Resin composition for sealing and electronic component device

Abstract

To provide a resin composition for sealing which is excellent in flowability.SOLUTION: A resin composition for sealing contains an epoxy resin, a curing agent, an inorganic filler, and an aromatic group-containing cyanoacrylate-based compound.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Epoxy resins are superior to other thermosetting resins in terms of moldability, adhesiveness, electrical properties, mechanical properties, moisture resistance, and the like, and therefore epoxy resin compositions have been commonly used as encapsulating resins for semiconductor devices. In recent years, in the electronic device market, there has been a trend toward smaller semiconductor devices, higher density, and higher density mounting of semiconductor elements, and as a result, surface-mounted packages have become mainstream for resin-encapsulated semiconductor devices, replacing the conventional pin-insertion type packages. Surface-mounted ICs (Integrated Circuits), LSIs (Large Scale Integrations), etc. have become thin and small packages in order to increase mounting density and reduce mounting height, and their mounting method is different from that of conventional insertion-type packages. That is, in pin-insertion packages, after inserting pins into a wiring board, soldering is performed from the back side of the wiring board, so that the package is not directly exposed to high temperatures. On the other hand, surface-mounted packages are temporarily attached to the surface of a wiring board and processed with a solder bath, reflow device, etc., so that the package is directly exposed to the soldering temperature (reflow temperature). As the reflow temperature increases, if the semiconductor device absorbs moisture, problems such as package cracking during mounting and peeling at the interface between the encapsulant and the metal frame, organic substrate, or semiconductor element occur. The smaller the internal stress at the encapsulant interface during reflow, the less likely peeling at the interface occurs. Therefore, a method of reducing stress, such as reducing elasticity at the reflow temperature, is required for the encapsulating resin composition. Furthermore, when encapsulating a semiconductor device, the encapsulating resin composition is required to have high fluidity.

[0003] As an encapsulating material having excellent reflow resistance, there has been disclosed an encapsulating epoxy resin composition that contains (A) an epoxy resin, (B) a phenolic resin curing agent, (C) an inorganic filler, and (D) a silane coupling agent having an acid anhydride group, and is a compound in which both the acid anhydride group and the alkoxy group are completely hydrolyzed without intermolecular condensation (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-46576 A Summary of the Invention [Problem to be solved by the invention]

[0005] The encapsulating epoxy resin composition disclosed in Patent Document 1 has excellent reflow resistance, but there is room for improvement in terms of fluidity. The present disclosure has been made in consideration of the above-mentioned conventional circumstances, and has an object to provide an encapsulating resin composition having excellent flowability and an electronic component device using the same. [Means for solving the problem]

[0006] Specific means for achieving the above object are as follows. <1> An encapsulating resin composition comprising an epoxy resin, a curing agent, an inorganic filler, and an aromatic group-containing cyanoacrylate compound. <2> The molecular weight of the aromatic group-containing cyanoacrylate compound is 200 or more. <1> The encapsulating resin composition according to claim 1 . <3> The aromatic group-containing cyanoacrylate compound contains at least one of a compound represented by the following general formula (IA) and a compound represented by the following general formula (IB): <1> or <2> The encapsulating resin composition according to claim 1 .

[0007] [ka]

[0008] (In the general formula (IA) and the general formula (IB), R 1 and R 2 each independently represents an aromatic group; R 3 represents a monovalent organic group, R 4 represents a hydrogen atom or a monovalent organic group. n represents an integer of 2 to 4. <4> The aromatic group-containing cyanoacrylate compound contains a compound represented by the general formula (IA). <3> The encapsulating resin composition according to claim 1 . <5> R in the compound represented by the general formula (IA) 3 is a branched alkyl group. <3> or <4> The encapsulating resin composition according to claim 1 . <6> The branched alkyl group has 3 to 12 carbon atoms. <5> The encapsulating resin composition according to claim 1 . <7> The content of the aromatic group-containing cyanoacrylate compound is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the epoxy resin. <1> ~ <6> 13. The encapsulating resin composition according to claim 12. <8> The content of the inorganic filler in the entire encapsulating resin composition is 68% by volume to 86% by volume. <1> ~ <7> 13. The encapsulating resin composition according to claim 12. <9> Spiral flow according to EMMI-1-66 is 100cm or more <1> ~ <8> 13. The encapsulating resin composition according to claim 12. <10> When cured, the hot hardness is 56 or more. <1> ~ <9> 13. The encapsulating resin composition according to claim 12. <11> When cured, the hot strength is 3 MPa or more. <1> ~ <10> 13. The encapsulating resin composition according to claim 12. <12> An element and a device for sealing the element <1> ~ <11> 13. An electronic component device comprising: a cured product of the encapsulating resin composition according to claim 12. <13> A lead frame is provided on one side of which the element is mounted. <12> The electronic component device according to claim 1 . Effect of the Invention

[0009] According to one embodiment of the present disclosure, it is possible to provide an encapsulating resin composition having excellent flowability and an electronic component device using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0011] In the present disclosure, the term "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple types of corresponding substances. When multiple types of substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the particles corresponding to each component may include multiple types of particles. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

[0012] In the description of groups (atomic groups) in the present disclosure, the description without specifying whether substituted or unsubstituted includes those having no substituents as well as those having a substituent. In the present disclosure, the number of structural units represents an integer value for a single molecule, but represents a rational number that is an average value for an aggregate of multiple types of molecules. In the present disclosure, the number of carbon atoms means the total number of carbon atoms contained in an entire group, and represents the number of carbon atoms forming the skeleton of the group when the group has no substituents, and represents the total number obtained by adding the number of carbon atoms forming the skeleton of the group to the number of carbon atoms in the substituents when the group has a substituent.

[0013] In the present disclosure, the weight average molecular weight (Mw) is a value measured using the following GPC measuring device under the following measurement conditions, and converted using a calibration curve of standard polystyrene. However, for compounds whose Mw cannot be accurately measured by GPC due to their small molecular weight, the molecular weight calculated from the chemical structure of the compound is used as the Mw or degree of polymerization of the compound. The following is an example of a measuring device, and a calibration curve may be created using a 5-sample set of standard polystyrene ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation).

[0014] (GPC measurement device) GPC equipment: High-speed GPC equipment "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation Column: TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation (Measurement conditions) Solvent: Tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35mL / min Sample concentration: 10mg / THF5mL Injection volume: 20μL

[0015] <Sealing resin composition> The encapsulating resin composition of the present disclosure contains an epoxy resin, a curing agent, an inorganic filler, and an aromatic group-containing cyanoacrylate compound. The encapsulating resin composition of the present disclosure has excellent fluidity. The reason why the encapsulating resin composition of the present disclosure has excellent fluidity is not clear, but is presumed to be as follows. The aromatic group-containing cyanoacrylate compound has both a polar portion containing a cyano group and a carbonyl group and a non-polar portion containing an organic group such as an aromatic ring. The polar portion of the aromatic group-containing cyanoacrylate compound is easily electrically connected to the polar portion of the epoxy resin or the curing agent. In addition, the non-polar portion of the aromatic group-containing cyanoacrylate compound can penetrate between the molecules of the epoxy resin or the curing agent to widen the distance between the molecules. The widening of the distance between the molecules weakens the intermolecular force between the epoxy resin and the curing agent. It is therefore presumed that the fluidity, typified by the spiral flow, is improved.

