JP2023034256A - Thermosetting resin composition and semiconductor device - Google Patents

Abstract

To provide a thermosetting resin composition excellent in reflow resistance.SOLUTION: The thermosetting resin composition contains a thermosetting resin, a curing agent, and an inorganic filler. The inorganic filler contains an inorganic filler surface-treated with a coupling agent containing a primary amino group. The content of the inorganic filler surface-treated with the coupling agent containing the primary amino group is 20-60 mass% based on the whole thermosetting resin composition.SELECTED DRAWING: None

Description

The present disclosure relates to thermosetting resin compositions and semiconductor devices.

In recent years, as electronic devices have become smaller, lighter, and have higher performance, mounting densities have been increasing. As a result, the mainstream of electronic component devices is changing from conventional pin insertion type packages to surface mount type packages.

A surface mount type package differs from a conventional pin insertion type package in mounting method. That is, when attaching pins to a wiring board, in the conventional pin-insertion type package, the pins are inserted into the wiring board and then soldered from the back side of the wiring board, so the package is not directly exposed to high temperatures. However, in a surface-mounted package, the entire electronic component device is treated with a solder bath, a reflow device, etc., so the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture rapidly expands during soldering, and the generated vapor pressure acts as peeling stress. Separation from the cured product of the sealing material composed of the curable resin composition may occur, which may cause package cracks, poor electrical characteristics, and the like. Therefore, it is desired to develop a sealing material having excellent adhesiveness to an insert and further excellent solder heat resistance (reflow resistance) and a cured product thereof.

In order to meet the above requirements, the use of a silane coupling agent as a modifier for the inorganic filler contained in the sealing material has been investigated. Specifically, the use of an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent (see, for example, Patent Document 1), the use of a sulfur atom-containing silane coupling agent (see, for example, Patent Document 2), and the like. being considered.

Furthermore, as an epoxy resin composition excellent in reflow resistance, (A) epoxy resin, (B) phenol resin, (C) curing accelerator, (D) phosphazene compound, (E) silica and (F) γ-aminopropyl An epoxy resin composition comprising at least one silane coupling agent selected from the group consisting of triethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidylpropyltriethoxysilane, and γ-glycidylpropyltrimethoxysilane as an essential component. is disclosed (see, for example, Patent Document 3). In Patent Document 3, silica surface-treated with a silane coupling agent is used. The content of surface-treated silica is 85% to 93% by mass in the total epoxy resin composition.

JP-A-11-147939 JP-A-2000-103940 Japanese Patent Application Laid-Open No. 2004-67774

However, even with the encapsulating material composed of the epoxy resin composition described in Patent Documents 1 and 2, the current situation is that reflow resistance cannot be sufficiently satisfied in practice.
On the other hand, in the epoxy resin composition described in Patent Document 3, since the content of surface-treated silica is high, the fluidity of the epoxy resin composition is deteriorated and unfilled portions are likely to occur in some cases. Unfilled portions tend to deteriorate the reflow resistance.
The present disclosure has been made in view of the above conventional circumstances, and an object thereof is to provide a thermosetting resin composition having excellent reflow resistance and a semiconductor device using this thermosetting resin composition.

Specific means for achieving the above object are as follows.
<1> containing a thermosetting resin, a curing agent, and an inorganic filler,
The inorganic filler comprises an inorganic filler surface-treated with a coupling agent containing a primary amino group,
A thermosetting resin composition, wherein the content of the inorganic filler surface-treated with the coupling agent containing the primary amino group is 20% by mass to 60% by mass with respect to the entire thermosetting resin composition.
<2> The thermosetting resin composition according to <1>, wherein the ratio of the inorganic filler surface-treated with the coupling agent containing the primary amino group to the total inorganic filler is 75% by mass or less. .
<3> The amount of the inorganic filler surface-treated with the coupling agent containing the primary amino group is the inorganic filler 100 before the surface treatment with the coupling agent containing the primary amino group. The thermosetting resin composition according to <1> or <2>, which is 0.1 parts by mass to 5 parts by mass with respect to parts by mass.
<4> The thermosetting resin composition according to any one of <1> to <3>, wherein the coupling agent is an aminoalkyltrialkoxysilane.
<5> The thermosetting according to any one of <1> to <4>, wherein the inorganic filler surface-treated with the coupling agent containing a primary amino group has an angle of repose of 50° to 60°. elastic resin composition.
<6> Any one of <1> to <5>, wherein the inorganic filler surface-treated with the coupling agent containing the primary amino group has a bulk density of 1.15 g/cm ³ to 1.40 g/cm ³ . 1. The thermosetting resin composition according to claim 1.
<7> A semiconductor device comprising a semiconductor element and a cured product of the thermosetting resin composition according to any one of <1> to <6> for encapsulating the semiconductor element.
<8> The semiconductor device according to <7>, which is a surface mount type.
<9> The semiconductor device according to <7> or <8>, wherein both surfaces of the semiconductor element are in contact with the cured product directly or via a metal substrate.

According to the present disclosure, it is possible to provide a thermosetting resin composition having excellent reflow resistance and a semiconductor device using this thermosetting resin composition.

Hereinafter, embodiments according to the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.

In the present disclosure, the term "process" includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .
In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present disclosure, each component may contain multiple types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
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 a value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

<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 is an inorganic material surface-treated with a coupling agent containing a primary amino group. The content of the inorganic filler containing the filler and surface-treated with the coupling agent containing the primary amino group is set to 20% by mass to 60% by mass. Hereinafter, the "inorganic filler surface-treated with a coupling agent containing a primary amino group" may be referred to as a specific inorganic filler.
Although the reason why the thermosetting resin composition of the present disclosure is excellent in reflow resistance is not clear, it is speculated as follows.
When the content of the specific inorganic filler is 20% by mass or more, the adhesion of the specific inorganic filler to the resin, the semiconductor element, the insert of the lead frame, etc. tends to improve. On the other hand, when the content of the specific inorganic filler is 60% by mass or less, the reaction between the primary amino groups present on the surface of the specific inorganic filler and the thermosetting resin such as epoxy resin is suppressed, resulting in thermosetting. It tends to suppress the occurrence of unfilled portions due to the deterioration of the fluidity of the resin composition. From the above, it is presumed that a thermosetting resin composition having excellent reflow resistance can be obtained by setting the content of the specific inorganic filler to 20% by mass to 60% by mass.

The thermosetting resin composition of the present disclosure contains a thermosetting resin, a curing agent, an inorganic filler, and optionally other components.
Each component contained in the thermosetting resin composition of the present disclosure will be described in detail below.

(Thermosetting resin)
A thermosetting resin composition contains a thermosetting resin.
The type of thermosetting resin is not particularly limited, and examples thereof include epoxy resins, phenol resins, thiol resins, urea resins, melamine resins, urethane resins, silicone resins, maleimide resins, and unsaturated polyester resins. For the purposes of this disclosure, "thermosetting resins" includes those that exhibit both thermoplastic and thermosetting properties, such as acrylic resins containing epoxy groups. The thermosetting resin may be solid or liquid at normal temperature and normal pressure (eg, 25° C., atmospheric pressure), and is preferably solid. Thermosetting resins may be used singly or in combination of two or more.

