a number of 0 to 10.

[0063] Among the phenolic resins represented by the above general formula (XII), i is 0 and R 23 MEH-7851 (product name, Meiwa Kasei Co., Ltd.), in which all are hydrogen atoms, is commercially available.

[0064] Among the phenolic resins represented by the above general formula (XIII), XL-225, XLC (Mitsui Chemicals, Inc., product name), MEH-7800 (Meiwa Chemical Industry Co., Ltd., product name), etc., in which i is 0 and k is 0, are commercially available.

[0065] Among the phenolic resins represented by the above general formula (XIV), SN-170 (trade name, Nippon Steel Chemical & Material Co., Ltd.), in which j is 0, k is 0, and p is 0, and R 27 is a hydroxyl group and p is 0, and SN-395 (product name, Nippon Steel Chemical & Material Co., Ltd.) is available as a commercially available product.

[0066] The dicyclopentadiene type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from a compound having a dicyclopentadiene skeleton. For example, a phenolic resin represented by the following general formula (XV) is preferable. Among the phenolic resins represented by the following general formula (XV), a phenolic resin in which i is 0 is commercially available.

[0067] [ka]

[0068] In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0069] The triphenylmethane type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from an aromatic aldehyde compound as a raw material. For example, a phenolic resin represented by the following general formula (XVI) is preferable.

[0070] Among the phenol resins represented by the following general formula (XVI), MEH-7500 (product name, Meiwa Kasei Co., Ltd.), in which i is 0 and k is 0, is commercially available.

[0071] [ka]

[0072] In formula (XVI), R 30 and R 31 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, and each k is independently an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0073] The copolymerized phenolic resin of triphenylmethane type phenolic resin and aralkyl type phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of aralkyl type phenolic resin and phenolic resin obtained from a compound having a benzaldehyde skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XVII) is preferable.

[0074] Among the phenolic resins represented by the following general formula (XVII), HE-510 (trade name, Air Water Chemical Co., Ltd.), in which i is 0, k is 0, and q is 0, is commercially available.

[0075] [ka]

[0076] In formula (XVII), R 32 ~R 34 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, each k is independently an integer of 0 to 4, and each q is independently an integer of 0 to 5. Each l and m is an average value and independently a number of 0 to 11, provided that the sum of l and m is a number of 1 to 11.

[0077] The novolac type phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds with an aldehyde compound under an acid catalyst. For example, a phenolic resin represented by the following general formula (XVIII) is preferred.

[0078] Among the phenolic resins represented by the following general formula (XVIII), i is 0 and R 35 are commercially available products such as Tamanor 758 and 759 (trade names, Arakawa Chemical Industries, Ltd.) and H-4 (trade name, Meiwa Chemical Industry Co., Ltd.).

[0079] [ka]

[0080] In formula (XVIII), R 35 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 36 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0081] R in the above general formulas (XII) to (XVIII) 22 ~R 36 The description of "may be the same or different" means, for example, that i R 22 This means that all of the R's may be the same or different from each other. 23 ~R 36 In addition, the numbers of each element in the formula may all be the same or different from each other. 22 ~R 36 may be the same or different. For example, R 22 and R 23 may be the same or different, and R 30 and R 31 may be the same or different.

[0082] In the above general formulas (XII) to (XVIII), n is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the thermosetting resin composition during melt molding also becomes low, making it difficult for filling defects, deformation of bonding wires (gold wires connecting elements and leads), etc. to occur. The average n in one molecule is preferably set in the range of 0 to 4.

[0083] Specific examples of the amine-based curing agent include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane, aromatic amine compounds such as diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, and 2-methylaniline, imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole, imidazoline compounds such as imidazoline, 2-methylimidazoline, and 2-ethylimidazoline, etc. Among these, aromatic amine compounds are preferred from the viewpoint of storage stability, and diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and dimethylthiotoluenediamine are more preferred.

[0084] The functional group equivalent of the curing agent (hydroxyl group equivalent in the case of a phenolic curing agent, active hydrogen equivalent in the case of an amine curing agent) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance, and electrical reliability, it is preferably 10 g / eq to 1000 g / eq, and more preferably 30 g / eq to 500 g / eq. The hydroxyl equivalent in the case of a phenolic curing agent is a value calculated based on the hydroxyl value measured in accordance with JIS K0070: 1992. The active hydrogen equivalent in the case of an amine curing agent is a value calculated based on the amine value measured in accordance with JIS K7237: 1995.

