Curable resin composition and electronic component device

Abstract

To provide a curable resin composition that prevents delamination from a lead frame even when a cured product undergoes moisture absorption under conditions of 85°C and 85% RH, and to provide an electronic component device comprising an element sealed with the curable resin composition.SOLUTION: This curable resin composition contains an epoxy resin. A cured product of the curable resin composition exhibits an adhesive strength of 0.40 MPa or more to AgCu at 260°C after being heated and humidified for 168 hours at 85°C and 85% RH.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, high-density mounting of semiconductor elements has been progressing. Along with this, resin-sealed semiconductor devices have shifted from conventional pin-insertion type packages to surface-mount type packages as the mainstream. Surface-mount type ICs (Integrated Circuits), LSIs (Large Scale Integrations), etc. have become thin and small packages in order to increase the mounting density and reduce the mounting height. Therefore, the occupied area of the element with respect to the package has increased, and the thickness of the package has become very thin.

[0003] Furthermore, these packages have a different mounting method from pin-insertion type packages. That is, in a pin-insertion type package, after inserting the pins into the wiring board, soldering is performed from the back surface of the wiring board, so the package has a structure in which it is not directly exposed to high temperatures. However, surface-mount type ICs are temporarily fixed on the surface of the wiring board and processed by 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 is moisture-absorbed, the moisture absorbed during reflow vaporizes, and the generated vapor pressure acts as a peeling stress, causing peeling between the support members such as elements and lead frames and the encapsulant, leading to the occurrence of package cracks and electrical characteristic defects. Therefore, the development of a sealing material having excellent adhesiveness to the support member and thus excellent solder heat resistance (reflow resistance) is desired.

[0004] As a sealing material having excellent reflow resistance, a curable resin composition containing an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and an alkoxysilane polymer having a specific structure has been proposed in Patent Document 1. In addition, for the purpose of improving reflow resistance, for example, the surface of the lead frame is roughened before plating treatment to improve the adhesiveness with the encapsulant.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Development of an encapsulant that suppresses peeling from the lead frame even under more severe moisture absorption conditions (for example, moisture absorption conditions of 85°C and 85% RH) is desired. The present disclosure has been made in view of the above situation, and provides a curable resin composition in which peeling from the lead frame is suppressed even when the cured product is moisture-absorbed under conditions of 85°C and 85% RH, and an electronic component device including an element encapsulated with this curable resin composition.

Means for Solving the Problems

[0007] <1> A curable resin composition containing an epoxy resin, wherein the adhesive strength at 260°C after heating and humidifying at 85°C and 85% RH for 168 hours with respect to AgCu of the cured product is 0.40 MPa or more. <2> Further containing a curing agent, The curable resin composition according to <1>, wherein the curing agent / epoxy resin, which is the equivalent ratio of the curing agent and the epoxy resin, is 0.8 or less. <3> The curable resin composition according to <1> or <2>, wherein the glass transition temperature of the cured product is higher than 110°C. <4> The curable resin composition according to any one of <1> to <3>, wherein the coefficient of thermal expansion α2 measured at 180°C to 200°C is 32.0 ppm / °C or more. <5> The epoxy resin includes at least one selected from the group consisting of a triphenylmethane type epoxy resin containing a t-Bu group and a biphenyl type epoxy resin. <1> ~ <4> 13. The curable resin composition according to claim 12, <6> Further containing inorganic filler <1> ~ <5> 13. The curable resin composition according to claim 12, <7> An element, The element is sealed. <1> ~ <6> A cured product of the curable resin composition according to any one of the above items. An electronic component device comprising: <8> A lead frame is provided on one surface of which the element is mounted. <7> The electronic component device according to claim 1 . <9> The lead frame comprises Ag; <8> The electronic component device according to claim 1 . Effect of the Invention

[0008] According to the present disclosure, it is possible to provide a curable resin composition that suppresses peeling from a lead frame even when the cured product is subjected to moisture absorption under conditions of 85°C and 85% RH, and an electronic component device including an element encapsulated with this curable resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0010] In the present disclosure, a 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 value or lower limit value described in one numerical range may be replaced with the upper limit value or lower limit value of the numerical range described in other step-by-step descriptions. Also, in the numerical ranges described in the present disclosure, the upper limit value or lower limit value of the numerical range may be replaced with the value shown in the synthesis example. In the present disclosure, each component may contain a plurality of corresponding compounds. When there are a plurality of substances corresponding to each component in the composition, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition, unless otherwise specified. In the present disclosure, the particles corresponding to each component may contain a plurality of types. When there are a plurality of types of particles corresponding to each component in the composition, the particle diameter of each component means a value for the mixture of the plurality of types of particles present in the composition, unless otherwise specified. In the present disclosure, the term "lamination" represents stacking layers, and two or more layers may be bonded, and two or more layers may be detachable. In the notation of the groups (atomic groups) of the present disclosure, the notation that does not indicate substitution and non-substitution includes both those having no substituent and 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 a plurality of types of molecules. In the present disclosure, the number of carbon atoms means the total number of carbon atoms contained in the entire group. When the group has no substituent, it represents the number of carbon atoms forming the skeleton of the group. When the group has a substituent, it represents the total number obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the skeleton of the group.

[0011] 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 the calibration curve of standard polystyrene. However, for compounds whose accurate Mw cannot be measured by GPC due to their small molecular weight, the molecular weight determined from the chemical structure of the compound is adopted as the Mw, Mn or degree of polymerization of the compound. Examples of measurement devices include the following. For the creation of a calibration curve, a set of 5 samples of standard polystyrene ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation) may be used.

[0012] (GPC Measurement Device) GPC Device: High-speed GPC device "HCL-8320GPC", detector is a differential refractometer or UV, manufactured by Tosoh Corporation Column: 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 °C Flow Rate: 0.35 mL / min Sample Concentration: 10 mg / 5 mL of THF Injection Volume: 20 μL

[0013] <Curable Resin Composition> The curable resin composition of the present disclosure contains an epoxy resin, and the adhesive strength at 260 °C after heating and humidifying the cured product at 85 °C and 85% RH for 168 hours against AgCu is 0.40 MPa or more.