The thermosetting resin preferably contains 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, at least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. A novolak type epoxy resin (phenol novolac type epoxy resin, ortho-cresol novolak-type epoxy resins, etc.); epoxidized triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst. A triphenylmethane type epoxy resin; a copolymer type epoxy resin obtained by epoxidizing a novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound in the presence of an acidic catalyst; bisphenol A, bisphenol diphenylmethane-type epoxy resins that are diglycidyl ethers such as F; biphenyl-type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; Sulfur atom-containing epoxy resins that are diglycidyl ethers; Epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; Glycidyl polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester-type epoxy resins that are esters; glycidylamine-type epoxy resins in which active hydrogens bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. are substituted with glycidyl groups; co-condensation resins of dicyclopentadiene and phenol compounds Dicyclopentadiene type epoxy resin which is obtained by epoxidizing the; vinylcyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2- (3,4-epoxy)cyclohexyl-5,5-spiro(3, 4-epoxy) Cyclohexane-m-dioxane and other cycloaliphatic epoxy resins; para-xylylene-modified epoxy resins that are glycidyl ethers of para-xylylene-modified phenol resins; meta-xylylene-modified epoxy resins that are glycidyl ethers of meta-xylylene-modified phenol resins; Terpene-modified epoxy resin that is glycidyl ether; dicyclopentadiene-modified epoxy resin that is glycidyl ether of dicyclopentadiene-modified phenol resin; cyclopentadiene-modified epoxy resin that is glycidyl ether of cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin polycyclic aromatic ring-modified epoxy resin that is a glycidyl ether of naphthalene ring-containing phenol resin naphthalene-type epoxy resin that is a glycidyl ether of naphthalene ring-containing phenol resin; halogenated phenol novolac-type epoxy resin; hydroquinone-type epoxy resin; trimethylolpropane-type epoxy resin; linear aliphatic epoxy resins obtained by oxidizing with a peracid such as peracetic acid; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins; Further examples of epoxy resins include epoxidized silicone resins and aminophenol-type epoxy resins, which are glycidyl ethers of aminophenol. These epoxy resins may be used singly or in combination of two or more.

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

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

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

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), the 3, 3', 5, and 5' positions are methyl groups when the positions where the oxygen atoms are substituted in R ⁸ are the 4 and 4' positions. YX-4000H (Mitsubishi Chemical Corporation, trade name) in which the other R ⁸ is a hydrogen atom, 4,4′-bis(2,3-epoxypropoxy)biphenyl in which all R ⁸ are hydrogen atoms, When all R ⁸ are hydrogen atoms and when the positions where oxygen atoms are substituted in R ⁸ are 4 and 4', 3, 3', 5, 5' positions are methyl groups and other R YL-6121H (Mitsubishi Chemical Co., Ltd., trade name), which is a mixture in which ⁸ is a hydrogen atom, is commercially available.

In formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms, all of which may be the same or different. n is the average value and represents a number from 0 to 10.

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), the 3,3',5,5' positions when the positions where the oxygen atoms are substituted in R ⁹ are the 4 and 4' positions are methyl groups and ^three of the 3,3′,5,5′ ^{positions of R 9 are} methyl groups, A mixed product in which one is a t-butyl group, the other R ⁹ is a hydrogen atom, and all of the R ¹⁰ are hydrogen atoms can be mentioned.

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

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 preferred. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and 3,3 when the positions of R ¹² substituted with oxygen atoms are 4 and 4′. YSLV-80XY (Nippon Steel Chemical & Materials Co., Ltd., trade name), which has methyl groups at the ', 5, 5' positions and hydrogen atoms at the other R ¹² , is available as a commercial product.

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

The sulfur atom-containing type epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. Examples thereof include epoxy resins represented by the following general formula (V). Among the epoxy resins represented by the following general formula (V), t-butyl groups are at the 3 and 3′ positions when the positions substituted with oxygen atoms in R ¹³ are the 4 and 4′ positions, YSLV-120TE (Nippon Steel Chemical & Materials Co., Ltd., trade name) having methyl groups at the 6 and 6′ positions and a hydrogen atom at the other R ¹³ is available as a commercial product.

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

The novolak-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak-type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolak-type phenolic resin such as a phenol novolak resin, a cresol novolak resin, or a naphthol novolak resin using a technique such as glycidyl etherification is preferable, and an epoxy represented by the following general formula (VI) Resin is more preferred. Among the epoxy resins represented by the general formula (VI) below, ESCN-190 and ESCN-195 (Sumitomo Chemical Co., Ltd.) in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group, and i = 1 , trade name), all of R ¹⁴ are hydrogen atoms and i = 0, N-770 and N-775 (DIC Corporation, trade name), all of R ¹⁴ are hydrogen atoms and i = 0 YDAN-1000-10C ( ^Nippon Steel Chemical & Materials Co., Ltd., Nippon Steel Chemical _& Materials Co., Ltd., (trade name), a portion in which all of R ¹⁴ are hydrogen atoms, i = 1 and R ¹⁵ is a methyl group, and a portion in which i = 2 and one of R ¹⁵ is a methyl group and one of R 15 is a benzyl group and benzyl group-modified cresol novolak epoxy resins having are available as commercial products.

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

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 starting material. For example, an epoxy resin represented by the following general formula (VII) is preferred. Among the epoxy resins represented by the following general formula (VII), HP-7200 (trade name of DIC Corporation) where i=0 is commercially available.

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

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-etherifying a triphenylmethane-type phenolic resin obtained from an aromatic aldehyde compound and a phenolic compound is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Co., Ltd., trade name) in which i is 0 and k is 0, EPPN-502H (Nippon Kayaku Co., Ltd., trade name) etc. are commercially available.

In formula (VIII), R ¹⁷ and R ¹⁸ each represent 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 the average value and represents a number from 0 to 10.

The copolymer type epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenolic 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 phenolic skeleton. . For example, an epoxy resin obtained by glycidyl-etherifying a novolac-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable. Among the epoxy resins represented by the following general formula (IX), NC-7300 (Nippon ^Kayaku Co., Ltd., trade name ) and the like are available as commercial products.

In formula (IX), R ¹⁹ to R ²¹ represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3, each j independently represents an integer of 0 to 2, and each k independently represents an integer of 0 to 4. l and m are average values, numbers from 0 to 10, and (l+m) shows numbers from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either one of formula (IX-1) or (IX-2) below. Definitions of R ¹⁹ to R ²¹ , i, j and k in formulas (IX-1) and (IX-2) are the same as definitions of R ¹⁹ to R ²¹ , i, j and k in formula (IX). . n is 1 (when linked via a methylene group) or 0 (when not linked via a methylene group).

Examples of the epoxy resin represented by the general formula (IX) include random copolymers containing l structural units and m structural units at random, alternating copolymers containing alternately, and copolymers containing regularly , block copolymers containing in block form, and the like. Any one of these may be used alone, or two or more may be used in combination.

As a copolymer type epoxy resin, Epiclon HP-5000 (DIC Corporation, trade name), which is a methoxynaphthalene/cresol formaldehyde cocondensation type epoxy resin containing the following two types of structural units in random, alternating or block order, is also available. preferable. In the following general formula, n and m are each an average value and a number of 0 to 10, (n+m) is a number of 0 to 10, preferably n and m are each an average value and 1 to 9 and (n+m) represents a number from 2 to 10.