[0085] When the curing agent is solid, the softening point or melting point is not particularly limited, but is preferably 40° C. to 180° C. from the viewpoints of moldability and heat resistance, and more preferably 50° C. to 130° C. from the viewpoint of handleability during production of the thermosetting resin composition.

[0086] When the thermosetting resin is an epoxy resin, the equivalent ratio of the epoxy resin to the curing agent (molar number of epoxy groups in the resin / molar number of active hydrogens in the curing agent) is not particularly limited, but from the viewpoint of keeping the unreacted amounts of each to a minimum, it is, for example, preferably 0.7 to 1.6, more preferably 0.8 to 1.4, and even more preferably 0.9 to 1.2.

[0087] (Inorganic filler) The thermosetting resin composition of the present disclosure contains an inorganic filler. The inorganic filler has a D90 of 25 μm or less, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. The D90 may be 3 μm or more. D90 for an inorganic filler is a value measured by a laser diffraction scattering particle size distribution measuring device, and for example, an inorganic filler is extracted from a thermosetting resin composition or a cured product using an organic solvent, nitric acid, aqua regia, etc., and then thoroughly dispersed using an ultrasonic disperser, etc., to prepare a dispersion. Using this dispersion, the D90 of the inorganic filler can be measured from the volume-based particle size distribution measured by the laser diffraction scattering particle size distribution measuring device. When the inorganic filler is separately available, the D90 of the inorganic filler may be measured by carrying out the above measurement on the obtained inorganic filler.

[0088] The type of inorganic filler is not particularly limited. Specifically, inorganic materials such as silica, such as spherical silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, aluminum nitride, boehmite, beryllia, magnesium oxide, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, mica, and titanates can be mentioned. Inorganic fillers having a flame retardant effect may be used. Examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate. Among them, spherical silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. The inorganic fillers may be used alone or in combination of two or more types. Examples of the state of the inorganic filler include powder, beads obtained by sphering powder, and fibers.

[0089] The average particle size of the inorganic filler is not particularly limited. For example, the volume average particle size is preferably 15 μm or less, more preferably 0.1 μm to 15 μm, even more preferably 0.2 μm to 12 μm, and particularly preferably 0.5 μm to 10 μm. When the volume average particle size is 15 μm, the filling ability into narrow gaps tends to be improved. Also, when the volume average particle size is 0.1 μm or more, the increase in viscosity of the thermosetting resin composition tends to be further suppressed. The volume average particle diameter of the inorganic filler can be measured as the volume average particle diameter (D50) by a laser diffraction scattering particle size distribution measuring device.

[0090] From the viewpoint of flowability of the thermosetting resin composition, the particle shape of the inorganic filler is preferably spherical rather than angular, and the particle size distribution of the inorganic filler is preferably distributed over a wide range.

[0091] The content of the inorganic filler in the thermosetting resin composition is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 60% by volume or more of the total solid content of the thermosetting resin composition, more preferably 60% by volume to 90% by volume, and even more preferably 65% ​​by volume to 88% by volume. When the content of the inorganic filler is 60% by volume or more of the total solid content of the thermosetting resin composition, the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the total solid content of the thermosetting resin composition, the increase in viscosity of the thermosetting resin composition is suppressed, and the fluidity is further improved, tending to improve the moldability.

[0092] (Cure accelerator) In the thermosetting resin composition of the present disclosure, when the thermosetting resin includes an epoxy resin and the curing agent includes a phenol-based curing agent, the thermosetting resin composition of the present disclosure may include a curing accelerator. The type of curing accelerator is not particularly limited and can be selected depending on the type of thermosetting resin, the desired properties of the thermosetting resin composition, and the like.