[0016] The components constituting the encapsulating resin composition will be described below. The encapsulating resin composition of the present disclosure includes an epoxy resin, a curing agent, an inorganic filler, and an aromatic group-containing cyanoacrylate compound, and may include various additives such as a curing accelerator, a coupling agent, a stress relaxation agent, a release agent, a colorant, a flame retardant, and an ion exchanger as necessary.

[0017] (Epoxy resin) The encapsulating resin composition of the present disclosure contains an epoxy resin. The type of the epoxy resin is not particularly limited as long as it has an epoxy group in the molecule. Specific examples of the epoxy resin are described below, but the epoxy resin is not limited to these specific examples.

[0018] Specifically, the novolac type epoxy resins are obtained by epoxidizing a novolac resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst (phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, etc.); the triphenylmethane type epoxy resins are obtained by epoxidizing a triphenylmethane type phenolic resin obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst; and the novolac resins are obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst (triphenylmethane type epoxy resins). diphenylmethane type epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl type epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene type epoxy resins which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing type epoxy resins which are diglycidyl ethers of bisphenol S, etc.; epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester type epoxy resins which are glycidyl esters of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine type epoxy resins in which active hydrogen bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is substituted with a glycidyl group; dicyclopentadiene type epoxy resins which are epoxidized co-condensation resins of dicyclopentadiene and phenolic compounds;Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which are epoxy-modified epoxy resins in which the olefin bonds in the molecule have been epoxidized; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenolic resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenolic resins; and dicyclopentadiene-modified phenolic resins, which are glycidyl ethers of dicyclopentadiene-modified phenolic resins. Examples of the epoxy resin include pentadiene-modified epoxy resins; cyclopentadiene-modified epoxy resins which are glycidyl ethers of cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified epoxy resins which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins; and the like. Furthermore, aminophenol-type epoxy resins which are glycidyl ethers of aminophenols are also included as epoxy resins. These epoxy resins may be used alone or in combination of two or more.

[0019] Among the above epoxy resins, from the viewpoint of the adhesion of the encapsulating resin composition of the present disclosure to the lead frame and the balance between heat resistance and fluidity, it is preferable to contain a biphenyl-type epoxy resin. The proportion of the biphenyl type epoxy resin in the total epoxy resin is preferably from 10 mass % to 50 mass %, more preferably from 15 mass % to 45 mass %, and further preferably from 20 mass % to 40 mass %.

[0020] 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 preferable.

[0021] [ka]

[0022] In formula (II), R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

[0023] 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 preferable.

[0024] [ka]

[0025] In formula (III), R 9 and R 10 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

[0026] The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable.

[0027] [ka]

[0028] In formula (IV), R 11 and R 12represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

[0029] The sulfur-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom, and examples thereof include epoxy resins represented by the following general formula (V).

[0030] [ka]

[0031] In formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

[0032] The novolac epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac phenolic resin, and examples thereof include epoxy resins represented by the following general formula (VI).

[0033] [ka]

[0034] In formula (VI), R 14 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 15 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0035] The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) can be mentioned.

[0036] [ka]

[0037] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0038] The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane type phenolic resin obtained from an aromatic aldehyde compound and a phenolic compound is preferred, and an epoxy resin represented by the following general formula (VIII) is more preferred.

[0039] [ka]

[0040] In formula (VIII), R 17 and R 18 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3, and each k independently represents an integer of 0 to 4. n is an average value and represents a number of 0 to 10.

[0041] The copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. For example, an epoxy resin represented by the following general formula (IX) can be mentioned.

[0042] [ka]

[0043] In formula (IX), R 19~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, and each k is independently an integer of 0 to 4. Each l and m is an average value and a number of 0 to 10, and (l+m) is a number of 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either one of the following formulas (IX-1) or (IX-2). In formulas (IX-1) and (IX-2), R 19 ~R 21 The definitions of i, j and k are as follows: 19 ~R 21 The definitions of i, j and k are the same as those of i, j and k. n is 1 (when bonding via a methylene group) or 0 (when bonding not via a methylene group).

[0044] [ka]

[0045] The epoxy resin represented by the above general formula (IX) may be a random copolymer containing l structural units and m structural units randomly, an alternating copolymer containing them alternately, a copolymer containing them regularly, a block copolymer containing them in a block form, etc. Any one of these may be used alone, or two or more may be used in combination.

[0046] Another preferred copolymer epoxy resin is Epicron HP-5000 (trade name, DIC Corporation), a methoxynaphthalene-cresol formaldehyde co-condensation epoxy resin containing the following two structural units in a random, alternating or block order. For example, an epoxy resin represented by the following general formula is included. In the following general formula, n and m each represent an average value and a number from 0 to 10, and (n+m) represents a number from 0 to 10, preferably n and m each represent an average value and a number from 1 to 9, and (n+m) represents a number from 2 to 10.

[0047] [ka]

[0048] The aralkyl type epoxy resin is not particularly limited as long as it is an epoxy resin made from a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol, cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof. For example, an epoxy resin obtained by glycidyl etherification of a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol, cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof is preferred, and an epoxy resin represented by the following general formulas (X) and (XI) is more preferred.

[0049] [ka]

[0050] In formulae (X) and (XI), R 38 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 37 , R 39 ~R 41 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, each k is independently an integer of 0 to 4, and each 1 is independently an integer of 0 to 4. Each n is an average value and is independently a number of 0 to 10.

[0051] R in the above general formulas (II) to (XI) 8 ~R 21 and R 37 ~R 41 With respect to the above, the term "may all be the same or different" means, for example, that 8 to 88 R 8 This means that all of the R may be the same or different. 9 ~R21 and R 37 ~R 41 In addition, the numbers of each element in the formula may all be the same or different. 8 ~R 21 and R 37 ~R 41 may be the same or different. For example, R 9 and R 10 may be the same or different. In addition, the monovalent organic group having 1 to 18 carbon atoms in the general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

[0052] In the above general formulas (II) to (XI), n is an average value, and each is preferably independently in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the encapsulating resin composition during melt molding decreases, and the occurrence of filling defects, deformation of bonding wires (gold wires connecting elements and leads), etc. tends to be suppressed. It is more preferable to set n in the range of 0 to 4.