The aralkyl-type epoxy resin is composed of at least one selected from the group consisting of phenol compounds such as phenol and cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof. There is no particular limitation as long as it is an epoxy resin made from a synthesized phenol resin. For example, a phenolic resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof is preferably an epoxy resin obtained by glycidyl etherification, and more preferably an epoxy resin represented by the following general formulas (X) and (XI).

Among epoxy resins represented by the following general formula (X), NC-3000S (Nippon Kayaku Co., Ltd., trade name) in which i is 0 and R ³⁸ is a hydrogen atom, i is 0 and R ³⁸ CER-3000 (Nippon Kayaku Co., Ltd., trade name), etc., which is a mixture of an epoxy resin in which is a hydrogen atom and an epoxy resin in which all R ⁸ in the general formula (II) are hydrogen atoms at a mass ratio of 80:20. available as a commodity. Further, among the epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel Chemical & Materials Co., Ltd., trade name) in which l is 0, j is 0, and k is 0, etc. are commercially available.

In formulas (X) and (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R ³⁷ , R ³⁹ to R ⁴¹ each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, l is each independently an integer of 0 to 4 show. n is an average value, each independently a number from 0 to 10.

Regarding R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ in general formulas (II) to (XI) above, “all of which may be the same or different” means, for example, 8 to R 41 in formula (II). It means that all 88 R ⁸ may be the same or different. Other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ also mean that the respective numbers contained in the formula may all be the same or different. Also, R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ may be the same or different. For example, all of R ⁹ and R ¹⁰ may be the same or different.
Further, the monovalent organic group having 1 to 18 carbon atoms in general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

n in the above general formulas (II) to (XI) is an average value, and preferably each independently in the range of 0 to 10. If 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, resulting in poor filling and bonding wires (gold wires that connect semiconductor elements and leads). There is a tendency that the occurrence of deformation, etc., is suppressed. More preferably, n is set in the range of 0-4.

Specific examples of preferred epoxy resins that can be used in thermosetting resin compositions have been described above along the general formulas (II) to (XI). includes 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl, and from the viewpoint of moldability and heat resistance, 4,4'-bis (2,3-Epoxypropoxy)-biphenyl may be mentioned.

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, more preferably 80 g/eq to 500 g/eq. is more preferred.

Epoxy resins may be liquid or solid. If the epoxy resin is solid, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of moldability and heat resistance, the temperature is preferably 40° C. to 180° C., and from the viewpoint of handleability during preparation of the thermosetting resin composition, it is more preferably 50° C. to 130° C.
In the present disclosure, softening point refers to a value measured by the ring and ball method of JIS K 7234:1986.
In the present disclosure, melting point refers to a value measured according to the visual observation method of JIS K 0064:1992.

The content of the epoxy resin in the thermosetting resin composition is preferably 0.5% by mass to 60% by mass, more preferably 2% by mass to 50% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc. % is more preferred.

(curing agent)
The thermosetting resin composition contains a curing agent.
The type of curing agent 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 epoxy resins 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. agents and the like. The curing agents may be used singly or in combination of two or more. The curing agent may be solid or liquid at normal 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.
Phenolic curing agents include, for example, phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. At least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde are condensed under an acidic catalyst or Novolac-type phenolic resin obtained by cocondensation; Aralkyl-type phenolic resin such as phenol aralkyl resin and naphthol aralkyl resin synthesized from the above phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc.; Para-xylylene and/or or meta-xylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization from the above phenolic compound and dicyclopentadiene; cyclopentadiene-modified Phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; Triphenylmethane type obtained by condensation or co-condensation of the above phenolic compound and an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst. Phenolic resin; Phenolic resins obtained by copolymerizing two or more of these can be mentioned. Furthermore, the phenol-based curing agent also includes a monohydric phenol compound having one phenolic hydroxyl group in one molecule. These phenol-based curing agents may be used singly or in combination of two or more.

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

The total proportion of the aralkyl-type phenolic resin and the melamine-modified phenolic resin in the total phenolic curing agent is preferably 40% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and 80% by mass. More preferably, it is from mass % to 100 mass %.
The proportion of the aralkyl-type phenolic resin in the total phenolic curing agent is preferably 40% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and 80% by mass to 100% by mass. It is even more preferable to have
The total proportion of the melamine-modified phenolic resin in the total phenolic curing agent is preferably 0% by mass to 15% by mass, more preferably 0% by mass to 10% by mass, and 0% by mass to 5% by mass. % is more preferred.

The melamine-modified phenolic resin may be obtained by mixing a phenolic compound such as phenol, melamine, and formalin, followed by a heating reaction.

Examples of aralkyl-type phenol resins include phenol aralkyl resins and naphthol aralkyl resins synthesized from phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, and the like. The aralkyl-type phenolic resin may be further copolymerized with another phenolic resin. Copolymerized aralkyl-type phenolic resins include copolymerized phenolic resins of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin, copolymerized phenolic resins of salicylaldehyde-type phenolic resin and aralkyl-type phenolic resin, and novolac-type phenolic resin. A copolymer type phenol resin of a resin and an aralkyl type phenol resin can be used.

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 dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof. . For example, phenol resins represented by the following general formulas (XII) to (XIV) are preferred.

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

Among the phenolic resins represented by the general formula (XII), MEH-7851 (Meiwa Kasei Co., Ltd., trade name) in which i is 0 and all R ²³ are hydrogen atoms is available as a commercial product. .

Among the phenolic resins represented by the above general formula (XIII), i is 0 and k is 0 XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Kasei Co., Ltd., (trade name) and the like are available as commercial products.

Among the phenolic resins represented by the general formula (XIV), j is 0, k is 0, and p is 0 SN-170 (Nippon Steel Chemical & Materials Co., Ltd., trade name), j is 0, k is 1, R ²⁷ is a hydroxyl group, and p is 0, such as SN-395 (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name), etc. are commercially available.

The dicyclopentadiene-type phenol resin is not particularly limited as long as it is a phenol resin obtained using a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferred. Among the phenolic resins represented by the following general formula (XV), phenolic resins in which i is 0 are commercially available.

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

The triphenylmethane-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained using an aromatic aldehyde compound as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferred.

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

In formula (XVI), R ³⁰ and R ³¹ each represent 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 the average value and is a number from 0 to 10.

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-type phenolic resin of phenolic resin obtained using a compound having a benzaldehyde skeleton as a raw material and aralkyl-type phenolic resin. . For example, a phenol resin represented by the following general formula (XVII) is preferred.

Among the phenol resins represented by the following general formula (XVII), i is 0, k is 0, q is 0 HE-510 (Air Water Chemical Co., Ltd., trade name), etc. are commercially available. available as a commodity.

In formula (XVII), R ³² to R ³⁴ each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them 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 each independently represents a number from 0 to 11. However, the sum of l and m is a number from 1 to 11.

The novolak-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensation or co-condensation of at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds and an aldehyde compound in the presence of an acidic catalyst. . For example, a phenol resin represented by the following general formula (XVIII) is preferred.

Among the phenolic resins represented by the following general formula (XVIII), i is 0 and R ³⁵ is all hydrogen atoms Tamanol 758, 759 (Arakawa Chemical Industries, Ltd., trade name), H-4 (Meiwa Kasei Co., Ltd., trade name) and the like are available as commercial products.