[0014] Since the adhesive strength of the curable resin composition of the present disclosure is 0.40 MPa or more, even when the cured product is hygroscopic at 85 °C and 85% RH for 168 hours, peeling from the lead frame is suppressed, and the ratio of the cured product peeling from the lead frame to the number of packages can be greatly reduced.

[0015] (Epoxy Resin) The curable resin composition of the present disclosure contains an epoxy resin. The epoxy resin may be used alone or in combination of two or more.

[0016] As the epoxy resin, a novolac epoxy resin 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, resorcinol, catechol, bisphenol A, bisphenol F, etc. and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc. with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst (phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, etc.); a triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc. under an acidic catalyst; a copolymer type epoxy resin obtained by epoxidizing a novolac resin obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst; a diphenylmethane type epoxy resin which is a diglycidyl ether of bisphenol A, bisphenol F, etc.; a biphenyl type epoxy resin which is a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a stilbene type epoxy resin which is a diglycidyl ether of a stilbene-based phenolic compound; a sulfur atom-containing type epoxy resin which is a diglycidyl ether of bisphenol S, etc.; an epoxy resin which is a glycidyl ether of alcohols such as butanediol, polyethylene glycol, polypropylene glycol, etc.; a glycidyl ester type epoxy resin which is a glycidyl ester of a polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.; a glycidylamine type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid, etc. is substituted with a glycidyl group; a dicyclopentadiene type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenolic compound;Vinylcyclohexene diepoxide, which is obtained by epoxidizing the olefin bond within the molecule, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane; Para-xylylene-modified epoxy resin, which is a glycidyl ether of para-xylylene-modified phenol resin; Meta-xylylene-modified epoxy resin, which is a glycidyl ether of meta-xylylene-modified phenol resin; Terpene-modified epoxy resin, which is a glycidyl ether of terpene-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin, which is a glycidyl ether of cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin, which is a glycidyl ether of polycyclic aromatic ring-modified phenol resin; Naphthalene-type epoxy resin, which is a glycidyl ether of naphthalene ring-containing phenol resin; Halogenated phenol novolak-type epoxy resin; Hydroquinone-type epoxy resin; Trimethylolpropane-type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Aralkyl-type epoxy resin, which is obtained by epoxidizing an aralkyl-type phenol resin such as a phenol aralkyl resin or a naphthol aralkyl resin; and the like. Further, aminophenol-type epoxy resin, which is a glycidyl ether of aminophenol, etc. are also mentioned as epoxy resins.;

[0017] The epoxy resin preferably contains at least one selected from the group consisting of triphenylmethane-type epoxy resins and biphenyl-type epoxy resins, and more preferably contains at least one selected from the group consisting of triphenylmethane-type epoxy resins containing a t-Bu group and biphenyl-type epoxy resins.

[0018] From the viewpoint of suppressing the peeling of the cured product of the curable resin composition from the support member (for example, a support member containing AgCu), the epoxy resin preferably contains a triphenylmethane-type epoxy resin.

[0019] The triphenylmethane type epoxy resin preferably contains an epoxy resin having at least one selected from the group consisting of an alkyl group and an alkoxy group (hereinafter also referred to as a specific triphenylmethane type epoxy resin). When the triphenylmethane type epoxy resin has at least one selected from the group consisting of an alkyl group and an alkoxy group, the monomer becomes bulky and the molecular weight of the monomer increases, resulting in a polymer with a widened intermolecular distance and low crosslink density after polymerization. This results in fewer molecules per unit volume, and the molecules are easily dissolved when tensile stress is applied, so that a reduction in the modulus of elasticity and an increase in the linear expansion coefficient of the cured product of the curable resin composition are expected. As a result, the stress (combination of strain, modulus of elasticity, linear expansion difference, and temperature difference) caused by the linear expansion difference between the support members is reduced and can be reduced to below the adhesive force of the resin, so that the cured product of the curable resin composition is prevented from peeling off from the support member. It is presumed that the reflow resistance is also improved.

[0020] The alkyl group in the specific triphenylmethane type epoxy resin preferably has a carbon number of 1 to 20, more preferably 1 to 16, and further preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but at least one of the alkyl groups is preferably branched and preferably contains a t-butyl group.

[0021] The alkoxy group contained in the specific triphenylmethane type epoxy resin preferably has a carbon number of 1 to 20, more preferably 1 to 16, and further preferably 1 to 10. The alkoxy group may be linear, branched, or cyclic.

[0022] It is preferable that the benzene ring contained in the specific triphenylmethane type epoxy resin has two or more alkyl groups, and it is more preferable that the benzene ring contained in the main chain has two or more alkyl groups. At least one of the two or more alkyl groups possessed by the benzene ring is preferably a branched alkyl group, and the branched alkyl group is preferably arranged at the ortho position with respect to the glycidyloxy group.

[0023] The specific triphenylmethane type epoxy resin may be an epoxy resin represented by the following formula (1).

[0024]

Chemical formula

[0025] In formula (1), each R independently represents an alkyl group or an alkoxy group, each i independently represents an integer from 1 to 3, and each k independently represents an integer from 0 to 4. n is an average value and represents a number from 0 to 10.

[0026] Examples of the alkyl group and alkoxy group represented by R are those described above. i represents an integer from 1 to 3, preferably 2 or 3, and more preferably 2. When i is 2, at least one of the Rs represented by the subscript i is preferably a branched alkyl group, more preferably a combination of a branched alkyl group and a linear alkyl group. For example, a combination of a t-butyl group and a methyl group can be mentioned. The t-butyl group and the methyl group may be arranged at any position on the benzene ring, but the t-butyl group is preferably arranged at the ortho position with respect to the glycidyloxy group. Also, the arrangement relationship between the t- butyl group and the methyl group may be any, and they may be arranged at the ortho, meta, or para position. Each k independently represents an integer from 0 to 4, and 0 is preferable.

[0027] Specific examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following formula (2).

[0028]

Chemical formula

[0029] The content of the specific triphenylmethane type epoxy resin is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass with respect to the total amount of the triphenylmethane type epoxy resin.

[0030] Among the above epoxy resins, from the viewpoints of the adhesiveness to the lead frame of the curable resin composition of the present disclosure and the balance between heat resistance and fluidity, it is preferable to contain a biphenyl type epoxy resin.

[0031] 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.

[0032]

Chemical formula

[0033] 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 all of them may be the same or different. n is an average value and represents a number from 0 to 10.