[0093] Specifically, diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole, derivatives of the cyclic amidine compounds, phenol novolak salts of the cyclic amidine compounds or their derivatives, and combinations of these compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, diazof compounds having intramolecular polarization obtained by adding a compound having a π bond, such as phenylmethane; cyclic amidinium compounds such as the tetraphenylborate salt of DBU, the tetraphenylborate salt of DBN, the tetraphenylborate salt of 2-ethyl-4-methylimidazole, and the tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the above tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide;organic phosphines such as primary phosphines, e.g., ethylphosphine, phenylphosphine, etc.; secondary phosphines, e.g., dimethylphosphine, diphenylphosphine, etc.; and tertiary phosphines, e.g., triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris(benzyl)phosphine; phosphine compounds, e.g., complexes of the organic phosphines and organic borons; and complexes of the organic phosphines or the phosphine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, compounds having intramolecular polarization obtained by adding a compound having a π bond, such as quinone compounds, such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and anthraquinone, and diazophenylmethane; compounds having intramolecular polarization obtained by adding a compound having a π bond, such as the organic phosphines or the phosphine compounds, and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, and 4-iodophenol; a compound having intramolecular polarization, which is obtained by reacting a halogenated phenol compound such as phenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation process;Examples of the tetra-substituted phosphonium include tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborate salts of tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetra-substituted phosphonium with phenolic compounds; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds. For example, examples of a curing accelerator that is particularly suitable when an epoxy resin is used as the thermosetting resin include triphenylphosphine and an adduct of triphenylphosphine and a quinone compound. Furthermore, for example, when an epoxy resin is used as the thermosetting resin, examples of curing accelerators that enable low-temperature curing include an adduct of tributylphosphine and 1,4-benzoquinone, dimethylaminopyridine, 2-ethyl-4-methylimidazole, 2-methylimidazole, and 1-benzyl-2-methylimidazole. The curing accelerators may be used alone or in combination of two or more.

[0094] When the thermosetting resin composition contains a curing accelerator, the content thereof is preferably 0.1 mass % to 8 mass %, more preferably 0.3 mass % to 6 mass %, and further preferably 0.5 mass % to 5 mass %, based on the total amount of the thermosetting resin and the curing agent.

[0095] (Coloring agent) The thermosetting resin composition of the present disclosure may contain a colorant. Examples of colorants include known colorants such as carbon black, black titanium oxide, organic dyes, organic pigments, red lead, and red iron oxide. The content of the colorant can be appropriately selected depending on the purpose, etc. The colorants may be used alone or in combination of two or more.

[0096] When the thermosetting resin composition contains a colorant, the content thereof is preferably from 0.01% by mass to 5% by mass, and more preferably from 0.05% by mass to 3% by mass.

[0097] (Ion exchanger) The thermosetting resin composition of the present disclosure may contain an ion exchanger. In particular, from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of semiconductor devices, it is preferable to contain an ion exchanger. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specifically, for example, hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth can be mentioned. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

[0098] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0 < X ≤ 0.5, m is a positive number)

[0099] When the thermosetting resin composition contains an ion exchanger, its content is not particularly limited as long as it is sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the thermosetting resin.

[0100] (Release agent) The thermosetting resin composition of the present disclosure may contain a release agent from the viewpoint of obtaining good mold release properties with the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, carnauba wax, higher fatty acids such as montanic acid and stearic acid, metal salts of higher fatty acids, ester waxes such as montanic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. can be mentioned. The release agent may be used alone or in combination of two or more.

[0101] When the thermosetting resin composition contains a release agent, the content is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the thermosetting resin. When the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the thermosetting resin, sufficient releasability tends to be obtained. When the amount of the release agent is 15 parts by mass or less relative to 100 parts by mass of the thermosetting resin, better adhesion tends to be obtained.

[0102] (Flame retardant) The thermosetting resin composition of the present disclosure may contain a flame retardant. The flame retardant is not particularly limited, and a conventionally known one may be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. The flame retardant may be used alone or in combination of two or more kinds.

[0103] When the thermosetting resin composition contains a flame retardant, the content is not particularly limited as long as it is a sufficient amount to obtain the desired flame retardant effect. For example, the content is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the thermosetting resin.