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

"All of which may be the same or different" described for R ²² to R ³⁶ in the general formulas (XII) to (XVIII) means, for example, that all i R ²² in formula (XII) are the same However, it means that they may be different from each other. Other R ²³ to R ³⁶ also mean that the respective numbers contained in the formula may all be the same or different from each other. Also, R ²² to R ³⁶ may be the same or different. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

n in the general formulas (XII) to (XVIII) is preferably in the range of 0-10. 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 becomes low, resulting in poor filling and deformation of the bonding wire (gold wire that connects the semiconductor element and the lead). etc. will be less likely to occur. The average n in one molecule is preferably set in the range of 0-4.

Examples of monohydric phenol compounds include “Tinuvin405”, “Tinuvin900”, “Tinuvin99-2”, “Tinuvin326”, “Tinuvin384-2”, “Tinuvin928” and the like (all of which are manufactured by BASF).
The proportion of the monohydric phenol compound in the total phenol-based curing agent is preferably 5% by mass to 20% by mass, more preferably 10% by mass to 19% by mass, more preferably 12% by mass to 12% by mass. More preferably, it is 18% by mass. In a certain aspect, it may be 5% by mass or less, 2% by mass or less, 1% by mass or less, or 0% by mass.

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

The functional group equivalent weight of the curing agent (hydroxyl group equivalent weight in the case of a phenol-based curing agent, and active hydrogen equivalent weight in the case of an amine-based 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, 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 according to JIS K0070:1992. In addition, the active hydrogen equivalent in the case of an amine-based curing agent is a value calculated based on the amine value measured according to JIS K7237:1995.

The softening point or melting point when the curing agent is solid is not particularly limited. From the viewpoint of moldability and heat resistance, the temperature is preferably 40° C. to 180° C., and from the viewpoint of handleability during production of the thermosetting resin composition, it is more preferably 50° C. to 130° C.

When the thermosetting resin is an epoxy resin, the equivalent ratio between the epoxy resin and the curing agent (the number of moles of epoxy groups in the resin/the number of moles of active hydrogen in the curing agent) is not particularly limited. From the viewpoint of suppressing the amount of reaction, it is preferably 0.7 to 1.3, for example.

(Curing accelerator)
The thermosetting resin composition may contain a curing accelerator. The type of curing accelerator is not particularly limited, and can be selected according to the type of curable resin, desired properties of the thermosetting resin composition, and the like.

From the viewpoint of curability and fluidity, the curing accelerator preferably contains a phosphonium compound. Specific examples of phosphonium compounds include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl/alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiaryl Tertiary phosphines such as phosphine, maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy- quinone compounds such as 5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane Compounds with intramolecular polarization; tertiary phosphines and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodinated phenol, 3-iodine phenol, 2-iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4 Halogenation of -bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, etc. A compound having intramolecular polarization obtained through a step of dehydrohalogenation after reacting a phenolic compound; a salt of a tetra-substituted phosphonium such as tetraphenylphosphonium and a tetra-substituted borate such as tetra-p-tolylborate; A salt of a tetra-substituted phosphonium and an anion resulting from deprotonation from a phenol compound, a salt of a tetra-substituted phosphonium and an anion resulting from deprotonation from a carboxylic acid compound, and the like.

The phosphonium compound preferably contains a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific curing accelerator).

In formula (I-1), R ¹ to R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ¹ to R ³ are bonded to each other to form a cyclic structure. R ⁴ to R ⁷ each independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms, and two or more of R ⁴ to R ⁷ are bonded together to form a cyclic structure. may be formed.

The “hydrocarbon group having 1 to 18 carbon atoms” described as R ¹ to R ³ in general formula (I-1) includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an aliphatic hydrocarbon group having 6 to 18 carbon atoms. Contains some aromatic hydrocarbon groups.

From the viewpoint of fluidity, the aliphatic hydrocarbon group having 1 to 18 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms.

The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. good too. From the viewpoint of ease of production, it is preferably a straight-chain or branched aliphatic hydrocarbon group.

Specific examples of linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Alkyl groups such as t-butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group, allyl group, vinyl group and the like can be mentioned. A linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of substituents include alkoxy groups such as methoxy group, ethoxy group, n-butoxy group and t-butoxy group, aryl groups such as phenyl group and naphthyl group, hydroxyl group, amino group and halogen atom. A straight-chain or branched aliphatic hydrocarbon group may have two or more substituents, which may be the same or different. When the linear or branched aliphatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aliphatic hydrocarbon group and the substituent is preferably 1-18. From the viewpoint of curability, unsubstituted alkyl groups are preferred, and unsubstituted alkyl groups having 1 to 8 carbon atoms are more preferred, such as n-butyl, isobutyl, n-pentyl, n-hexyl and n-octyl. groups are more preferred.

Specific examples of alicyclic hydrocarbon groups having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, and cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group. The alicyclic hydrocarbon group may or may not have a substituent. Examples of substituents include alkyl groups such as methyl group, ethyl group, n-butyl group and t-butyl group, alkoxy groups such as methoxy group, ethoxy group, n-butoxy group and t-butoxy group, phenyl group and naphthyl group. aryl groups, hydroxyl groups, amino groups, halogen atoms, and the like. An alicyclic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3-18. When the alicyclic hydrocarbon group has a substituent, the position of the substituent is not particularly limited. From the viewpoint of curability, an unsubstituted cycloalkyl group is preferable, an unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cyclohexyl group, a cyclopentyl group and a cycloheptyl group are more preferable.

The aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may or may not have a substituent. Examples of substituents include alkyl groups such as methyl group, ethyl group, n-butyl group and t-butyl group, alkoxy groups such as methoxy group, ethoxy group, n-butoxy group and t-butoxy group, phenyl group and naphthyl group. aryl groups, hydroxyl groups, amino groups, halogen atoms, and the like. The aromatic hydrocarbon group may have two or more substituents, in which case the substituents may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6-18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

Specific examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl and t-butyl. phenyl group, methoxyphenyl group, ethoxyphenyl group, n-butoxyphenyl group, t-butoxyphenyl group and the like. The position of the substituent in these aromatic hydrocarbon groups may be any of the ortho position, meta position and para position. From the viewpoint of fluidity, an unsubstituted aryl group having 6 to 12 carbon atoms or 6 to 12 carbon atoms including substituents is preferable, and an unsubstituted aryl group having 6 to 10 carbon atoms or carbon atoms including substituents An aryl group of numbers 6 to 10 is more preferred, and a phenyl group, p-tolyl group and p-methoxyphenyl group are even more preferred.

The term “two or more of R ¹ to R ³ may combine with each other to form a cyclic structure” described as R ¹ to R ³ in general formula (I-1) means that R ¹ to R ³ It means that two or three of them are combined to form one divalent or trivalent hydrocarbon group as a whole. Examples of R ¹ to R ³ in this case include alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene which can form a cyclic structure by bonding with a phosphorus atom; alkenylene groups such as ethylene, propylene and butylenylene groups; Substituents capable of forming a cyclic structure by bonding with a phosphorus atom, such as aralkylene groups such as methylenephenylene groups, and arylene groups such as phenylene, naphthylene and anthracenylene groups, can be mentioned. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms and the like.