[0053] The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 40 g / eq to 1000 g / eq, more preferably 45 g / eq to 500 g / eq, and further preferably 50 g / eq to 350 g / eq. The epoxy equivalent of the epoxy resin is a value measured by a method conforming to JIS K 7236:2009.

[0054] The epoxy resin may be a solid or a liquid at 25°C. When the epoxy resin is a solid at 25°C, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of the balance between moldability and heat resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C. Furthermore, from the viewpoint of handleability during production of the encapsulating resin composition, the softening point or melting point of the epoxy resin is preferably 50°C to 130°C. In the present disclosure, the softening point refers to a value measured by the ring and ball method of JIS K 7234:1986. In the present disclosure, the melting point refers to a value measured in accordance with the visual observation method of JIS K 0064:1992.

[0055] From the viewpoint of the balance between moldability and heat resistance, the Mw of the epoxy resin is preferably 550-1,050, and more preferably 650-950.

[0056] The total content of the epoxy resin in the encapsulating resin composition is preferably 0.5% by mass to 60% by mass, more preferably 2% by mass to 50% by mass, and even more preferably 3% by mass to 45% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, etc.

[0057] (hardening agent) The encapsulating resin composition of the present disclosure preferably contains a curing agent. The type of the curing agent is not particularly limited, and can be selected from those generally used as components of encapsulating resin compositions. The curing agent may be used alone or in combination of two or more types. In the present disclosure, a curing agent is required to have a structure capable of reacting with an epoxy resin contained in the encapsulating resin composition to cure the encapsulating resin composition, and even a compound that is contained in a small amount and contributes little to the curing reaction of the encapsulating resin composition is considered to be included in the curing agent.

[0058] Examples of the curing agent include a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, a polymercaptan-based curing agent, a polyaminoamide-based curing agent, an isocyanate-based curing agent, and a blocked isocyanate-based curing agent. Among these, from the viewpoint of heat resistance, the curing agent is preferably a phenol-based curing agent or an amine-based curing agent.Furthermore, from the viewpoint of adhesion of the encapsulating resin composition of the present disclosure to a lead frame and from the viewpoint of heat resistance, the curing agent is preferably a phenol-based curing agent.

[0059] Examples of phenol-based curing agents include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule.Specific examples of the phenol-based curing agent include polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; novolac-type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde, under an acid catalyst; phenolic compounds synthesized from the above-mentioned phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, and the like; Examples of the phenolic curing agent include aralkyl-type phenolic resins such as nol aralkyl resins and naphthol aralkyl resins; paraxylylene and / or metaxylylene modified phenolic resins; melamine modified phenolic resins; terpene modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above phenolic compounds and dicyclopentadiene; cyclopentadiene modified phenolic resins; polycyclic aromatic ring modified phenolic resins; biphenyl type phenolic resins; triphenylmethane type phenolic resins obtained by condensing or co-condensing the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acid catalyst; and phenolic resins obtained by copolymerizing two or more of these. These phenolic curing agents may be used alone or in combination of two or more.

[0060] Examples of the aralkyl type phenolic resin include phenol aralkyl resins and naphthol aralkyl resins synthesized from a phenolic compound and dimethoxy-para-xylene, bis(methoxymethyl)biphenyl, etc. The aralkyl type phenolic resin may be further copolymerized with other phenolic resins. Examples of the copolymerized aralkyl type phenolic resin include a copolymerized phenolic resin of a triphenylmethane type phenolic resin and an aralkyl type phenolic resin, a copolymerized phenolic resin of a salicylaldehyde type phenolic resin and an aralkyl type phenolic resin, and a copolymerized phenolic resin of a novolac type phenolic resin and an aralkyl type phenolic resin.

[0061] The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds and naphthol compounds, and dimethoxy-para-xylene, bis(methoxymethyl)biphenyl or a derivative thereof. For example, phenolic resins represented by the following general formulas (XII) to (XIV) are preferred.

[0062] [ka]

[0063] In formulas (XII) to (XIV), R 23 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 22 , R 24 , R 25 and R 28 R represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 26 and R 27 represents a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, each k is independently an integer of 0 to 4, and each p is independently an integer of 0 to 4. Each n is an average value and is independently a number of 0 to 10.

[0064] From the viewpoint of adhesion to a lead frame and heat resistance of the encapsulating resin composition of the present disclosure, the aralkyl phenol resin is preferably a phenol resin represented by general formula (XIII). From the viewpoint of the adhesion to the lead frame and the heat resistance of the encapsulating resin composition of the present disclosure, it is preferable that i and k are both 0 in general formula (XIII).

[0065] The dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XV) can be mentioned.

[0066] [ka]

[0067] In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0068] The triphenylmethane type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from an aromatic aldehyde compound as a raw material. For example, a phenolic resin represented by the following general formula (XVI) is preferable.

[0069] [ka]

[0070] In formula (XVI), R 30 and R 31 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, and each k is independently an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0071] The copolymerized phenolic resin of triphenylmethane type phenolic resin and aralkyl type phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of aralkyl type phenolic resin and phenolic resin obtained from a compound having a benzaldehyde skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XVII) is preferable.

[0072] [ka]

[0073] In formula (XVII), R 32 ~R 34 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i is independently an integer of 0 to 3, each k is independently an integer of 0 to 4, and each q is independently an integer of 0 to 5. Each l and m is an average value, and each is independently a number of 1 to 11.

[0074] The novolac type phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds with an aldehyde compound under an acid catalyst. For example, a phenolic resin represented by the following general formula (XVIII) is preferred.

[0075] [ka]

[0076] In formula (XVIII), R 35 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 36 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0077] R in the above general formulas (XII) to (XVIII)22 ~R 36 The description of "may be the same or different" means, for example, that i R 22 This means that all of the R's may be the same or different from each other. 23 ~R 36 In addition, the numbers of each element in the formula may all be the same or different from each other. 22 ~R 36 may be the same or different. For example, R 22 and R 23 may be the same or different, and R 30 and R 31 may be the same or different.

[0078] In the above general formulas (XII) to (XVIII), n is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the encapsulating resin composition during melt molding also becomes low, making it difficult for filling defects, deformation of bonding wires (gold wires connecting elements and leads), etc. to occur. The average n in one molecule is preferably set in the range of 0 to 4.

[0079] Specific examples of the amine curing agent include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, and 2-methylaniline; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole; and imidazoline compounds such as imidazoline, 2-methylimidazoline, and 2-ethylimidazoline.

[0080] The functional group equivalent of the curing agent (hydroxyl group equivalent in the case of a phenol-based curing agent, active hydrogen equivalent 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, and more preferably 30 g / eq to 500 g / eq. The hydroxyl equivalent in the case of a phenol-based curing agent is a value calculated based on the hydroxyl value measured in accordance with JIS K 0070: 1992. The active hydrogen equivalent in the case of an amine-based curing agent is a value calculated based on the amine value measured in accordance with JIS K 7237: 1995.