[0104] (Stress reliever) The thermosetting resin composition of the present disclosure may contain a stress relaxation agent such as silicone oil or silicone rubber particles. By containing a stress relaxation agent in the thermosetting resin composition, the warpage deformation of the package and the occurrence of package cracks can be further reduced. Examples of the stress relaxation agent include known stress relaxation agents (flexible agents) that are generally used. Specifically, examples of the stress relaxation agent include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder, and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. The stress relaxation agent may be used alone or in combination of two or more types. Among them, silicone-based stress relaxation agents are preferred. Examples of the silicone-based stress relaxation agent include those having an epoxy group, those having an amino group, and those modified with polyether.

[0105] When the thermosetting resin composition contains a stress relaxation agent, the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the thermosetting resin.

[0106] (Coupling Agent) The thermosetting resin composition of the present disclosure may contain a coupling agent. The type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of the coupling agent include silane coupling agents and titanium coupling agents. The coupling agents may be used alone or in combination of two or more types.

[0107] Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane.

[0108] Examples of titanium coupling agents include 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(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0109] When the thermosetting resin composition contains a coupling agent, the content of the coupling agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the inorganic filler, from the viewpoint of adhesion at the interface between the thermosetting resin and the inorganic filler.

[0110] (solvent) The thermosetting resin composition of the present disclosure may contain a solvent. The solvent contained in the thermosetting resin composition may or may not dissolve either the thermosetting resin or the curing agent. When the thermosetting resin composition contains a solvent, the dispersibility of the inorganic filler is further improved, and appearance defects (particularly, the phenomenon in which the encapsulated element is visible through the composition (chip show-through)) tend to be further suppressed.

[0111] The boiling point of the solvent at normal pressure is preferably 50°C to 180°C, more preferably 60°C to 170°C, even more preferably 70°C to 160°C, particularly preferably 70°C to 140°C, and extremely preferably 70°C to 120°C. The solvent may be used alone or in combination of two or more kinds. When two or more kinds of solvents are used in combination, it is preferable that the boiling point at normal pressure of the solvent having the highest boiling point is within the above-mentioned range.

[0112] Specific examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, etc. Among these, methyl isobutyl ketone or methyl ethyl ketone is preferred.

[0113] When the thermosetting resin composition contains a solvent, the content of the solvent in the entire thermosetting resin composition is preferably 0.1% by mass to 2% by mass, and more preferably 0.1% by mass to 0.5% by mass. When the content of the solvent in the entire thermosetting resin composition is 2% by mass or less, blocking of the thermosetting resin composition is unlikely to occur, and the thermosetting resin composition tends to be easily supplied to a molding machine such as a press. When the content of the solvent in the entire thermosetting resin composition is 0.1% by mass or more, the flowability during molding tends to be further improved. The content of the solvent is calculated based on the change in mass before and after heating the thermosetting resin composition at 175° C. for one hour.

[0114] (Physical Properties of Thermosetting Resin Composition) The viscosity of the thermosetting resin composition is not particularly limited. It is preferable to adjust the viscosity to a desired value depending on the molding method, the composition of the thermosetting resin composition, etc. When the thermosetting resin composition is used for sealing material applications, it is preferable to adjust the viscosity of the thermosetting resin composition depending on the tendency of wire sweep during molding. For example, when the thermosetting resin composition is used as an encapsulant, from the viewpoint of reducing wire sweep, etc., the viscosity of the thermosetting resin composition is preferably 200 Pa·s or less at 175° C., more preferably 150 Pa·s or less, even more preferably 100 Pa·s or less, particularly preferably 70 Pa·s or less, and extremely preferably 50 Pa·s or less. The lower limit of the viscosity of the thermosetting resin composition is not particularly limited, and may be, for example, 2 Pa·s or more at 175° C. The viscosity of the thermosetting resin composition can be measured by a Koka type flow tester (for example, manufactured by Shimadzu Corporation).

[0115] From the viewpoint of reducing wire sweep, the disc flow of the thermosetting resin composition at 180° C. is preferably 115 mm or more, and more preferably 120 mm or more. The disc flow of the thermosetting resin composition at 180° C. may be 200 mm or less. The disc flow was measured by using a flat plate mold for measuring disc flow, which had an upper mold of 200 mm (W) × 200 mm (D) × 25 mm (H) and a lower mold of 200 mm (W) × 200 mm (D) × 15 mm (H). 5 g of the thermosetting resin composition was weighed out on a balance and placed in the center of the lower mold heated to 180°C. After 5 seconds, the upper mold heated to 180°C was closed and compression molded under conditions of a load of 78 N and a curing time of 90 seconds. The long diameter (mm) and short diameter (mm) of the molded product were measured with a vernier caliper, and the average value (mm) was obtained to determine the disc flow.