The “organic group having 1 to 18 carbon atoms” described as R ⁴ to R ⁷ in general formula (I-1) above is an aliphatic group having 1 to 18 carbon atoms which may or may not be substituted. It is meant to include aromatic hydrocarbon groups, aromatic hydrocarbon groups, aliphatic hydrocarbon oxy groups, aromatic hydrocarbon oxy groups, acyl groups, hydrocarbon oxycarbonyl groups, and acyloxy groups.

Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group include those mentioned above as examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R ¹ to R ³ .

Examples of the aliphatic hydrocarbonoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a 2-butoxy group, a t-butoxy group, a cyclopropyloxy group, a cyclohexyloxy group, and a cyclopentyloxy group. , an allyloxy group, an oxy group having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon groups such as a vinyloxy group, and these aliphatic hydrocarbon oxy groups are further alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino and those substituted with groups, hydroxyl groups, halogen atoms, and the like.

Examples of the aromatic hydrocarbon oxy group include a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, a phenoxyphenoxy group having a structure in which an oxygen atom is bonded to the above aromatic hydrocarbon group, such as a phenoxyphenoxy group. groups, and those in which these aromatic hydrocarbon oxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.

Examples of the acyl group include aliphatic hydrocarbon carbonyl groups such as formyl group, acetyl group, ethylcarbonyl group, butyryl group, cyclohexylcarbonyl group and allylcarbonyl group, and aromatic hydrocarbon carbonyl groups such as phenylcarbonyl group and methylphenylcarbonyl group. and the like, in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

Examples of the hydrocarbon oxycarbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group and cyclohexyloxycarbonyl group, phenoxycarbonyl group, methylphenoxycarbonyl group and the like. aromatic hydrocarbon oxycarbonyl groups, these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. things, etc.

Examples of the acyloxy group include aliphatic hydrocarbon carbonyloxy groups such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an allylcarbonyloxy group and a cyclohexylcarbonyloxy group, a phenylcarbonyloxy group and a methylphenylcarbonyloxy group. etc., these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. and the like.

The term “two or more of R ⁴ to R ⁷ may combine with each other to form a cyclic structure” described as R ⁴ to R ⁷ in the general formula (I-1) means that two to four may be combined to form one divalent to ^tetravalent organic group ^as a whole. In this case, R ⁴ to R ⁷ include alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene; alkenylene groups such as ethylene, propylene, butyleneylene; aralkylene groups such as methylenephenylene; and arylene groups such as phenylene, naphthylene and anthracenylene. Substituents capable of forming a cyclic structure such as groups, their oxy groups or dioxy groups are included. These substituents may be further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms and the like.

R ⁴ to R ⁷ in general formula (I-1) are not particularly limited. For example, each independently selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. preferable. Among them, from the viewpoint of availability of raw materials, a hydrogen atom, a hydroxyl group, an aryl group substituted with at least one selected from the group consisting of an unsubstituted or alkyl group and an alkoxy group, or a chain or cyclic alkyl group preferable. Aryl groups that are unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, and the like. is mentioned. Chain or cyclic alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, t-butyl, octyl and cyclohexyl groups. From the viewpoint of curability, it is preferred that all of R ⁴ to R ⁷ are hydrogen atoms, or that at least one of R ⁴ to R ⁷ is a hydroxyl group and the rest are all hydrogen atoms.

More preferably, two or more of R ¹ to R ³ in general formula (I-1) are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and R ⁴ to R ⁷ are All are hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms. More preferably, all of R ¹ to R ³ are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and all of R ⁴ to R ⁷ are hydrogen atoms, or at least one is a hydroxyl group. and the rest are all hydrogen atoms.

From the viewpoint of rapid curability, the specific curing accelerator preferably contains a compound represented by the following general formula (I-2).

In formula (I-2), R ¹ to R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, and two or more of R ¹ to R ³ are bonded to each other to form a cyclic structure. R ⁴ to R ⁶ each independently represent a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R ⁴ to R ⁶ are bonded together to form a cyclic structure. may

Specific examples of R ¹ to R ⁶ in general formula (I-2) are the same as specific examples of R ¹ to R ⁷ in general formula (I-1), and preferred ranges are also the same.

Specific examples of the specific curing accelerator include addition reaction products of triphenylphosphine and 1,4-benzoquinone, addition reaction products of tri-n-butylphosphine and 1,4-benzoquinone, tricyclohexylphosphine and 1,4 -addition reaction product with benzoquinone, addition reaction product between dicyclohexylphenylphosphine and 1,4-benzoquinone, addition reaction product between cyclohexyldiphenylphosphine and 1,4-benzoquinone, addition reaction product between triisobutylphosphine and 1,4-benzoquinone reaction products, addition reaction products of tricyclopentylphosphine and 1,4-benzoquinone, and the like.

A specific curing accelerator can be obtained, for example, as an adduct of a tertiary phosphine compound and a quinone compound.
Specific examples of the third phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, and tris(4-ethylphenyl)phosphine. , tris(4-n-propylphenyl)phosphine, tris(4-n-butylphenyl)phosphine, tris(isopropylphenyl)phosphine, tris(t-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris( 4-ethoxyphenyl)phosphine and the like. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferred.

Specific examples of quinone compounds include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone and anthraquinone. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferred.

The thermosetting resin composition may contain a curing accelerator other than the phosphonium compound.
Specific examples of curing accelerators other than phosphonium compounds include 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU). Cyclic amidine compounds such as diazabicycloalkenes such as diazabicycloalkene, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; the cyclic amidine compounds or the Phenol novolak salts of derivatives; These compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3- quinone compounds such as dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone; and compounds with π bonds such as diazophenylmethane. Cyclic amidiniums such as tetraphenylborate salt of DBU, tetraphenylborate salt of DBN, tetraphenylborate salt of 2-ethyl-4-methylimidazole, tetraphenylborate salt of N-methylmorpholine, etc. Compounds; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate , tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and ammonium salt compounds such as tetrapropylammonium hydroxide.

When the thermosetting resin composition contains a specific curing accelerator as a curing accelerator, the content of the specific curing accelerator is preferably 30% by mass or more of the total curing accelerator, and is 50% by mass or more. is more preferable, and 70% by mass or more is even more preferable.

When the thermosetting resin composition contains a curing accelerator, the amount is preferably 0.1 parts by mass to 30 parts by mass with respect to a total of 100 parts by mass of the thermosetting resin and the curing agent, and 1 mass parts to 15 parts by mass is more preferable. When the amount of the curing accelerator is 0.1 parts by mass or more with respect to the total of 100 parts by mass of the thermosetting resin and the curing agent, there is a tendency for good curing in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to the total of 100 parts by mass of the thermosetting resin and the curing agent, the curing speed is not too fast and a good molded article tends to be obtained.

(Inorganic filler)
A thermosetting resin composition contains an inorganic filler. Inorganic fillers include specific inorganic fillers, inorganic fillers not surface-treated with a coupling agent, and inorganic fillers surface-treated with a coupling agent other than a coupling agent containing a primary amino group. of inorganic fillers.
The type of inorganic filler is not particularly limited. Specifically, silica such as spherical silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Inorganic materials such as spinel, mullite, titania, talc, clay, and mica. Inorganic fillers having a flame retardant effect may also be used. 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 preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more types. Examples of the state of the inorganic filler include powders, beads obtained by spheroidizing powders, fibers, and the like.