[0081] When the curing agent is solid at 25° C., its softening point or melting point is not particularly limited. From the viewpoints of moldability and heat resistance, the softening point or melting point of the curing agent is preferably 40° C. to 180° C. Furthermore, from the viewpoint of handleability during production of the encapsulating resin composition, the softening point or melting point of the curing agent is preferably 50° C. to 130° C.

[0082] When the curing agent is a phenol-based curing agent, the equivalent ratio of the phenolic hydroxyl groups (active hydrogen) of the phenol-based curing agent to the epoxy groups of the epoxy resin in the encapsulating resin composition (the number of moles of the phenolic hydroxyl groups (active hydrogen) of the phenol-based curing agent / the number of moles of the epoxy groups of the epoxy resin) is not particularly limited, and can be, for example, 0.5 to 1.2, or alternatively 0.5 to 1.0, 0.55 to 0.9, or 0.6 to 0.8. When the equivalent ratio is 0.5 or more and less than 1.0, the adhesion between the cured product of the encapsulating resin composition and the supporting member tends to be improved. Although the reason for this is not clear, it is presumed that this is because the value of tan δ near the reflow temperature can be increased, and the internal stress of the cured resin during reflow is alleviated.

[0083] When the curing agent includes a phenol-based curing agent, from the viewpoint of adhesion of the encapsulating resin composition of the present disclosure to a lead frame, the content of the phenol-based curing agent relative to the total mass of the curing agent is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 70% by mass to 100% by mass.

[0084] When the phenol-based curing agent contains an aralkyl-type phenol resin, from the viewpoint of adhesion of the encapsulating resin composition of the present disclosure to a lead frame, the content of the aralkyl-type phenol resin relative to the total mass of the phenol-based curing agent is more preferably 60 mass% to 100 mass%, and further preferably 70 mass% to 100 mass%.

[0085] (Inorganic filler) The encapsulating resin composition of the present disclosure contains an inorganic filler. By containing an inorganic filler in the encapsulating resin composition, the hygroscopicity of the encapsulating resin composition is reduced, and the strength in a cured state tends to be improved. When the encapsulating resin composition is used as an encapsulant for a semiconductor package, it is preferable that the encapsulating resin composition contains an inorganic filler.

[0086] The inorganic material constituting the inorganic filler is not particularly limited. Specific examples of the inorganic material include silica such as spherical silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, aluminum nitride, boehmite, beryllia, magnesium oxide, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, mica, and titanates. An inorganic filler made of an inorganic material having a flame retardant effect may be used, such as aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as a composite hydroxide of magnesium and zinc, and zinc borate. The inorganic fillers may be used alone or in combination of two or more.

[0087] The shape of the inorganic filler is not particularly limited, and examples thereof include powder, spheres, fibers, etc. From the viewpoints of flowability during molding of the encapsulating resin composition and mold wear, a spherical shape is preferred.

[0088] The average particle diameter of the inorganic filler is not particularly limited. From the viewpoint of the balance between the viscosity, filling property, and the like of the encapsulating resin composition, the volume average particle diameter of the inorganic filler is preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 30 μm, and further preferably 0.5 μm to 25 μm. The volume average particle diameter of the inorganic filler can be measured as the volume average particle diameter (D50) by a laser diffraction scattering particle size distribution measuring device.

[0089] The particle size of the inorganic filler may be top cut, may be top cut at 100 μm or less, may be top cut at 85 μm or less, may be top cut at 75 μm or less, or may be top cut at 53 μm or less. The top cut particle size can be determined from the particle size distribution when the above volume average particle size (D50) is measured.

[0090] When the encapsulating resin composition contains an inorganic filler, the content thereof is not particularly limited. The content of the inorganic filler in the entire encapsulating resin composition is preferably 30% by mass to 90% by mass, more preferably 35% by mass to 80% by mass, and further preferably 40% by mass to 70% by mass. When the content of the inorganic filler is 30% by mass or more of the entire encapsulating resin composition, the properties of the cured product, such as the thermal expansion coefficient, thermal conductivity, and elastic modulus, tend to be further improved. When the content of the inorganic filler is 90% by mass or less of the entire encapsulating resin composition, an increase in the viscosity of the encapsulating resin composition is suppressed, and the flowability is further improved, tending to result in better moldability.

[0091] The content of the inorganic filler in the entire encapsulating resin composition is preferably 68 vol % to 86 vol %, more preferably 70 vol % to 84 vol %, and further preferably 72 vol % to 82 vol %. When the content of the inorganic filler is 68% by volume or more of the entire encapsulating resin composition, the properties of the cured product, such as the thermal expansion coefficient, thermal conductivity, elastic modulus, etc., tend to be further improved. When the content of the inorganic filler is 86% by volume or less of the entire encapsulating resin composition, an increase in the viscosity of the encapsulating resin composition is suppressed, and the flowability is further improved, tending to result in better moldability.

[0092] (Aromatic group-containing cyanoacrylate compounds) The encapsulating resin composition of the present disclosure contains an aromatic group-containing cyanoacrylate compound. In the present disclosure, the term "aromatic group-containing cyanoacrylate compound" refers to a cyanoacrylate compound that contains at least one aromatic group in the molecule. The aromatic group-containing cyanoacrylate compounds may be used alone or in combination of two or more.

[0093] The molecular weight of the aromatic group-containing cyanoacrylate compound is preferably 200 or more, more preferably 250 or more, and even more preferably 300 or more, from the viewpoint of suppressing volatilization of the aromatic group-containing cyanoacrylate compound. The molecular weight of the aromatic group-containing cyanoacrylate compound is preferably 1500 or less, more preferably 1000 or less, and even more preferably 500 or less, from the viewpoint of improving the mixability of the aromatic group-containing cyanoacrylate compound. The molecular weight of the aromatic group-containing cyanoacrylate compound is preferably 200 to 1500.

[0094] Examples of the aromatic group-containing cyanoacrylate compound include a compound represented by the following general formula (IA) and a compound represented by the following general formula (IB).

[0095] [ka]

[0096] In general formula (IA) and general formula (IB), R 1 and R 2 each independently represents an aromatic group; R 3 represents a monovalent organic group, R 4 represents a hydrogen atom or a monovalent organic group, and n represents an integer of 2 to 4. R 1 and R 2 Examples of the aromatic group represented by the formula (I) include an aryl group and an aralkyl group. R 1 and R 2 The number of carbon atoms in the aryl group represented by the following formula is preferably 6 to 25, more preferably 6 to 15, and further preferably 6 to 10. Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. The aryl group may have a substituent. Examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group, a carboxy group, a hydroxy group, an amino group, and a halogen atom. R 1 and R 2 The number of carbon atoms in the aralkyl group represented by the formula (I) is preferably 7 to 25, more preferably 7 to 15, and further preferably 7 to 11. Examples of the aralkyl group include a benzyl group and a phenethyl group. The aralkyl group may have a substituent. The substituent that the aralkyl group may have is the same as that of the aryl group. R 1 and R 2 The aromatic group represented by the formula (I) is preferably a phenyl group, and more preferably an unsubstituted phenyl group.