[0116] (Method for producing thermosetting resin composition) The thermosetting resin composition of the present disclosure may be produced through any process. A typical method for producing a thermosetting resin composition includes thoroughly mixing predetermined amounts of components with a mixer or the like to form a mixture, then melt-kneading the mixture with a mixing roll, an extruder, etc., cooling, and pulverizing. More specifically, for example, a method includes homogeneously stirring and mixing predetermined amounts of the above-mentioned components, kneading the mixture in a kneading device described below that has been heated to 70°C to 140°C in advance, cooling, and pulverizing. A solvent may be added to the mixture. The content of the solvent in the mixture may be the same as or different from the content of the solvent in the thermosetting resin composition obtained through kneading.

[0117] The thermosetting resin composition of the present disclosure may be produced by kneading a mixture of a thermosetting resin, a curing agent, and a slurry containing an inorganic filler and a solvent while removing the solvent. By kneading the mixture while removing the solvent, the disc flow of the thermosetting resin composition of the present disclosure at 180° C. tends to exceed 110 mm. When the thermosetting resin composition is produced using a slurry containing an inorganic filler and a solvent, the above-mentioned solvent may be derived from the solvent contained in the slurry. In the case where the mixture is kneaded while removing the solvent to produce the thermosetting resin composition, the mixture may contain other components, such as a curing accelerator, a stress relaxation agent, and an ion exchanger, which are contained in the thermosetting resin composition as necessary. The mixture is obtained by mixing a slurry containing a thermosetting resin, a curing agent, an inorganic filler, and a solvent, and other components such as a curing accelerator, a stress relaxation agent, an ion exchanger, etc., which are used as necessary, using a mixer such as a stirrer or a planetary mixer, an ultrasonic disperser, a wet disperser such as a jet mill, etc. The mixing conditions when preparing the mixture are appropriately set depending on the types of components contained in the mixture, the ratio of the components, etc.

[0118] From the viewpoint of liquid transportability during kneading, the solid content ratio of the mixture is preferably 35% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and even more preferably 65% ​​by mass to 85% by mass.

[0119] In the case of producing a thermosetting resin composition by kneading the mixture while removing the solvent, the kneading device for kneading the mixture is not particularly limited. Examples of the kneading device include screw-type kneaders such as a single-screw kneader, a twin-screw kneader, and a multi-screw kneader having three or more screws, and roll mills such as a two-roll mill and a three-roll mill. The stirring blade of the screw mixer may be supported at the base and the tip, or only at the base. From the viewpoint of improving mixing performance and productivity, it is preferable that the stirring blade is supported only at the base. Among these, a screw type kneader, which is an example of a closed system kneading device that allows removal of the solvent by reducing pressure, is preferred, and a twin-screw kneader is more preferred from the viewpoint of easy control of shear force. In addition, when the thermosetting resin composition contains a curing accelerator, the curing accelerator may be added to a first kneaded product obtained by kneading a mixture not containing the curing accelerator at a first kneading temperature, and the first kneaded product to which the curing accelerator has been added may be further kneaded at a second kneading temperature that is lower than the first kneading temperature, thereby producing the thermosetting resin composition.

[0120] The kneading temperature of the mixture is not particularly limited, and is preferably a temperature near the melting point or softening point of the thermosetting resin from the viewpoint of suppressing uneven distribution of the thermosetting resin. When two or more types of thermosetting resins are used in combination, the kneading temperature of the mixture is preferably a temperature near the melting point or softening point of the thermosetting resin having the highest melting point or softening point. The kneading temperature of the mixture is preferably in the range of 10° C. lower to 70° C. higher than the melting or softening point of the thermosetting resin (when multiple types of thermosetting resins are used in combination, the thermosetting resin with the highest melting or softening point), more preferably in the range of 8° C. lower to 60° C. higher, and even more preferably in the range of 6° C. lower to 30° C. higher. By kneading at such a temperature, the thermosetting resin can be melted and fluidity can be maintained, thereby allowing good stirring and mixing. In one embodiment, the kneading temperature of the mixture is preferably 30°C to 150°C, more preferably 50°C to 140°C, and even more preferably 60°C to 130°C. In the present disclosure, the "kneading temperature of the mixture" refers to the temperature of the heating section of the kneading device when the mixture is kneaded by the kneading device.