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 80% by mass to 95% by mass of the entire thermosetting resin composition, more preferably 82% by mass to 93% by mass, and 84% by mass to 91% by mass. % is more preferred. When the content of the inorganic filler is 80% by mass or more of the entire thermosetting resin composition, the properties of the cured product, such as thermal expansion coefficient, thermal conductivity and elastic modulus, tend to be further improved. When the content of the inorganic filler is 95% by mass or less of the entire thermosetting resin composition, the increase in viscosity of the thermosetting resin composition is suppressed, the fluidity is further improved, and the moldability is better. tend to become
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 70% to 90% by volume of the total thermosetting resin composition, more preferably 72% to 88% by volume, and 75% to 85% by volume. % is more preferred. When the content of the inorganic filler is 70% by volume or more of the entire thermosetting resin composition, the properties of the cured product, such as thermal expansion coefficient, thermal conductivity and elastic modulus, tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire thermosetting resin composition, the increase in viscosity of the thermosetting resin composition is suppressed, the fluidity is further improved, and the moldability is better. tend to become

The average particle size of the inorganic filler is not particularly limited. For example, the volume average particle size is preferably 0.2 μm to 50 μm, more preferably 0.5 μm to 30 μm.
When the volume average particle size is 0.2 μm or more, the increase in viscosity of the thermosetting resin composition tends to be more suppressed. When the volume average particle size is 50 µm or less, the filling property into narrow gaps tends to be further improved. The volume average particle size of the inorganic filler refers to a value measured as a volume average particle size (D50) by a laser diffraction scattering method particle size distribution analyzer.

From the viewpoint of fluidity of the thermosetting resin composition, the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably distributed over a wide range.

In the present disclosure, the inorganic filler includes the specific inorganic filler, and the content of the specific inorganic filler is 20% by mass to 60% by mass of the entire thermosetting resin composition. The content of the specific inorganic filler is preferably 21% by mass to 55% by mass, more preferably 22% by mass to 50% by mass, of the entire thermosetting resin composition.

In the present disclosure, the ratio of the specific inorganic filler to the total inorganic filler is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. When the ratio of the specific inorganic filler to the inorganic filler is 75% by mass or less, thickening of the thermosetting resin composition is suppressed, and storage stability tends to be improved. The ratio of the specific inorganic filler to the inorganic filler may be 20% by mass or more.

A surface treatment method for the inorganic filler is appropriately selected according to the type of the inorganic filler. When the inorganic filler is silica, for example, the silica surface treatment method includes adding a solution containing a coupling agent to a slurry containing silica, stirring, separating the surface-treated silica by filtration or the like, and drying. and a method of spraying a coupling agent onto silica and drying it.

The amount of the specific inorganic filler treated with the coupling agent is preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the inorganic filler before surface treatment with a coupling agent containing a primary amino group. .3 to 4 parts by mass is more preferable, and 0.5 to 3 parts by mass is even more preferable. When the amount of the specific inorganic filler treated with the coupling agent is 0.1 parts by mass or more, the dispersibility of the specific inorganic filler is improved, and the adhesiveness and moldability of the thermosetting resin composition tend to be improved. . When the amount of the specific inorganic filler treated with the coupling agent is 5 parts by mass or less, aggregation of the specific inorganic filler tends to be less likely to occur.

A coupling agent containing a primary amino group used for surface treatment of an inorganic filler may be a coupling agent having at least one primary amino group ( _-NH2 group) in the molecule. Specific examples of coupling agents having a primary amino group in the molecule include 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyl triethoxysilane, 3-aminopropyltrimethoxysilane, isopropyltri(N-aminoethyl-aminoethyl) titanate and the like.
As the coupling agent having a primary amino group in the molecule, a silane coupling agent having a primary amino group in the molecule is preferable, and aminoalkyltrialkoxysilane is more preferable. Aminoalkyltrialkoxysilanes include 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane. Among these, at least one of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane is more preferred, and 3-aminopropyltriethoxysilane is particularly preferred.

The bulk density of the specific inorganic filler is preferably 1.15 g/cm ³ to 1.40 g/cm ³ , more preferably 1.20 g/cm ³ to 1.38 g/cm ³ , and 1.25 g/cm ³ to 1 0.35 g/cm ³ is more preferred. If the specific inorganic filler has a bulk density of 1.15 g/cm ³ or more, the dispersibility of the specific inorganic filler in the thermosetting resin composition tends to be further improved. If the specific inorganic filler has a bulk density of 1.40 g/cm ³ or less, the fluidity of the thermosetting resin composition tends to be further improved.
In the present disclosure, bulk density refers to a value measured by the following method.
The bulk density was measured by tilting a measuring cylinder with a capacity of 200 ml, gradually adding the sample powder to the marked line of 200 ml using a spoon, plugging the measuring cylinder, and then dropping the measuring cylinder from a height of 5 cm 400 times. It is measured by a method of calculating from the mass and volume of the sample powder after dropping.

The angle of repose of the specific inorganic filler is preferably 50° to 60°, more preferably 51° to 58°, even more preferably 52° to 57°. When the specific inorganic filler has an angle of repose of 50° or more, uneven distribution of the specific inorganic filler in the thermosetting resin composition tends to be more suppressed. If the angle of repose of the specific inorganic filler is 60° or less, aggregation of the specific inorganic filler in the thermosetting resin composition tends to be more suppressed.
In the present disclosure, the angle of repose refers to a value measured by an injection method.

[Various additives]
In addition to the components described above, the thermosetting resin composition may contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, and stress relaxation agents exemplified below. The thermosetting resin composition may contain various additives such as ultraviolet absorbers well known in the technical field, if necessary, in addition to the additives exemplified below.

(coupling agent)
The thermosetting resin composition may contain a coupling agent. In the present disclosure, the thermosetting resin composition containing a coupling agent means that the coupling agent is integrally blended with the thermosetting resin composition.
The type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of coupling agents include silane coupling agents and titanium coupling agents. A coupling agent may be used individually by 1 type, or may use 2 or more types together.

Specific examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyl Epoxy silane coupling agents such as dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino ) Amine-based silane coupling agents such as propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- Mercapto-based silane coupling agents such as mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, and the like can be mentioned.

Titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2, 2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyltitanate, isopropyldimethacrylisostearoyltitanate , isopropyltridodecylbenzenesulfonyltitanate, isopropylisostearoyldiacryltitanate, isopropyltri(dioctylphosphate)titanate, isopropyltricumylphenyltitanate, tetraisopropylbis(dioctylphosphite)titanate and the like.

When the thermosetting resin composition contains a coupling agent, the coupling agent includes an amine-based silane coupling agent and an epoxy-based silane coupling agent from the viewpoint of improving the adhesiveness and moldability of the thermosetting resin composition. At least one of the agents is preferred.
When the thermosetting resin composition contains a coupling agent, the content of the coupling agent is based on 100 parts by mass of the inorganic filler from the viewpoint of the adhesion of the interface between the thermosetting resin and the inorganic filler. , preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, even more preferably 0.05 to 5 parts by mass.