[0034] 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.

[0035]

Chemical formula

[0036] In formula (III), R 9 and R 10 each represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. n is an average value and represents a number from 0 to 10.

[0037] 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.

[0038]

Chemical formula

[0039] In formula (IV), R 11 and R 12 each represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. n is an average value and represents a number from 0 to 10.

[0040] The sulfur atom-containing type epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, an epoxy resin represented by the following general formula (V) can be mentioned.

[0041]

Chemical formula

[0042] In formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. n is an average value and represents a number from 0 to 10.

[0043] 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 represented by the following general formula (VI) can be mentioned.

[0044] [Chem.]

[0045] 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 from each other. R 15 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different from each other. i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0046] 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.

[0047] [Chem.]

[0048] 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 from each other. i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0049] The copolymer-type 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 using 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.

[0050] [Chem.]

[0051] In formula (IX), R 19 ~R 21represents a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. i each independently represents an integer from 0 to 3, j each independently represents an integer from 0 to 2, and k each independently represents an integer from 0 to 4. l and m are each average values, numbers from 0 to 10, and (l + m) represents a number from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either of the following formula (IX-1) or (IX-2). In formula (IX-1) and (IX-2), R 19 ~R 21 , the definitions of i, j, and k are the same as those of R 19 ~R 21 in formula (IX), i, j, and k. n is 1 (when bonded via a methylene group) or 0 (when not bonded via a methylene group).

[0052]

Chemical formula

[0053] Examples of the epoxy resin represented by the above general formula (IX) include 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 of them may be used in combination.

[0054] As the copolymer-type epoxy resin, Epiklon HP-5000 (trade name, manufactured by DIC Corporation), which is a methoxynaphthalene-cresol formaldehyde co-condensed type epoxy resin containing the following two structural units in a random, alternating, or block order, is also preferable. For example, an epoxy resin represented by the following general formula may be mentioned. In the following general formula, n and m are each average values, numbers from 0 to 10, and (n + m) represents a number from 0 to 10. Preferably, n and m are each average values, numbers from 1 to 9, and (n + m) represents a number from 2 to 10.

[0055]

Chemical formula

[0056] 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 and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof. For example, an epoxy resin obtained by glycidyl etherifying a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof is preferred, and epoxy resins represented by the following general formulas (X) and (XI) are more preferred.

[0057]

Chemical formula

[0058] In formulas (X) and (XI), R 38 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 from each other. R 37 , R 39 ~R 41 represent monovalent organic groups having 1 to 18 carbon atoms, and all of them may be the same or different from each other. i is an integer of 0 to 3 independently, j is an integer of 0 to 2 independently, k is an integer of 0 to 4 independently, and l represents an integer of 0 to 4 independently. n is an average value and is a number of 0 to 10 independently.

[0059] Regarding R 8 ~R 21 and R 37 ~R 41 in the above general formulas (II) to (VII), (IX) to (XI), "all of them may be the same or different from each other" means, for example, that all of the 8 to 88 R 8 in formula (II) may be the same or different from each other. For the other R 9 ~R21 and R 37 ~R 41 For each of them included in the formula, it means that all of the respective numbers may be the same or different. Also, R 8 ~R 21 and R 37 ~R 41 may each be the same or different. For example, all of R 9 and R 10 may be the same or different. Also, the monovalent organic group having 1 to 18 carbon atoms in the general formulas (III) to (VII), (IX) to (XI) is preferably an alkyl group or an aryl group.

[0060] In the above general formulas (II) to (VII), (IX) 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, the viscosity during melt molding of the curable resin composition decreases, and the occurrence of filling defects, deformation of bonding wires (gold wires connecting the element and the lead), etc. tends to be suppressed. More preferably, n is set in the range of 0 to 4.

[0061] 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 even more preferably 50 g / eq to 350 g / eq. The epoxy equivalent of the epoxy resin shall be the value measured by the method according to JIS K 7236:2009.

[0062] The epoxy resin may be solid or liquid at 25°C. When the epoxy resin is 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. Further, from the viewpoint of handleability during the production of the curable 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 the value measured by the ring and ball method of JIS K 7234:1986. In the present disclosure, the melting point refers to the value measured in accordance with the visual method of JIS K 0064:1992.

[0063] From the viewpoint of the balance between moldability and heat resistance, the Mw of the epoxy resin is preferably 550 to 1050, more preferably 650 to 950.

[0064] The proportion of the triphenylmethane type epoxy resin in 100 parts by mass of the total amount of the epoxy resin in the curable resin composition is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 25 parts by mass or more. The upper limit value of the proportion is not particularly limited, and may be 95 parts by mass or less, 90 parts by mass or less, 85 parts by mass or less, or 50 parts by mass or less.

[0065] The proportion of the biphenyl type epoxy resin in 100 parts by mass of the total amount of the epoxy resin in the curable resin composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. The upper limit value of the proportion is not particularly limited, and may be 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less.

[0066] The total content of the epoxy resin in the curable 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.

[0067] (Hardening agent) The curable resin composition of the present disclosure preferably contains a hardening agent. The type of the hardening agent is not particularly limited and can be selected from those generally used as components of the curable resin composition. The hardening agent may be used alone or in combination of two or more. In the present disclosure, the hardening agent only needs to have a structure capable of reacting with the epoxy resin contained in the curable resin composition and curing the curable resin composition, and even a compound with a small content and a small contribution to the curing reaction of the curable resin composition is included in the hardening agent.

[0068] Examples of the hardening agent include phenolic hardening agents, amine hardening agents, acid anhydride hardening agents, polymercaptan hardening agents, polyaminoamide hardening agents, isocyanate hardening agents, blocked isocyanate hardening agents, etc. Among these, from the viewpoint of heat resistance, the hardening agent is preferably a phenolic hardening agent or an amine hardening agent. Also, from the viewpoints of the adhesiveness of the curable resin composition of the present disclosure to the lead frame and heat resistance, the hardening agent is preferably a phenolic hardening agent.

[0069] Examples of phenolic curing agents include phenolic resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenyl; phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc. At least one phenolic compound selected from the group consisting of, and aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc. are condensed or co-condensed under an acidic catalyst to obtain a novolak-type phenolic resin; the above phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc. are synthesized from aralkyl-type phenolic resins such as phenolic 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 compound 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 compound and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; phenolic resins obtained by copolymerizing two or more of these, etc. These phenolic curing agents may be used alone or in combination of two or more.