[0097] R 3 Examples of the monovalent organic group represented by the formula (I) include an alkyl group, an aryl group, and an aralkyl group, and an alkyl group is preferred. R 3 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 2 to 13 carbon atoms, and from the viewpoint of improving reflow resistance, is further preferably an alkyl group having 3 to 12 carbon atoms, and particularly preferably an alkyl group having 5 to 10 carbon atoms. R 3The alkyl group represented by the formula (I) may be linear, branched, or cyclic, and is preferably a branched alkyl group from the viewpoint of improving reflow resistance. R 3 From the viewpoint of improving reflow resistance, the alkyl group represented by the following formula is preferably a branched alkyl group having 3 to 12 carbon atoms, and more preferably a branched alkyl group having 5 to 10 carbon atoms. R 3 Specific examples of the aryl group and aralkyl group represented by the formula: 1 and R 2 The same is true for

[0098] R 4 Examples of the monovalent organic group represented by the formula (I) include an alkyl group, an aryl group, and an aralkyl group, and an alkyl group is preferred. R 4 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms. R 4 Specific examples of the aryl group and aralkyl group represented by the formula: 1 and R 2 The same is true for In formula (IB), n is preferably 3 to 4, and more preferably 4.

[0099] The aromatic group-containing cyanoacrylate compound preferably contains at least one of a compound represented by general formula (IA) and a compound represented by general formula (IB), and more preferably contains a compound represented by general formula (IA). 3 It is more preferable that the monovalent organic group represented by the formula (IA) is a branched alkyl group. 3 It is particularly preferable that the monovalent organic group represented by the following formula (I) is a branched alkyl group having 3 to 12 carbon atoms.

[0100] Specific examples of aromatic group-containing cyanoacrylate compounds include compound (1), compound (2), and compound (3) below, but the aromatic group-containing cyanoacrylate compounds used in the present disclosure are not limited to the specific examples below.

[0101] [ka]

[0102] The content of the aromatic group-containing cyanoacrylate compound is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 5 to 15 parts by mass, per 100 parts by mass of the epoxy resin in total. If the content of the aromatic group-containing cyanoacrylate compound is 1 part by mass or more per 100 parts by mass of the epoxy resin in total, the flowability of the encapsulating resin composition tends to be improved. If the content of the aromatic group-containing cyanoacrylate compound is 50 parts by mass or less per 100 parts by mass of the epoxy resin in total, the releasability of the encapsulating resin composition from a mold tends to be improved. When two or more aromatic group-containing cyanoacrylate compounds are used in combination, the proportion of the compound represented by general formula (IA) in the aromatic group-containing cyanoacrylate compounds is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more.

[0103] (Cure accelerator) The encapsulating resin composition of the present disclosure may contain a curing accelerator. The type of the curing accelerator is not particularly limited and can be selected according to the type of epoxy resin, the desired properties of the encapsulating resin composition, and the like. The curing accelerator may be used alone or in combination of two or more types. Specific examples of the curing accelerator are described below, but are not limited thereto. Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole, derivatives of the cyclic amidine compounds, phenol novolac salts of the cyclic amidine compounds or their derivatives, and combinations of these compounds with maleic anhydride, quinone compounds such as 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and the like. compounds having intramolecular polarization obtained by adding a compound having a π bond, such as 2-phenylphenylmethane; cyclic amidinium compounds, such as the tetraphenylborate salt of DBU, the tetraphenylborate salt of DBN, the tetraphenylborate salt of 2-ethyl-4-methylimidazole, and the tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds, such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the above tertiary amine compounds; ammonium salt compounds, such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide;organic phosphines such as primary phosphines, e.g., ethylphosphine, phenylphosphine, etc.; secondary phosphines, e.g., dimethylphosphine, diphenylphosphine, etc.; and tertiary phosphines, e.g., triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris(benzyl)phosphine; phosphine compounds, e.g., complexes of the organic phosphines and organic borons; and complexes of the organic phosphines or the phosphine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, compounds having intramolecular polarization obtained by adding a compound having a π bond, such as quinone compounds, such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and anthraquinone, and diazophenylmethane; compounds having intramolecular polarization obtained by adding a compound having a π bond, such as the organic phosphines or the phosphine compounds, and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, and 4-iodophenol; a compound having intramolecular polarization, which is obtained by reacting a halogenated phenol compound such as phenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation process;Examples of the tetra-substituted phosphonium include tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborate salts of tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetra-substituted phosphonium with phenolic compounds; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds. Suitable curing accelerators include triphenylphosphine, and adducts of triphenylphosphine with quinone compounds.

[0104] When the encapsulating resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.1 to 8 parts by mass, more preferably 0.3 to 7 parts by mass, and even more preferably 0.5 to 6 parts by mass, relative to 100 parts by mass of the total amount of the epoxy resin and the curing agent. By setting the content of the curing accelerator within the above numerical range, the curing speed of the encapsulating resin composition of the present disclosure becomes an appropriate numerical value, and the production of a molded product becomes easy.

[0105] (Various additives) In addition to the above-mentioned components, the encapsulating resin composition of the present disclosure may contain various additives such as a coupling agent, a stress relaxation agent, a release agent, a colorant, a flame retardant, an ion exchanger, etc. The encapsulating resin composition of the present disclosure may also contain a siloxane compound having a structural unit having an epoxy group and an alkoxy group and having a degree of polymerization of 2. The encapsulating resin composition may contain various additives known in the art, as necessary, in addition to the additives exemplified below.

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

[0107] The silane coupling agent is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane.

[0108] Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

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

[0110] (Stress reliever) The encapsulating resin composition of the present disclosure may contain a stress relaxation agent such as silicone oil or silicone rubber particles. By containing a stress relaxation agent in the encapsulating resin composition, 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 known stress relaxation agents (flexible agents) that are generally used. Specifically, examples of the stress relaxation agent include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers, natural rubber (NR), acrylonitrile-butadiene copolymer (NBR), acrylic rubber, urethane rubber, and silicone powder, and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. The stress relaxation agent may be used alone or in combination of two or more types. Among them, silicone-based stress relaxation agents are preferred. Examples of the silicone-based stress relaxation agent include those having an epoxy group, those having an amino group, and those modified with polyether. Triphenylphosphine oxide may also be used as a stress relieving agent.