(Ion exchanger)
The thermosetting resin composition may contain an ion exchanger. In particular, when the thermosetting resin composition is used as a sealing molding material, it preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. The ion exchangers may be used singly or in combination of two or more. Among them, hydrotalcite represented by the following general formula (B) is preferable.

Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _X/2 ·mH ₂ O (B)
(0<X≤0.5, m is a positive number)

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 to 30 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the total of the thermosetting resin and the curing agent.

(Release agent)
The thermosetting resin composition may contain a mold release agent from the viewpoint of obtaining good releasability from the mold during molding. The release agent is not particularly limited, and conventionally known agents can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. The release agent may be used singly or in combination of two or more.

When the thermosetting resin composition contains a release agent, the amount thereof is preferably 0.01 to 15 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the total of the thermosetting resin and the curing agent. 10 parts by mass is more preferable. When the amount of the release agent is 0.01 parts by mass or more with respect to the total of 100 parts by mass of the thermosetting resin and the curing agent, there is a tendency that sufficient releasability can be obtained. When the amount of the release agent is 15 parts by mass or less with respect to the total of 100 parts by mass of the thermosetting resin and the curing agent, better adhesion tends to be obtained.

(Flame retardants)
The thermosetting resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, and metal hydroxides. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more types.

When the thermosetting resin composition contains a flame retardant, its amount is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 to 300 parts by mass, more preferably 2 to 150 parts by mass, based on 100 parts by mass of the thermosetting resin and the curing agent.

(coloring agent)
The thermosetting resin composition may further contain a coloring agent. Examples of coloring agents include known coloring agents such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the coloring agent can be appropriately selected according to the purpose and the like. The colorants may be used singly or in combination of two or more.

(Stress relaxation agent)
The thermosetting resin composition may contain stress relaxation agents such as silicone oil and silicone rubber particles. By containing the stress relaxation agent, it is possible to further reduce the warpage deformation of the package and the occurrence of package cracks. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexible agents). Specifically, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic Rubber particles such as rubber, urethane rubber, silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, indene, alkylindene Copolymers of indenes such as styrene, styrenes such as alkylstyrene and phenols, and indene-containing copolymers containing aromatic olefins such as coumarone as other constituent monomers, epoxy-modified silicone resins, etc. . A stress relaxation agent may be used individually by 1 type, or may be used in combination of 2 or more types.
When the thermosetting resin composition contains a stress relaxation agent, the content of the stress relaxation agent is 1 part by mass to 50 parts by mass with respect to a total of 100 parts by mass of the thermosetting resin and the curing agent. preferable.

(Method for preparing thermosetting resin composition)
The method for preparing the thermosetting resin composition is not particularly limited. As a general method, there can be mentioned a method of thoroughly mixing components in predetermined amounts with a mixer or the like, melt-kneading the mixture with a mixing roll, an extruder or the like, cooling, and pulverizing. More specifically, for example, predetermined amounts of the components described above are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like preheated to 70° C. to 140° C., cooled, and pulverized. can be mentioned.

The thermosetting resin composition is preferably solid at normal temperature and normal pressure (eg, 25° C., atmospheric pressure). When the thermosetting resin composition is solid, its shape is not particularly limited, and examples thereof include powder, granules, tablets, pellets, and granules. When the thermosetting resin composition is in the form of tablets or pellets, it is preferable from the standpoint of handleability that the dimensions and weight are suitable for the package molding conditions.

A method for curing the thermosetting resin composition is not particularly limited. The thermosetting resin composition may be cured by low-pressure transfer molding, injection molding, compression molding, or the like, and then post-cured.
The post-curing conditions can be appropriately set in consideration of the composition of the thermosetting resin composition. The curing temperature for post-curing is, for example, preferably 160°C to 240°C, more preferably 160°C to 220°C, even more preferably 175°C to 200°C. The curing time for post-curing is, for example, preferably 1 hour to 48 hours, more preferably 3 hours to 24 hours, and even more preferably 5 hours to 24 hours.

<Semiconductor device>
A semiconductor device of the present disclosure includes a semiconductor element and a cured product of the thermosetting resin composition of the present disclosure that seals the semiconductor element.
Examples of semiconductor elements include, but are not limited to, diodes, transistors, thyristors, ICs (Integrated Circuits), LSIs (Large Scale Integration), and the like.
As a semiconductor device, specifically, a semiconductor element is fixed on a lead frame, a terminal portion of the semiconductor element such as a bonding pad and a lead portion are connected by wire bonding, bumps, or the like, and then a thermosetting resin composition is applied. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead Package) having a structure sealed by transfer molding or the like using , TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), QFN (Quad Flat Non-leaded), etc.; TCP (Tape Carrier Package) having a structure sealed with a composition; a semiconductor element connected to a wiring formed on a support member by wire bonding, flip chip bonding, soldering, etc. is sealed with a thermosetting resin composition. COB (Chip On Board) modules, hybrid ICs, multi-chip modules, etc., having a structure having a structure; a semiconductor element is mounted on the surface of a support member on which terminals for wiring board connection are formed on the back surface, and the semiconductor element and the semiconductor element are bonded by bumps or wire bonding. BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), etc., having a structure in which a semiconductor element is sealed with a thermosetting resin composition after connecting to a wiring formed on a support member. is mentioned. In addition, even if these semiconductor devices are stacked (laminated) type packages in which two or more semiconductor elements are stacked on a substrate, two or more semiconductor elements can be mounted at one time using a thermosetting resin composition. It may be a batch mold type package sealed with .

The semiconductor device of the present disclosure is preferably a surface-mounted semiconductor device from the viewpoint of high-density mounting.
In the semiconductor device of the present disclosure, both surfaces of the semiconductor element may be in contact with the cured thermosetting resin composition of the present disclosure either directly or via a metal substrate. Examples of metal substrates include lead frames, Ag-plated substrates, Au-plated substrates, Ni/Pd/Au-plated substrates, and the like.
The contact area between the semiconductor element and the cured product is increased by bringing both surfaces of the semiconductor element into contact with the cured product of the thermosetting resin composition directly or via the metal substrate. When the contact area between the semiconductor element and the cured product increases, peeling tends to occur at the interface between the semiconductor element and the cured product, and as a result, the reflow resistance may deteriorate. Since the thermosetting resin composition of the present disclosure is excellent in reflow resistance, the heat of the present disclosure can be applied to a semiconductor device having a configuration in which both surfaces of a semiconductor element are in contact with a cured product of the thermosetting resin composition directly or via a metal substrate. If a curable resin composition is applied, the effect of preventing deterioration of reflow resistance tends to be exhibited.

EXAMPLES The present disclosure will be specifically described below with reference to Examples, but the scope of the present disclosure is not limited to these Examples.

[Preparation of thermosetting resin composition]
The following materials were mixed in the composition (parts by mass) shown in Table 1, and roll kneading was performed under the conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes to obtain the heat of Examples 1 to 3 and Comparative Examples 1 to 3. A curable resin composition was prepared. When a thermosetting resin composition was prepared with the same composition as in Example 1 except that inorganic filler 2 was used instead of all of the inorganic fillers, kneading became difficult. Therefore, the thermosetting resin composition in which all of the inorganic fillers were the inorganic filler 2 was not evaluated.
The "equivalent ratio (epoxy/phenol)" in Table 1 means the equivalent ratio between the epoxy resin and the curing agent.