[0121] The method for removing at least a part of the solvent contained in the mixture when the mixture is kneaded is not particularly limited. When a screw type kneader is used as the kneading device, it is preferable to remove the solvent by reducing the pressure inside the screw type kneader. When a screw type kneader is used as the kneading device, from the viewpoint of distilling off the solvent, the pressure inside the screw type kneader is preferably 0.001 MPa to 0.08 MPa, more preferably 0.003 MPa to 0.06 MPa, and even more preferably 0.005 MPa to 0.05 MPa.

[0122] The thermosetting resin composition obtained through kneading may be cooled and pulverized to obtain a powdered thermosetting resin composition. The thermosetting resin composition obtained through kneading may be molded into a grain, tablet, pellet, or granule (cylindrical granules, etc.). The method of pulverizing or molding the thermosetting resin composition is not particularly limited, and a conventionally known method may be used.

[0123] (Uses of thermosetting resin composition) The use of the thermosetting resin composition of the present disclosure is not particularly limited, and can be used in various mounting techniques, for example, as a sealant for electronic component devices. The thermosetting resin composition of the present disclosure can also be used in various applications in which it is desirable for the resin composition to have good fluidity and curability, such as resin molded bodies for various modules, resin molded bodies for motors, resin molded bodies mounted on vehicles, and sealants for electronic circuit protection materials.

[0124] <Electronic component equipment> The electronic component device of the present disclosure includes an element encapsulated with the thermosetting resin composition of the present disclosure.

[0125] Examples of electronic component devices include devices obtained by mounting elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) on a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, and then sealing the resulting element portion with a thermosetting resin composition. More specifically, typical resin-sealed ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) have a structure in which an element is fixed on a lead frame, terminal parts of the element such as bonding pads and lead parts are connected by wire bonding, bumps, or the like, and then sealed by transfer molding or the like using a thermosetting resin composition; TCP (Tape Carrier Package) has a structure in which an element connected to a tape carrier by bumps is sealed with a thermosetting resin composition; and COB (Chip On Board) has a structure in which an element connected to wiring formed on a support member by wire bonding, flip chip bonding, solder, or the like, is sealed with a thermosetting resin composition. Examples of suitable printed wiring boards include a BGA (Ball Grid Array), CSP, MCP (Multi Chip Package), and SiP, which have a structure in which an element is mounted on the surface of a support member having terminals for connecting a wiring board formed on the back side thereof, the element is connected to wiring formed on the support member by bump or wire bonding, and the element is then sealed with a thermosetting resin composition.The thermosetting resin composition can also be suitably used in printed wiring boards.

[0126] Methods for encapsulating electronic device components using a thermosetting resin composition include low pressure transfer molding, injection molding, compression molding, and the like. EXAMPLES

[0127] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples.

[0128] <Preparation of Thermosetting Resin Composition> The following components were prepared.

[0129] (thermosetting resin) Epoxy resin 1: Diphenylmethane type epoxy resin (bisphenol type epoxy resin) (product name: YSLV-80XY, Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 190g / eq) Epoxy resin 2: Biphenylene aralkyl type epoxy resin, epoxy equivalent 277g / eq, Nippon Kayaku Co., Ltd., product name "NC-3000") Hardener: Biphenyl skeleton type phenol aralkyl resin with hydroxyl equivalent of 199g / eq and softening point of 89℃ (Meiwa Kasei Co., Ltd., product name "MEH-7851") -Cure accelerator: Phosphorus-based cure accelerator Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane Release agent: Carnauba wax (Cerarica NODA Co., Ltd.) Colorant: Carbon black, product name "MA-100", Mitsubishi Chemical Corporation Ion exchanger: Hydrotalcite (product name "DHT-4A", Kyowa Chemical Industry Co., Ltd.) Solvent 1: Methyl ethyl ketone Solvent 2: Methyl isobutyl ketone Inorganic filler 1: Silica particles with a D90 of 20 μm and a volume average particle size of 11 μm Inorganic filler 2: Silica particles with a D90 of 4 μm and a volume average particle size of 2 μm Inorganic filler 3: Silica particles with a D90 of 31 μm and a volume average particle size of 20 μm