[0111] When the encapsulating resin composition contains a stress relaxation agent, the content thereof is preferably 10 parts by mass to 60 parts by mass, and more preferably 20 parts by mass to 50 parts by mass, per 100 parts by mass of the epoxy resin contained in the encapsulating resin composition.

[0112] (Release agent) When a mold is used during molding, the encapsulating resin composition of the present disclosure may contain a mold release agent from the viewpoint of mold releasability. The mold release agent is not particularly limited, and a conventionally known one may be used. Examples of the mold release agent 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, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. The mold release agent may be used alone or in combination of two or more types.

[0113] When the encapsulating resin composition of the present disclosure contains a release agent, the content of the release agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the epoxy resin contained in the encapsulating resin composition. When the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the epoxy resin, sufficient releasability tends to be obtained. When the amount is 15 parts by mass or less, better releasability tends to be obtained.

[0114] (Coloring agent) The encapsulating resin composition of the present disclosure may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the colorant can be appropriately selected depending on the purpose. The colorant may be used alone or in combination of two or more types.

[0115] When the encapsulating resin composition contains a colorant, the content thereof is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 4% by mass.

[0116] (Flame retardant) The encapsulating resin composition of the present disclosure may contain a flame retardant. The flame retardant is not particularly limited, and a conventionally known one may be used. Examples of the flame retardant include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. The flame retardant may be used alone or in combination of two or more kinds.

[0117] When the resin composition for sealing of the present disclosure contains a flame retardant, its content is not particularly limited as long as it is an amount sufficient to obtain a desired flame retardant effect. The content of the flame retardant is preferably 1 part by mass to 300 parts by mass, more preferably 2 parts by mass to 150 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the resin composition for sealing.

[0118] (Ion exchanger) The resin composition for sealing of the present disclosure may contain an ion exchanger. When the resin composition for sealing is used as a sealing material for a semiconductor package, it is preferable to contain an inorganic ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device including the element to be sealed. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specifically, hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth can be mentioned. The ion exchanger may be used alone or in combination of two or more. Specifically, as the ion exchanger, hydrotalcite represented by the following general formula (A) can be mentioned.

[0119] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O···(A) (0 < X ≦ 0.5, m is a positive number)

[0120] When the resin composition for sealing of the present disclosure contains an ion exchanger, its content is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. The content of the ion exchanger is preferably 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the resin composition for sealing.

[0121] (Physical properties of the resin composition for sealing or its cured product) From the viewpoint of protecting the chip from external forces, the storage modulus of the cured product of the encapsulating resin composition at 260° C. is preferably 320 MPa or less, more preferably 310 MPa or less, and even more preferably 300 MPa or less. The storage modulus of the cured product of the encapsulating resin composition at 260° C. is preferably 80 MPa or more, more preferably 100 MPa or more, even more preferably 120 MPa or more, and particularly preferably 170 MPa or more.

[0122] The storage modulus of the cured product of the encapsulating resin composition is measured using a viscoelasticity measuring device (e.g., RSAIII manufactured by TA Instruments) under conditions of a span distance of 40 mm and a frequency of 1 Hz, by a three-point bending method in which the temperature is raised from 20°C to 300°C at a rate of 5°C / min, and the modulus at 260°C is determined. The cured product is produced by the method described later in the measurement of the linear expansion coefficient. The cured product used has a rectangular shape with short sides of 5.1 mm, long sides of 20 mm, and a thickness of 2 mm.

[0123] The linear expansion coefficient of the cured product of the encapsulating resin composition at 180° C. to 200° C. is preferably 32 ppm / ° C. or more, more preferably 34 ppm / ° C. or more, and even more preferably 36 ppm / ° C. or more. From the viewpoint of approximating the linear expansion coefficient of other members used together with the cured product, the upper limit of the linear expansion coefficient is preferably 60 ppm / ° C. or less, more preferably 55 ppm / ° C. or less, even more preferably 50 ppm / ° C. or less, and particularly preferably 42 ppm / ° C. or less.

[0124] In the present disclosure, the linear expansion coefficient is the slope of the tangent at 180°C to 200°C when the distortion of the cured material is plotted against the temperature by thermal mechanical analysis (TMA) based on JIS K 7197:2012. The test load is 5 g and the heating rate is 5°C / min. The linear expansion coefficient can be measured using a thermomechanical analyzer (for example, TMA / SS6100 manufactured by Seiko Instruments Inc.). The cured product is produced by molding the encapsulating resin composition using a transfer molding machine under conditions of a mold temperature of 175° C., molding pressure of 6.9 MPa, and curing time of 90 seconds, and then post-curing for 5 hours at 175° C. The cured product has a rectangular shape with short sides of 5.1 mm, long sides of 20 mm, and a thickness of 2 mm.

[0125] The adhesive strength of the cured product of the encapsulating resin composition to Ag (silver) is preferably 0.10 MPa or more, more preferably 0.15 MPa or more, and even more preferably 0.20 MPa or more. There is no particular upper limit to the adhesive strength.

[0126] In measuring the adhesive strength of the cured product of the encapsulating resin composition to Ag (silver), the encapsulating resin composition is applied onto an Ag substrate, cured at 175°C for 120 seconds, and then post-cured at 175°C for 5 hours to prepare a sample. The cured product of the sample has a shape of 3.0 mm short side, 3.5 mm long side, and 2.9 mm thick. The sample is heated at 85°C and 85% RH for 168 hours, and then a shear strength test is performed using a bond tester (e.g., Nordson, product name 4000 Optima) to apply a tool of the device to the cured product at 260°C to measure the adhesive strength.

[0127] From the viewpoint of fluidity, the encapsulating resin composition of the present disclosure has a spiral flow measured by the following method of preferably 100 cm or more, more preferably 105 cm or more, and even more preferably 110 cm or more. The upper limit of the spiral flow is not particularly limited, and may be 200 cm or less.

[0128] The spiral flow is measured using a spiral flow measurement mold conforming to EMMI-1-66, and the flow distance is determined when the encapsulating resin composition is molded under conditions of a mold temperature of 175°C, molding pressure of 6.9 MPa, and curing time of 90 seconds.

[0129] From the viewpoint of fluidity, the gel time of the encapsulating resin composition at 175° C. is preferably 15 seconds or more, more preferably 18 seconds or more, even more preferably 20 seconds or more, and particularly preferably 21 seconds or more. From the viewpoint of curability, the gel time is preferably 50 seconds or less, more preferably 47 seconds or less, and even more preferably 44 seconds or less.

[0130] The gel time is measured from the time when 0.5 g of the encapsulating resin composition is placed on a hot plate preheated to 175°C to the time when the encapsulating resin composition loses its viscosity. It is preferable to heat the encapsulating resin composition while periodically stirring it with a spatula or the like. "The encapsulating resin composition loses its viscosity" refers to the phenomenon in which the encapsulating resin composition breaks or is destroyed when the encapsulating resin composition is kneaded with a spatula or the like.