・ Epoxy resin 1: methoxynaphthalene with an epoxy equivalent of 250 g / eq and a softening point of 58 ° C. A copolymer type epoxy resin of cresol and formaldehyde ・ Epoxy resin 2: an epoxy equivalent of 196 g / eq and a softening point of 106 ° C. Biphenyl type epoxy resin ・Curing agent 1: aralkyl-type phenolic resin with a hydroxyl equivalent of 175 g/eq and a softening point of 70°C Curing agent 2: a melamine-modified phenolic resin with a hydroxyl equivalent of 120 g/eq and a softening point of 90°C Curing agent 3: 2-[4- [(2-Hydroxy-3-(2′-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine curing accelerator : Addition reaction product of triphenylphosphine and 1,4-benzoquinone Coupling agent 1: 3-glycidoxypropyltrimethoxysilane Coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane Release Agent 1: Montan acid ester Release agent 2: Polyethylene oxide Colorant: Carbon black Ion exchanger: Hydrotalcite Stress relaxation agent 1: Indene-containing copolymer Stress relaxation agent 2: Epoxy-modified silicone resin Inorganic filler 1: Silica filler not surface-treated with a coupling agent (spherical silica having an average particle size of 20 μm, angle of repose: 49°, bulk density: 1.42 g/cm ³ )
Inorganic filler 2: 3-aminopropyltriethoxysilane-treated silica filler (spherical silica having a volume average particle size of 20 μm, angle of repose: 53°, bulk density: 1.28 g/cm ³ , silica before treatment with a coupling agent: 100 Amount of 3-aminopropyltriethoxysilane treated per part by mass: 1 part by mass)

[evaluation]
Each thermosetting resin composition was evaluated under the following conditions.
The cured product of the thermosetting resin composition was evaluated using the cured product prepared under the following conditions. Table 1 shows the evaluation results.
The cured product was obtained by molding a thermosetting resin composition using a transfer molding machine at a mold temperature of 175°C, a molding pressure of 8.3 MPa, and a curing time of 120 seconds, followed by post-curing at 175°C for 6 hours. Obtained.

<Liquidity>
(Evaluation of spiral flow (SF))
Using a spiral flow measurement mold according to EMMI-1-66, a thermosetting resin composition is molded with 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. Then, the flow distance (inch) was obtained.

(Measurement of gel time)
The gel time (GT) of the thermosetting resin composition was measured using a JSR Trading Co., Ltd. curelastometer. 3 g of the thermosetting resin composition was measured at 180° C. using a cureastometer manufactured by JSR Trading Co., Ltd. The gel time (seconds) was defined as the time until the torque curve began to rise.

-Adhesive strength after moisture absorption-
A thermosetting resin composition is applied to a silver-plated product (adhesive strength after moisture absorption 1) or a Ni-Pd-Au plated product (adhesive strength 2 after moisture absorption) of a Cu lead frame as an adherend, and heat is applied. The curable resin composition was cured under the above conditions to prepare a test piece (attachment surface: 10 mm ² ). The test piece was then humidified for 96 hours under conditions of 85°C and 85% RH. Using a bond tester manufactured by DAGE, the shear speed (moving speed of the jig) was set to 50 μm / sec, and a force was applied in the shear direction at a height of about 100 μm from the adherend surface of the cured product in the obtained test piece. was added to measure the breaking or peeling force between the adherend and the cured product of the thermosetting resin composition. The breaking or peeling force was measured while heating the specimen to 260°C.

-Reflow resistance 1-
28-pin SO (Small Outline) package with a 3.2 mm × 2.2 mm × 0.37 mm silicon chip mounted on a 5.2 mm × 4.1 mm die pad (lead frame material: copper alloy, die pad upper surface and lead tip Silver-plated products) were sealed using the curable resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2, and then post-cured under the conditions described above. It was visually confirmed that there were no cracks on the outside of the molded product obtained, and it was confirmed by an ultrasonic flaw detector (manufactured by Hitachi, Ltd., FS-200) that there was no peeling inside. After drying the molded product at 125° C. for 12 hours, it was humidified under conditions of 60° C. and 60% RH for 120 hours. After that, the reflow temperature was set to 260°C in accordance with JEDEC regulations, and the reflow process was performed three times at the same temperature. Each was observed on the device. The ratio of the number of packages in which either cracks or peeling occurred to 16 test packages was obtained.

-Reflow resistance 2-
QFN (Quad Flat Non-leaded) package with a 3.0 mm x 3.0 mm x 0.37 mm silicon chip mounted on a 6.0 mm x 6.0 mm die pad (lead frame material: copper alloy, Ni-Pd-Au plating Treated products) were sealed using the curable resin compositions of Example 3 and Comparative Example 3, and then post-cured under the conditions described above. It was visually confirmed that there were no cracks on the outside of the molded product obtained, and it was confirmed by an ultrasonic flaw detector (FS-200, manufactured by Hitachi, Ltd.) that there was no peeling inside. After drying the molded product at 125° C. for 12 hours, it was humidified under conditions of 85° C. and 60% RH for 168 hours. After that, the reflow temperature was set to 260°C in accordance with JEDEC regulations, and the reflow process was performed three times at the same temperature. Each was observed on the device. The ratio of the number of packages in which either cracks or peeling occurred to 16 test packages was obtained.

From Table 1, it can be seen that the thermosetting resin compositions of Examples are superior in reflow resistance to the thermosetting resin compositions of Comparative Examples.

Claims (9)

containing a thermosetting resin, a curing agent, and an inorganic filler,
The inorganic filler comprises an inorganic filler surface-treated with a coupling agent containing a primary amino group,
A thermosetting resin composition, wherein the content of the inorganic filler surface-treated with the coupling agent containing the primary amino group is 20% by mass to 60% by mass with respect to the entire thermosetting resin composition. 2. The thermosetting resin composition according to claim 1, wherein the ratio of the inorganic filler surface-treated with the coupling agent containing the primary amino group to the total inorganic filler is 75% by mass or less. The coupling agent treatment amount of the inorganic filler surface-treated with the coupling agent containing the primary amino group is 100 parts by mass of the inorganic filler before surface treatment with the coupling agent containing the primary amino group. 3. The thermosetting resin composition according to claim 1 or 2, wherein the content is 0.1 to 5 parts by mass. The thermosetting resin composition according to any one of claims 1 to 3, wherein the coupling agent is an aminoalkyltrialkoxysilane. The thermosetting resin composition according to any one of claims 1 to 4, wherein the inorganic filler surface-treated with a coupling agent containing a primary amino group has an angle of repose of 50° to 60°. thing. 6. The bulk density of the inorganic filler surface-treated with the coupling agent containing the primary amino group is 1.15 g/cm ³ to 1.40 g/cm ³ . The thermosetting resin composition according to . A semiconductor device comprising a semiconductor element and a cured product of the thermosetting resin composition according to any one of claims 1 to 6, which seals the semiconductor element. 8. The semiconductor device according to claim 7, which is of a surface mount type. 9. The semiconductor device according to claim 7, wherein both surfaces of said semiconductor element are in contact with said cured product directly or via a metal substrate.