[0130] The components shown in Table 1 were mixed in a container and stirred with a stirrer for 1 hour. Then, using a twin-screw kneader (twin-screw extruder), the mixture was melt-kneaded at 100°C under a reduced pressure of 0.02 MPa. The molten material was then cooled with a press roll through which cold water at 10°C was circulated, and the resulting sheet was pulverized to prepare a powdered thermosetting resin composition. In Table 1, the numerical values of each component represent parts by mass. In Table 1, "filler amount" means the volume-based content rate of the inorganic filler contained in the thermosetting resin composition. Note that in Table 1, "-" indicates that the corresponding component was not used. Also, the "solvent content rate" in Table 1 represents the solvent content rate of the mixture before kneading by a twin-screw kneader.

[0131] <Measurement of D90> The prepared thermosetting resin composition was dissolved in acetone to extract the inorganic filler. The D90 of the extracted inorganic filler was measured using a laser diffraction scattering method particle size distribution measuring device (manufactured by Horiba, Ltd., LA-920). The obtained results are shown in Table 1.

[0132] <Residual solvent rate after kneading> 5 g of the thermosetting resin composition was treated at 175 °C for 1 hour using an explosion-proof dryer, and the residual solvent rate after kneading was calculated from the following formula and evaluated according to the following criteria from the viewpoint of void generation after molding. The results are shown in Table 1. Note that "-" indicates that the evaluation was not performed for the corresponding comparative example. Residual solvent rate after kneading (mass %) = ((mass before heat treatment - mass after heat treatment) / mass before heat treatment) × 100 A; Residual solvent rate is 0.5 mass % or less B; Residual solvent rate exceeds 0.5 mass % and is 2 mass % or less C; Residual solvent rate exceeds 2 mass %

[0133] <Flowability> (Evaluation of spiral flow (SF)) Using a mold for measuring spiral flow according to EMMI-1-66, the thermosetting resin composition was molded by a transfer molding machine under the conditions of a mold temperature of 180 °C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain the flow distance (inch). The results are shown in Table 1. (Evaluation of disk flow (DF)) Using a flat plate mold for measuring disc flow having an upper mold of 200mm (W) x 200mm (D) x 25mm (H) and a lower mold of 200mm (W) x 200mm (D) x 15mm (H), 5g of the thermosetting resin composition weighed with a balance was placed on the center of the lower mold heated to 180 ° C., and after 5 seconds, the upper mold heated to 180 ° C. was closed and compression molded under conditions of a load of 78N and a curing time of 120 seconds, and the major axis (mm) and minor axis (mm) of the molded product were measured with a caliper, and the average value (mm) was taken as the disc flow. The results are shown in Table 1.

[0134] (Evaluation of hot hardness) The hot hardness of the thermosetting resin composition was evaluated as follows. The thermosetting resin composition was molded into a test piece for measuring hot hardness (a disk having a diameter of 50 mm and a thickness of 3 mm) using a transfer molding machine under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Immediately after molding, the hot hardness (Shore D) of the test piece was measured using a Shore D hardness tester. The results are shown in Table 1.

[0135] (Melt viscosity at 175℃) The thermosetting resin composition was heated to melt, and the melt viscosity (ηFT) at 175° C. was measured using a Koka type flow tester. The results are shown in Table 1.

[0136] (Gel time measurement) The gel time (GT) of the thermosetting resin composition was measured using a Curastometer manufactured by JSR Trading Co., Ltd. Measurement was performed at 180°C using 3 g of the thermosetting resin composition using a Curastometer manufactured by JSR Trading Co., Ltd., and the time until the torque curve rose was taken as the gel time (seconds). The results are shown in Table 1.