[0131] The viscosity of the encapsulating resin composition of the present disclosure at 175° C. is preferably 0.01 Pa·s to 1000 Pa·s, more preferably 0.1 Pa·s to 200 Pa·s, even more preferably 1 Pa·s to 50 Pa·s, and particularly preferably 1 Pa·s to 20 Pa·s. The viscosity of the encapsulating resin composition at 175° C. is measured using a flow tester viscometer at a pressure of 1 MPa, with a nozzle diameter of 1 mm and a length of 10 mm.

[0132] From the viewpoint of heat resistance, etc., the glass transition temperature (Tg) of the cured product of the encapsulating resin composition is preferably 80° C. or higher, more preferably 85° C. or higher, and even more preferably 90° C. or higher. There is no particular upper limit to the Tg, and it may be 200° C. or lower, or 180° C. or lower.

[0133] In the present disclosure, the glass transition temperature of the cured product is defined as the temperature at the intersection of a tangent line at 40°C to 60°C and a tangent line at 200°C to 220°C, obtained by measuring the linear expansion coefficient.

[0134] From the viewpoint of moldability, handleability, and the like of the encapsulating resin composition, the hot hardness of the cured product is preferably 55 or more, more preferably 56 or more, even more preferably 57 or more, and particularly preferably 58 or more. There is no particular upper limit to the hot hardness, and it may be 90 or less, 80 or less, or 70 or less.

[0135] The hot hardness of the cured product is measured at 175°C using a Shore hardness tester Type D (e.g., manufactured by Kobunshi Keiki Co., Ltd.) for a rectangular parallelepiped test piece for hot hardness measurement having dimensions of 4 mm x 80 mm x 10 mm. The test piece is obtained by curing and molding the encapsulating resin composition using a transfer molding machine and a disk mold under conditions of 175°C, 120 seconds, and a pressure of 7 MPa. The measurement is performed in the press immediately after the preparation of the test piece.

[0136] From the viewpoint of moldability, handling, etc. of the encapsulating resin composition, the hot strength of the cured product is preferably 3 MPa or more, more preferably 3.5 MPa or more, and even more preferably 4 MPa or more. The upper limit of the hot strength is not particularly limited, and may be 20 MPa or less, 15 MPa or less, or 10 MPa or less.

[0137] The hot strength of the cured product is measured using a rectangular parallelepiped test piece for measuring hot strength, measuring 4 mm × 80 mm × 10 mm, using a load tester (e.g., Aiko Engineering Co., Ltd., tabletop tester 1301K). The test piece is obtained by curing and molding the curable resin composition using a transfer molding machine and a disk mold under conditions of 175°C, 120 seconds, and a pressure of 7 MPa.

[0138] (Method of producing encapsulating resin composition) The method for producing the encapsulating resin composition is not particularly limited. A general method includes a method in which a predetermined amount of components is thoroughly mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder, or the like, cooled, and pulverized. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like that has been heated to 70°C to 140°C in advance, cooled, and pulverized can be mentioned.

[0139] The encapsulating resin composition is preferably a solid at 25° C. When the encapsulating resin composition is a solid at 25° C., the shape of the encapsulating resin composition is not particularly limited, and examples thereof include powder, granules, tablets, etc. When the encapsulating resin composition is in tablet form, it is preferable from the viewpoint of handleability that the dimensions and mass are set to be suitable for the molding conditions of the package.

[0140] (Uses of encapsulating resin composition) The use of the encapsulating resin composition of the present disclosure is not particularly limited, and it can be used in various mounting techniques, for example, as an encapsulant for electronic component devices. In addition, the encapsulating resin composition of the present disclosure can be used in various applications in which it is desirable for the resin composition to have good fluidity and curability, such as resin molded articles for various modules, resin molded articles for motors, resin molded articles for vehicles, and encapsulants for electronic circuit protection materials.

[0141] <Electronic component equipment> The electronic component device of the present disclosure includes an element and a cured product of the encapsulating resin composition that encapsulates the element.

[0142] The electronic component device may include a support member on which an element is mounted. Examples of the support member include a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, an organic substrate, etc. Among the above support members, a lead frame is preferred from the viewpoint of adhesion to the cured product of the encapsulating resin composition. The lead frame may have an element mounted on one side thereof.

[0143] The lead frame may or may not have a roughened surface, but from the standpoint of manufacturing costs, a lead frame is preferred, and from the standpoint of adhesion, a roughened lead frame is preferred. The surface roughening method is not particularly limited, and examples thereof include alkali treatment, silane coupling treatment, sand matt treatment, plasma treatment, and corona discharge treatment.

[0144] The lead frame preferably contains Ag, and may further contain Cu and the like.

[0145] Examples of elements included in an electronic component device include active elements such as silicon chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils.

[0146] Specific configurations of the electronic component device include, but are not limited to, the following configurations. (1) General resin-sealed ICs such as DIPs (Dual Inline Packages), PLCCs (Plastic Leaded Chip Carriers), QFPs (Quad Flat Packages), SOPs (Small Outline Packages), SOJs (Small Outline J-lead Packages), TSOPs (Thin Small Outline Packages), and TQFPs (Thin Quad Flat Packages), which have a structure in which an element is fixed on a lead frame, and terminals of the element such as bonding pads and leads are connected using wire bonding, bumps, or the like, and then sealed using a sealing resin composition; (2) TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier using bumps is encapsulated using an encapsulating resin composition; (3) COB (Chip On Board) modules, hybrid ICs, multi-chip modules, etc., having a structure in which elements are connected to wiring formed on a support member by wire bonding, flip chip bonding, solder, etc., and then encapsulated with an encapsulating resin composition; (4) BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), SiP (System in a Package), etc., which have a structure in which an element is mounted on the surface of a support member having terminals for connecting a wiring board formed on the back surface thereof, the element is connected to the wiring formed on the support member using bumps or wire bonding, and then the element is encapsulated using an encapsulating resin composition.

[0147] The method for encapsulating an element using the encapsulating resin composition is not particularly limited, and any known method can be applied. As the encapsulating method, for example, low pressure transfer molding is generally used, but injection molding, compression molding, casting, etc. may also be used. EXAMPLES

[0148] [Examples 1 to 3 and Comparative Example 1] The materials shown in Table 1 were premixed (dry blended), then kneaded for about 15 minutes with a biaxial roll (roll surface temperature: about 80°C), cooled, and pulverized to produce a powdered encapsulating resin composition. The equivalent ratio of the phenolic hydroxyl group (active hydrogen) of the phenolic curing agent to the epoxy group of the epoxy resin was 0.7.

[0149] Details of the materials in Table 1 are as follows. In Table 1, the content of the inorganic filler indicates the volume ratio or mass ratio in the encapsulating resin composition. The other components are in parts by mass.