[0070] Examples of the aralkyl phenol resin include phenol aralkyl resins, naphthol aralkyl resins, etc. which are synthesized from phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. The aralkyl phenol resin may be further copolymerized with other phenol resins. Examples of the copolymerized aralkyl phenol resin include copolymerized phenol resins of triphenylmethane type phenol resin and aralkyl type phenol resin, copolymerized phenol resins of salicylaldehyde type phenol resin and aralkyl type phenol resin, copolymerized phenol resins of novolak type phenol resin and aralkyl type phenol resin, etc.

[0071] The aralkyl phenol resin is not particularly limited as long as it is a phenol resin synthesized from at least one selected from the group consisting of phenol 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 preferable.

[0072] [Chemical formula]

[0073] In formulas (XII) to (XIV), R 23 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 22 , R 24 , R 25 and R 28 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 represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i is an integer of 0 to 3 independently, j is an integer of 0 to 2 independently, k is an integer of 0 to 4 independently, and p is an integer of 0 to 4 independently. n is an average value and is a number of 0 to 10 independently.

[0074] From the viewpoints of the adhesiveness and heat resistance of the curable resin composition of the present disclosure to the lead frame, an aralkyl-type phenol resin is preferably a phenol resin represented by the general formula (XIII). From the viewpoints of the adhesiveness and heat resistance of the curable resin composition of the present disclosure to the lead frame, further, in the general formula (XIII), it is preferable that both i and k are 0.

[0075] The dicyclopentadiene-type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) can be mentioned.

[0076]

Chemical formula

[0077] 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 an average value and represents a number of 0 to 10.

[0078] The triphenylmethane-type phenol resin is not particularly limited as long as it is a phenol resin obtained from an aromatic aldehyde compound as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferable.

[0079]

Chemical formula

[0080] In formula (XVI), R 30 and R 31 represent monovalent organic groups 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, and k is each independently an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0081] The copolymerized phenolic resin of a triphenylmethane type phenolic resin and an aralkyl type phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of a phenolic resin obtained from a compound having a benzaldehyde skeleton as a raw material and an aralkyl type phenolic resin. For example, the phenolic resin represented by the following general formula (XVII) is preferable.

[0082]

Chemical formula

[0083] In formula (XVII), R 32 ~R 34 represent monovalent organic groups having 1 to 18 carbon atoms, and all of them may be the same or different. i is an integer of 0 to 3 independently, k is an integer of 0 to 4 independently, and q is an integer of 0 to 5 independently. l and m are average values and are numbers of 1 to 11 independently.

[0084] The novolak 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 a phenol compound and a naphthol compound with an aldehyde compound under an acidic catalyst. For example, the phenolic resin represented by the following general formula (XVIII) is preferable.

[0085]

Chemical formula

[0086] In formula (XVIII), R 35 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 36 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0087] R in the above general formulas (XII) to (XVIII)22 ~R 36 The description of "each may be the same or different" regarding, for example, the i R's in formula (XII) 22 means that all of them may be the same or different from each other. For the other R's 23 ~R 36 it also means that each number included in the formula may be the same or different from each other. Also, R 22 ~R 36 may be the same or different from each other. 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.

[0088] In the above general formulas (XII) to (XVIII), n is preferably in the range of 0 to 10. When it is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity during melt molding of the curable resin composition 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.

[0089] Specific examples of the amine-based curing agent 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 compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole; imidazoline compounds such as imidazoline, 2-methylimidazoline, 2-ethylimidazoline, etc.

[0090] The functional group equivalent weight of the curing agent (the hydroxyl group equivalent weight in the case of a phenolic curing agent and the active hydrogen equivalent weight in the case of an amine curing agent) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance, and electrical reliability, it is preferably from 10 g / eq to 1000 g / eq, and more preferably from 30 g / eq to 500 g / eq. In the case of a phenolic curing agent, the hydroxyl group equivalent weight refers to a value calculated based on the hydroxyl value measured in accordance with JIS K 0070:1992. Further, in the case of an amine curing agent, the active hydrogen equivalent weight refers to a value calculated based on the amine value measured in accordance with JIS K 7237:1995.

[0091] 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 from 40°C to 180°C. Further, from the viewpoint of handleability during the production of the curable resin composition, the softening point or melting point of the curing agent is preferably from 50°C to 130°C.

[0092] When the curing agent is a phenolic curing agent, the equivalent ratio of the phenolic hydroxyl group (active hydrogen) of the phenolic curing agent to the epoxy group of the epoxy resin in the curable resin composition (the number of moles of the phenolic hydroxyl group (active hydrogen) of the phenolic curing agent / the number of moles of the epoxy group of the epoxy resin) is not particularly limited, and can be, for example, from 0.5 to 1.2, may be 0.5 or more and less than 1.0, may be from 0.55 to 0.9, or may be from 0.6 to 0.8. When the equivalent ratio is 0.5 or more and less than 1.0, the adhesiveness between the cured product of the curable resin composition and the support member tends to be improved. The reason for this is not clear, but the value of tanδ near the reflow temperature can be increased, and the internal stress of the resin cured product during reflow tends to be relaxed. From the viewpoint of improving the adhesiveness between the cured product of the curable resin composition and the support member, it is preferable that the equivalent ratio is 0.8 or less.

[0093] When the curing agent contains a phenolic curing agent, from the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to the lead frame, the content of the phenolic 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.

[0094] When the phenolic curing agent contains an aralkyl type phenolic resin, from the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to the lead frame, the content of the aralkyl type phenolic resin relative to the total mass of the phenolic curing agent may be greater than 0% by mass and 100% by mass or less, and may also be 50% by mass to 70% by mass or 80% by mass to 100% by mass. The phenolic curing agent may not contain an aralkyl type phenolic resin.

[0095] When the phenolic curing agent contains a triphenylmethane type phenolic resin, from the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to the lead frame, the content of the triphenylmethane type phenolic resin relative to the total mass of the phenolic curing agent may be greater than 0% by mass and 90% by mass or less, and may also be 20% by mass to 50% by mass or 70% by mass to 90% by mass.