[0137] (Measurement of elongation, elastic modulus and bending strength) The cured product of the thermosetting resin composition was cut into a rectangular parallelepiped of 2.0 mm × 5.0 mm × 40 mm to prepare a test piece for evaluating bending strength. Using this test piece, a bending test was performed using a Tensilon universal material testing machine (Instron 5948, Instron Corporation) under the conditions of a support distance of 32 mm and a crosshead speed of 1 mm / min. Using the measured results, a bending stress (σ)-displacement curve was created from equation (1), and the maximum stress was taken as the bending strength. In addition, the elastic modulus was calculated from the slope of the point where the stress and displacement in the bending stress-displacement curve showed linearity. σ(MPa)=(3PL / 2bh 2 ) / 9.8...Equation (1) Similarly, the following equation (2) is defined as elongation (ε). ε(%)=(6h / L)·Ymax·100···Formula (2) P: Bending load (kgf) L: Distance between fulcrums (mm) b: Test piece width (mm) h: test piece thickness (mm) Y: Deflection (mm) Ymax: Deflection at break

[0138] (Evaluation of tip transparency) A compression molding substrate was prepared with chips arranged on one side of the substrate. The substrate used had dimensions of 240 mm wide x 74 mm long x 0.45 mm thick. The silicon chips used were 10 mm wide x 8 mm long x 0.4 mm thick and made of silicon. The compression molding substrate was obtained by arranging a total of 12 chips (3 wide x 4 long) at a distance of 8 mm from each other in the center of one side of the substrate. Next, the thermosetting resin composition to be measured was compression molded by a compression molding device onto the surface of the compression molding substrate on which the chips were arranged. The molding conditions for compression molding were as follows: mold temperature: 175°C, molding pressure: approximately 10 MPa, curing time: 120 seconds, and vacuum retention time: 3 seconds. In addition, the thickness of the cured material of the thermosetting resin composition in the compression molded body obtained by the above compression molding was 0.8 mm in the area where the chip was not placed (i.e., the area where the cured material was provided on the substrate) and 0.08 mm on the chip. The obtained compression molded product was visually observed for the presence or absence of chip show-through and evaluated according to the following criteria. The results are shown in Table 1. A: The chip cannot be seen through visually. B: A slight chip showing through is observed. C: The chip is visible through the glass.

[0139] (Evaluation of under-chip filling) A test piece for evaluating the filling property under the tip was prepared by the same method for preparing a compression molded body as that used for the tip see-through evaluation. In this case, the tip used was changed to one having a tunnel structure with a gap of 0.08 mm. The width of the tunnel was set to 1.0 mm in this case. The evaluation method was based on the filling rate of the tunnel when the volume inside the tunnel structure with a width of 1.0 mm, height of 0.08 mm, and length of 6 mm was set to 100%. The evaluation criteria were as follows. The filling rate was determined by SAT (Scanning Acoustic Tomography). The results are shown in Table 1. A: 100% filling rate B: Filling rate is 95% or more but less than 100% C: Filling rate is 90% or more but less than 95% D: Filling rate is less than 90%

[0140] [Table 1]

[0141] As is clear from the evaluation results in Table 1, the thermosetting resin compositions of the examples have excellent filling properties and suppress the occurrence of chip show-through.

Claims

1. Contains a thermosetting resin, a curing agent, and an inorganic filler; The inorganic filler has a particle size of 25 μm or less when a cumulative amount from the small diameter side in a volume-based particle size distribution measured by a laser scattering diffraction method particle size distribution measuring device is 90%; The volume average particle size of the inorganic filler is 11 μm to 15 μm, The inorganic filler is silica, A thermosetting resin composition having a disk flow at 180°C of more than 110 mm.

2. The thermosetting resin composition according to claim 1 , wherein the content of the inorganic filler is 60% by volume or more of the total solid content of the thermosetting resin composition.

3. 3. The thermosetting resin composition according to claim 1, wherein the thermosetting resin comprises an epoxy resin, the curing agent comprises a phenol-based curing agent, and further comprises a curing accelerator.

4. The thermosetting resin composition according to any one of claims 1 to 3, further comprising a solvent, the content of the solvent being 0.1 mass% to 2 mass% of the total thermosetting resin composition.

5. An electronic component device comprising an element encapsulated with the thermosetting resin composition according to any one of claims 1 to 4.

Images