[0150] Epoxy resin A: Naphthalene type, epoxy equivalent 251g / eq Epoxy resin B: Biphenyl type, epoxy equivalent 196g / eq

[0151] Hardener A: Phenol aralkyl resin, hydroxyl equivalent 175g / eq Hardener B: Alkyl-modified phenolic resin, hydroxyl equivalent 223g / eq

[0152] Curing accelerator: 1,4-benzoquinone adduct of triphenylphosphine Inorganic filler: Spherical silica particles with a top cut of 75 μm and a volume average particle size of 19 μm

[0153] Coupling agent A: N-phenyl-3-aminopropyltrimethoxysilane Coupling agent B: 3-glycidoxypropyltrimethoxysilane

[0154] Release agent: Ethanediol montanic acid ester Colorant: Carbon black Ion exchanger: Hydrotalcite

[0155] Aromatic group-containing cyanoacrylate compound (1): Compound (1) above, molecular weight = 1060, white granules at 25°C Aromatic group-containing cyanoacrylate compound (2): Compound (2) above, molecular weight = 277, white powder at 25°C Aromatic group-containing cyanoacrylate compound (3): Compound (3) above, molecular weight = 361, pale yellow liquid at 25°C Stress relaxant A: Triphenylphosphine oxide Stress relief agent B: Silicone resin

[0156] <<Evaluation of encapsulating resin composition>> The properties of the encapsulating resin compositions prepared in the examples and comparative examples were measured and evaluated by the following methods. The evaluation results are shown in Table 2.

[0157] <Spiral flow measurement> The spiral flow of the encapsulating resin composition was measured by the above-mentioned method.

[0158] <Gel time measurement> The gel time of the encapsulating resin composition was measured by the above-mentioned method.

[0159] <Viscosity measurement> The viscosity of the encapsulating resin composition at 175° C. was measured by the method described above.

[0160] <Measurement of Linear Expansion Coefficient of Cured Product> Using the above method, the linear expansion coefficient of the cured product of the resin composition for sealing was measured at 180°C to 200°C. As the thermomechanical analyzer, TMA / SS6100 manufactured by Seiko Instruments Inc. was used.

[0161] <Glass Transition Temperature (Tg) of Cured Product> The temperature at the intersection of the tangent line at 40°C to 60°C and the tangent line at 200°C to 220°C obtained by the measurement of the above linear expansion coefficient was defined as the glass transition temperature of the cured product.

[0162] <Measurement of Storage Elastic Modulus of Cured Product> Using the above method, the storage elastic modulus of the cured product of the resin composition for sealing was measured at 260°C. As the viscoelasticity measuring apparatus, RSAIII manufactured by TA Instruments was used.

[0163] <Measurement of Adhesion Strength to Ag (Silver)> Using the above method, the adhesion strength to Ag (silver) of the cured product of the resin composition for sealing was measured. As the measuring apparatus, 4000 Optima manufactured by Nordson was used.

[0164] <Measurement of Hardness at High Temperature> Using the above method, the hardness at high temperature of the cured product of the resin composition for sealing was measured. As the measuring apparatus, Shore hardness tester type D manufactured by Kobunshi Keiki Co., Ltd. was used.

[0165] <Measurement of Strength at High Temperature> Using the above method, the strength at high temperature of the cured product of the resin composition for sealing was measured. As the measuring apparatus, tabletop testing machine 1301K manufactured by AIKO Engineering Co., Ltd. was used.

[0166] <Evaluation of Peelability at High Temperature and High Humidity> The encapsulating resin composition obtained as described above was used to mold using a transfer molding machine under conditions of a mold temperature of 175°C, a molding pressure of 11.3 MPa, and a curing time of 120 seconds. The resulting cured product was then heated at 175°C for 5 hours to produce an 80-pin flat package (lead frame material: AgCu) with external dimensions of 20 mm in length, 14 mm in width, and 2 mm in thickness and equipped with an encapsulated silicon chip (8 mm in length, 10 mm in width, 0.4 mm in thickness). The above packages were heated under two conditions: 85° C., 60% RH for 168 hours (MSL2), and 30° C., 60% RH for 696 hours (MSL2a). After that, each package was subjected to a reflow process for 10 seconds at 260°C, and the presence or absence of peeling inside the package was observed using an ultrasonic flaw detector (Nordson SONOSCAN, Gen-6 CSAM). Peelability was evaluated based on the number of packages that peeled out of the number of test packages.

[0167] [Table 1]

[0168] [Table 2]

[0169] As shown in Table 2, the spiral flow of the encapsulating resin compositions of the Examples is higher than that of the encapsulating resin compositions of the Comparative Examples, which shows that the encapsulating resin compositions of the Examples have excellent fluidity.

Claims

1. An encapsulating resin composition comprising an epoxy resin, a curing agent, an inorganic filler, and an aromatic group-containing cyanoacrylate compound.

2. 2. The encapsulating resin composition according to claim 1, wherein the aromatic group-containing cyanoacrylate compound has a molecular weight of 200 or more.

3. The encapsulating resin composition according to claim 1, wherein the aromatic group-containing cyanoacrylate compound contains at least one of a compound represented by the following general formula (IA) and a compound represented by the following general formula (IB): 【Chemistry 1】 (In general formula (IA) and general formula (IB), R １ and R ２ each independently represents an aromatic group; R ３ represents a monovalent organic group; R ４ represents a hydrogen atom or a monovalent organic group; and n represents an integer of 2 to 4.

4. 4. The encapsulating resin composition according to claim 3, wherein the aromatic group-containing cyanoacrylate compound contains a compound represented by general formula (IA).

5. R in the compound represented by the general formula (IA) ３ The encapsulating resin composition according to claim 3 , wherein the monovalent organic group represented by the formula:

6. 6. The encapsulating resin composition according to claim 5, wherein the branched alkyl group has 3 to 12 carbon atoms.

7. 2. The encapsulating resin composition according to claim 1, wherein the content of the aromatic group-containing cyanoacrylate compound is 1 to 50 parts by mass based on 100 parts by mass of the epoxy resin.

8. 2. The encapsulating resin composition according to claim 1, wherein the content of the inorganic filler in the entire encapsulating resin composition is 68% by volume to 86% by volume.

9. 2. The encapsulating resin composition according to claim 1, which has a spiral flow in accordance with EMMI-1-66 of 100 cm or more.

10. 2. The encapsulating resin composition according to claim 1, which has a hot hardness of 56 or more when cured.

11. 2. The encapsulating resin composition according to claim 1, which has a hot strength of 3 MPa or more when cured.

12. An electronic component device comprising: an element; and a cured product of the encapsulating resin composition according to any one of claims 1 to 11 for encapsulating the element.

13. The electronic component device according to claim 12 , further comprising a lead frame having one surface on which the element is mounted.

Images