[0096] (Inorganic filler) The curable resin composition of the present disclosure may contain an inorganic filler. By including an inorganic filler in the curable resin composition, the hygroscopicity of the curable resin composition is reduced, and the strength in the cured state tends to be improved. When the curable resin composition is used as a sealing material for a semiconductor package, it is preferable to contain an inorganic filler.

[0097] The inorganic material constituting the inorganic filler is not particularly limited. Specific examples of the inorganic material include spherical silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, aluminum nitride, boehmite, beryllia, magnesium oxide, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, talc, clay, mica, titanate, and the like. An inorganic filler composed of an inorganic material having a flame retardant effect may also be used. Examples of the inorganic material having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxide of magnesium and zinc, and zinc borate. The inorganic filler may be used alone or in combination of two or more.

[0098] The shape of the inorganic filler is not particularly limited, and examples thereof include powdery, spherical, fibrous, and the like. From the viewpoints of fluidity and mold wear during molding of the curable resin composition, it is preferably spherical.

[0099] The average particle diameter of the inorganic filler is not particularly limited. From the viewpoint of the balance of viscosity, fillability, etc. of the curable 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 even more 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 method particle size distribution measuring device.

[0100] The particle diameter of the inorganic filler may be top-cut, may be top-cut at 100 μm or less, or may be top-cut at 75 μm or less. The top-cut particle diameter can be determined from the particle size distribution when the above volume average particle diameter (D50) is measured.

[0101] When the curable resin composition contains an inorganic filler, its content is not particularly limited. The content of the inorganic filler with respect to the entire curable resin composition is preferably 30% to 90% by mass, more preferably 35% to 80% by mass, and even more preferably 40% to 70% by mass. When the content of the inorganic filler is 30% by mass or more of the entire curable resin composition, the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 90% by mass or less of the entire curable resin composition, the increase in the viscosity of the curable resin composition is suppressed, and the fluidity is further improved, and the moldability tends to be better.

[0102] The content of the inorganic filler with respect to the entire curable resin composition is preferably 68% to 86% by volume, more preferably 70% to 84% by volume, and even more preferably 72% to 82% by volume. When the content of the inorganic filler is 68% by volume or more of the entire curable resin composition, the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 86% by volume or less of the entire curable resin composition, the increase in the viscosity of the curable resin composition is suppressed, and the fluidity is further improved, and the moldability tends to be better.

[0103] (Curing accelerator) The curable 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 the epoxy resin, the desired properties of the curable resin composition, etc. The curing accelerator may be used alone or in combination of two or more. Specific examples of the curing accelerator are described below, but are not limited thereto. As the hardening accelerator, 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, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or their derivatives; compounds having intramolecular polarization formed by adding compounds having a π bond, such as quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and diazophenylmethane; cyclic amidinium compounds such as tetrabutylammonium tetrafluoroborate of DBU, tetrabutylammonium tetrafluoroborate of DBN, tetrabutylammonium tetrafluoroborate of 2-ethyl-4-methylimidazole, tetrabutylammonium tetrafluoroborate of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide;Organic phosphines such as primary phosphines like ethylphosphine and phenylphosphine, secondary phosphines like dimethylphosphine and diphenylphosphine, and tertiary phosphines like 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, etc.; phosphine compounds such as complexes of the organic phosphines with organic borons; compounds having intramolecular polarization formed by adding a compound having a π bond, such as maleic anhydride, 1,4-benzoquinone, 2,5-xylenequinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone, etc., or diazophenylmethane, to the organic phosphine or the phosphine compound; compounds having intramolecular polarization obtained by reacting the organic phosphine or the phosphine compound with a halogenated phenol compound such as 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 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, 4-bromo-4'-hydroxybiphenyl, etc., and then undergoing a dehydrohalogenation step.Tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetra-substituted phosphonium tetrafluoroborate salts such as tetraphenylphosphonium tetra-p-tolylborate, salts of tetra-substituted phosphonium and phenolic compounds, etc.; phosphobetaine compounds; adducts of phosphonium compounds and silane compounds, etc. are mentioned. Suitable curing accelerators include triphenylphosphine, quinone compound adducts of triphenylphosphine, etc.

[0104] When the curable resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.1% by mass to 8% by mass, more preferably 0.3% by mass to 7% by mass, and even more preferably 0.5% by mass to 6% by mass with respect 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 rate of the curable resin composition of the present disclosure becomes an appropriate value, and the production of molded articles becomes easy.

[0105] (Various additives) In addition to the above-mentioned components, the curable resin composition of the present disclosure may contain various additives such as coupling agents, stress relievers, mold release agents, colorants, flame retardants, ion exchangers, ultraviolet absorbers, etc. Further, the curable resin composition of the present disclosure may contain a siloxane compound having a structural unit having an epoxy group and an alkoxy group and having a polymerization degree of 2. The curable resin composition may contain various additives well-known in the art as needed in addition to the additives exemplified below.

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

[0107] The silane coupling agent is not particularly limited, and examples thereof include methyltrimethoxysilane, bis(3-(triethoxysilyl)propyl)tetrasulfide, 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, methacryloxyoctyltrimethoxysilane, and the like.

[0108] Examples of the titanium coupling agent include isopropyltriisostearoyl titanate, isopropyltris(dioctyl pyrophosphate) titanate, isopropyltri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearyldiacryl titanate, isopropyltri(dioctyl phosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis(dioctyl phosphite) titanate, and the like.

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

[0110] (Stress reliever) The curable resin composition of the present disclosure may contain a stress reliever such as silicone oil and silicone rubber particles. By including a stress reliever in the curable resin composition, warpage deformation of the package and generation of package cracks can be further reduced. Examples of the stress reliever include generally used known stress relievers (plasticizers). Specifically, examples of the stress reliever include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, natural rubber (NR), acrylonitrile-butadiene copolymer (NBR), acrylic rubber, urethane rubber, rubber particles such as 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 reliever may be used alone or in combination of two or more. Among them, silicone-based stress relievers are preferred. Examples of the silicone-based stress reliever include those having an epoxy group, those having an amino group, and those obtained by polyether-modifying these.

[0111] When the curable resin composition contains a stress reliever, its content is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition.

[0112] (Release agent) When using a mold during molding, the curable resin composition of the present disclosure may contain a mold release agent from the perspective of mold release properties with the mold. The mold release agent is not particularly limited, and conventionally known ones can be used. Examples of the mold release agent include carnauba wax, higher fatty acids such as montanic acid and stearic acid, metal salts of higher fatty acids, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The mold release agent may be used alone or in combination of two or more.

[0113] When the curable resin composition of the present disclosure contains a mold release agent, the content of the mold release agent is preferably 0.01 part by mass to 15 parts by mass, more preferably 0.1 part by mass to 10 parts by mass, based on 100 parts by mass of the epoxy resin contained in the curable resin composition. When the amount of the mold release agent is 0.01 part by mass or more based on 100 parts by mass of the resin component, mold release properties tend to be sufficiently obtained. When it is 15 parts by mass or less, better mold release properties tend to be obtained.

[0114] (Colorant) The curable 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 according to the purpose and the like. The colorant may be used alone or in combination of two or more.

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

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

[0117] When the curable resin composition 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, based on 100 parts by mass of the epoxy resin contained in the curable resin composition.

[0118] (Ion exchanger) The curable resin composition of the present disclosure may contain an ion exchanger. When the curable resin composition 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, examples of the ion exchanger include hydrotalcite represented by the following general formula (A).

[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 curable resin composition 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 6 parts by mass, based on 100 parts by mass of the epoxy resin contained in the curable resin composition.

[0121] (Physical properties of the curable resin composition) From the perspective of fluidity, the spiral flow of the curable resin composition of the present disclosure is preferably 90 cm or more, more preferably 120 cm or more, and even more preferably 140 cm or more. The upper limit value of the spiral flow is not particularly limited, and may be, for example, 170 cm or less.

[0122] The measurement of the spiral flow is to determine the flow distance when the curable resin composition is molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds using a spiral flow measurement mold according to EMMI-1-66.

[0123] From the perspectives of fluidity and curability, the gel time of the curable resin composition at 175°C is preferably 15 seconds or more, more preferably 18 seconds or more, and even more preferably 21 seconds or more.

[0124] The gel time is measured as the time from when 0.5 g of the thermosetting resin composition is placed on a hot plate preheated to 175°C to the time when the viscosity of the resin is lost. It is preferable to heat while periodically stirring the resin with a spatula or the like. "The viscosity of the resin is lost" refers to the phenomenon that the resin breaks or is destroyed when the resin is kneaded using a spatula or the like.

[0125] The linear expansion coefficient (α1) of the cured product of the curable resin composition at 10°C to 30°C may be 8.0 ppm / °C or more, or may be 9.0 ppm / °C to 12.0 ppm / °C.

[0126] From the perspective of suppressing warpage in the package of the cured product of the curable resin composition of the present disclosure, the linear expansion coefficient of the cured product of the curable resin composition at 180°C to 200°C is preferably 32.0 ppm / °C or more, more preferably 33.0 ppm / °C or more, and even more preferably 34.0 ppm / °C or more. Conventionally, it was considered that the smaller the linear expansion coefficient, the more the peeling from the lead frame could be suppressed. However, in the curable resin composition of the present disclosure, it has been found that a linear expansion coefficient of 32.0 ppm / °C or more at 180°C to 200°C of the cured product is more effective in suppressing peeling from the lead frame. The reason for this is not clear, but it is presumed to be the effect of reducing thermal stress by suppressing warpage caused by the difference in linear expansion coefficient between members. In particular, in the curable resin composition of the present disclosure, it is possible to lower the glass transition temperature (Tg), and the allowable range of the linear expansion coefficient can be widened. From the perspective of suppressing the generation of thermal stress with the package member, the upper limit value of the linear expansion coefficient is preferably 60 ppm / °C or less, more preferably 55 ppm / °C or less, and even more preferably 50 ppm / °C or less.

[0127] In the present disclosure, the linear expansion coefficient α1 and the linear expansion coefficient α2 are the slopes of the tangent lines at 10°C to 30°C and the slopes of the tangent lines at 180°C to 200°C when the strain of the cured product is plotted against temperature by a thermomechanical analysis method (TMA: Thermal Mechanical Analysis) based on JIS K 7197:2012. The test load is 98 mN, and the temperature increase rate is 5°C / min for measurement. 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 curable resin composition using a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and then performing post-curing under the conditions of 175°C for 5 hours. The cured product has a rectangular shape with a short side of 5.1 mm, a long side of 20 mm, and a thickness of 2 mm.

[0128] From the viewpoint of heat resistance and the like, the glass transition temperature (Tg) of the cured product of the curable resin composition is preferably greater than 110°C, more preferably 112°C or higher, and even more preferably 115°C or higher. The upper limit value of the Tg is not particularly limited and may be 200°C or lower, or may be 180°C or lower.

[0129] In the present disclosure, the glass transition temperature of the cured product is defined as the temperature at the intersection of the tangent line at 10°C to 30°C and the tangent line at 200°C to 220°C obtained by the measurement of the above linear expansion coefficient.

[0130] From the viewpoint of the adhesion of the cured product of the curable resin composition of the present disclosure to the lead frame, the elastic modulus at 260°C of the cured product of the curable resin composition is preferably 1000 MPa or less, more preferably 900 MPa or less, and even more preferably 800 MPa or less, although it depends on the filler amount.

[0131] The elastic modulus of the cured product of the curable resin composition is measured using a viscoelasticity measuring device (for example, RSAIII manufactured by TA Instruments) under the conditions of a span distance of 40 mm and a frequency of 1 Hz, and the temperature is raised from 20°C to 300°C at a rate of 5°C / min by the three-point bending method to obtain the elastic modulus at 260°C. The cured product is prepared by the method described in terms of the linear expansion coefficient. As the cured product, a cured product having a rectangular shape with a short side of 5.1 mm, a long side of 20 mm, and a thickness of 2 mm is used.

[0132] From the viewpoint of the adhesion of the cured product of the curable resin composition of the present disclosure to the lead frame, the adhesive force (also referred to as adhesive force 1) at room temperature (for example, 25°C) of the cured product to AgCu is preferably 7.0 MPa or more, and more preferably 7.5 MPa or more. The upper limit value of the adhesive force 1 is not particularly limited.

[0133] From the perspective of the adhesiveness of the cured product of the curable resin composition of the present disclosure to the lead frame, the adhesive strength (also referred to as adhesive strength 2) at 260 °C after heating and humidifying at 85 °C and 85% RH for 168 hours with respect to AgCu of the cured product is 0.40 MPa or more, preferably 0.42 MPa or more, and more preferably 0.45 MPa or more. Also, the upper limit value of the adhesive strength 2 is not particularly limited.

[0134] In the measurement of the adhesive strength 1, first, the curable resin composition is molded by transfer molding on an Ag-plated Cu substrate, cured under the conditions of 175 °C and a curing time of 120 seconds, and then post-cured under the conditions of 175 °C for 5 hours to prepare a sample. The cured product of the sample has a shape with a short side of 3.0 mm, a long side of 3.5 mm, and a thickness of 2.9 mm. This sample is measured by performing a shear strength test in which the tool of the apparatus is applied to the cured product under the conditions of room temperature (for example, 25 °C) using a bond tester apparatus (for example, manufactured by Nordson Corporation, product name 4000 Optima).

[0135] In the measurement of the adhesive strength 2, a sample is prepared in the same manner as in the measurement of the adhesive strength 1. This sample is heated and humidified at 85 °C and 85% RH for 168 hours, and then measured by performing a shear strength test in which the tool of the apparatus is applied to the cured product under the conditions of 260 °C using a bond tester apparatus (for example, manufactured by Nordson Corporation, product name 4000 Optima).

[0136] Regarding the curable resin composition of the present disclosure, the curing shrinkage rate (shrinkage rate 1 in the examples) of the molded product molded under the conditions of a mold temperature of 175 °C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds may be 0.37% or more, may be 0.38% or more, or may be 0.40% or more. The upper limit of the curing shrinkage rate of the aforementioned molded product is not particularly limited.

[0137] (Manufacturing method of curable resin composition) The manufacturing method of the curable resin composition is not particularly limited. As a general method, there can be mentioned a method in which components in predetermined compounding amounts are sufficiently mixed by a mixer or the like, and then melt-kneaded by a mixing roll, an extruder, etc., cooled, and pulverized. More specifically, for example, there can be mentioned a method in which a predetermined amount of the above-described components is uniformly stirred and mixed, and kneaded by a kneader, a roll, an extruder, etc. that have been pre-heated to 70°C to 140°C, cooled, and pulverized.

[0138] The curable resin composition is preferably solid at 25°C. When the curable resin composition is solid at 25°C, the shape of the curable resin composition is not particularly limited, and examples include powdery, granular, tablet-like, etc. From the viewpoint of handleability, when the curable resin composition is tablet-like, the dimensions and mass should be such that they match the molding conditions of the package.

[0139] (Use of the curable resin composition) The use of the curable resin composition of the present disclosure is not particularly limited, and for example, it can be used in various mounting techniques as a sealing material for electronic component devices. Further, the curable resin composition of the present disclosure can be used in various applications where it is desirable for the resin composition to have good fluidity and curability, such as resin molded bodies for various modules, resin molded bodies for motors, resin molded bodies for in-vehicle use, sealing materials for protective materials for electronic circuits, etc.

[0140] <Electronic component device> The electronic component device of the present disclosure includes an element and a cured product of the above-described curable resin composition that seals the element.

[0141] The electronic component device can include a support member on which the element is mounted. Examples of the support member include a lead frame, a 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 above-described curable resin composition.

[0142] The lead frame may or may not have a roughened surface. From the perspective of manufacturing cost, a lead frame is preferred, and from the perspective of adhesiveness, a roughened lead frame is preferred. The roughening method is not particularly limited, and examples thereof include alkali treatment, silane coupling treatment, sand mat treatment, plasma treatment, corona discharge treatment, etc.

[0143] The lead frame preferably contains Ag, and may further contain Cu or the like.

[0144] Examples of the elements included in the electronic component device include active elements such as silicon chips, transistors, diodes, thyristors, etc., and passive elements such as capacitors, resistors, coils, etc.

[0145] Specific configurations of the electronic component device include, but are not limited to, the following configurations. (1) General resin-sealed ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead Package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc., which have a structure in which an element is fixed on a lead frame, and the terminal portion and lead portion of the element such as bonding pads are connected using wire bonding, bumps, etc., and then sealed using a curable resin composition; (2) TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier using bumps is sealed using a curable resin composition; (3) COB (Chip On Board) modules, hybrid ICs, multi-chip modules, etc., which have a structure in which an element connected to wiring formed on a support member using wire bonding, flip chip bonding, solder, etc. is sealed using a curable resin composition; (4) A structure having a structure in which an element is mounted on the surface of a support member having terminals for wiring board connection formed on the inner surface, the element is connected to the wiring formed on the support member using bumps or wire bonding, and then the element is encapsulated using a curable resin composition, such as BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), SiP (System in a Package), etc.

[0146] The method of encapsulating the element using the curable resin composition is not particularly limited, and known methods can be applied. As the encapsulation method, for example, low-pressure transfer molding is common, but injection molding, compression molding, casting, etc. may also be used.

Examples

[0147] Hereinafter, the present disclosure will be specifically described by way of examples, but the present disclosure is not limited to these examples. Also, the numerical values in the table mean "parts by mass" unless otherwise specified.

[0148] [Examples 1 to 3 and Comparative Examples 1 to 2] After preliminarily mixing (dry blending) the materials of the formulation shown in Table 1, they were kneaded with a twin-screw roll (roll surface temperature: about 80 °C) for about 15 minutes, cooled, and pulverized to produce a powdery curable 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 set to 0.7.

[0149] The details of the materials in Table 1 are as follows.

[0150] · Epoxy resin 1: A triphenylmethane type epoxy resin represented by formula (2), epoxy equivalent 214 g / eq · Epoxy resin 2: A sulfur atom-containing type epoxy resin, epoxy equivalent 238 g / eq to 254 g / eq, melting point 116 °C to 126 °C · Epoxy resin 3: A biphenyl type epoxy resin, epoxy equivalent 241 g / eq · Epoxy resin 4: Methoxynaphthalene-cresol-formaldehyde co-condensed epoxy resin, epoxy equivalent 250 g / eq · Epoxy resin 5: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq · Epoxy resin 6: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq · Epoxy resin 7: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq

[0151] · Hardener 1: Aralkyl type phenolic resin, hydroxyl equivalent 175 g / eq · Hardener 2: Triphenylmethane type phenolic resin, hydroxyl equivalent 104 g / eq · Hardener 3: Alkyl modified phenolic resin, hydroxyl equivalent 224 g / eq · Hardener 4: Biphenylaralkyl type phenolic resin, hydroxyl equivalent 204 g / eq · Hardener 5: Aminotriazine modified phenolic resin, amine equivalent 120 g / eq · UV absorber 1: Benzotriazole based UV absorber · UV absorber 2: Triazine based UV absorber · Curing accelerator 1: 1,4-Benzoquinone adduct of triphenylphosphine · Curing accelerator 2: Triphenylphosphine · Coupling agent 1: N-Phenyl-3-aminopropyltrimethoxysilane · Coupling agent 2: 3-Glycidoxypropyltrimethoxysilane · Coupling agent 3: Bis(3-(triethoxysilyl)propyl)tetrasulfide · Coupling agent 4: 3-Mercaptopropyltrimethoxysilane · Coupling agent 5: Methyltrimethoxysilane · Release agent: Ester wax such as montanic acid ester · Colorant: Carbon black · Ion exchanger 1: Unfired hydrotalcite compound (Mg / Al = 3.0) · Ion exchanger 2: Unfired hydrotalcite compound (Mg / Al = 2.25) · Ion exchanger 3: Unfired hydrotalcite compound (Mg / Al = 3.0) · Stress reliever 1: Silicone-based stress reliever having an epoxy group · Stress reliever 2: Triphenylphosphine oxide · Stress reliever 3: Coumarone resin, softening point 100 °C, Nichido Chemical Co., Ltd. · Stress reliever 4: Indene polymer · Inorganic filler 1: Spherical silica particles with a volume average particle diameter of 26.9 μm · Inorganic filler 2: Spherical silica particles with a volume average particle diameter of 0.5 μm · Inorganic filler 3: Spherical silica particles with a volume average particle diameter of 20 μm

[0152] <<Evaluation of the curable resin composition>> The properties of the curable 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.

[0153] <Measurement of spiral flow> The spiral flow of the curable resin composition was measured by the above method.

[0154] <Measurement of gel time> The gel time of the curable resin composition was measured by the above method.

[0155] <Measurement of linear expansion coefficient> The thermal expansion coefficients (α1) from 10 °C to 30 °C and (α2) from 180 °C to 200 °C of the cured product of the curable resin composition were measured by the above method. As the thermomechanical analyzer, TMA / SS6100 manufactured by Seiko Instruments Inc. was used.

[0156] <Glass transition temperature (Tg) of the cured product> The temperature at the intersection of the tangent line at 10 °C to 30 °C and the tangent line at 200 °C to 220 °C obtained from the measurement of the above linear expansion coefficient was defined as the glass transition temperature of the cured product.

[0157] <Measurement of shrinkage rate 1> Using the mold with dimensions already measured, by transfer molding, disk-shaped molded articles (test pieces) of the curable resin compositions obtained in the above Examples and Comparative Examples were molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and then the test pieces were allowed to cool to 25°C. After cooling, the average value of the diameters at two points on each of the front and back of the test piece was designated as Rm (mm), and the average value of the inner diameters at two points on the mold corresponding to the front of the test piece and the average value of the inner diameters at two points on the mold corresponding to the back of the test piece were designated as Rd (mm). By substituting into the following formula, the curing shrinkage rate (shrinkage rate 1) of the curable resin composition was determined. Shrinkage rate 1 (%) = [(Rd - Rm) / Rd] × 100

[0158] <Measurement of shrinkage rate 2> Using the mold with dimensions already measured, by transfer molding, disk-shaped cured articles (test pieces) of the curable resin compositions obtained in the above Examples and Comparative Examples were molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and then the test pieces were allowed to cool to 25°C. After cooling to 25°C, the test pieces were heated in an oven heated to 175°C for 5 hours, and then the test pieces were allowed to cool to 25°C. After cooling, the average value of the diameters at two points on each of the front and back of the test piece was designated as Rm (mm), and the average value of the inner diameters at two points on the mold corresponding to the front of the test piece and the average value of the inner diameters at two points on the mold corresponding to the back of the test piece were designated as Rd (mm). By substituting into the following formula, the curing shrinkage rate (shrinkage rate 2) of the curable resin composition was determined. Shrinkage rate 2 (%) = [(Rd - Rm) / Rd] × 100

[0159] <Measurement of adhesion force 1 to AgCu> Using the above method, the adhesion force 1 to AgCu of the cured product of the curable resin composition was measured. As the measuring device, Model 4000 Optima manufactured by Nordson was used.

[0160] <Measurement of adhesion force 2 to AgCu> The adhesive strength 2 of the cured product of the curable resin composition with respect to AgCu was measured by the above method. As the measuring apparatus, the product name 4000 Optima manufactured by Nordson was used.

[0161] <Peelability evaluation under high temperature and moisture absorption> An 80-pin flat package (lead frame material: AgCu) with outer dimensions of 20 mm in length, 14 mm in width, and 2 mm in thickness, on which a silicon chip (8 mm in length, 10 mm in width, and 0.4 mm in thickness) sealed using the cured product of the curable resin composition formed under the above conditions was mounted, was produced. The above package was heated under the conditions of 85°C and 85% RH for 168 hours (MSL1). Thereafter, at 260°C, a 10-second reflow process was performed for each, and the presence or absence of peeling inside the package was observed using an ultrasonic flaw detector (manufactured by Hitachi Construction Machinery Co., Ltd., HYE-FOCUS). The peelability was evaluated based on the number of packages in which peeling occurred with respect to the number of test packages (16 pieces).

[0162]

Table 1

[0163]

Table 2

[0164] As shown in Table 2, it can be seen that under the heating and humidifying conditions of 85°C and 85% RH for 168 hours, peeling is significantly suppressed in the examples compared to the comparative examples.

Claims

1. A curable resin composition containing an epoxy resin, wherein the adhesive strength at 260°C after heating and humidifying the cured product at 85°C and 85% RH for 168 hours with respect to AgCu is 0.40 MPa or more.

2. Further containing a curing agent, The curable resin composition according to claim 1, wherein the equivalent ratio of the curing agent to the epoxy resin, which is the equivalent ratio of the curing agent to the epoxy resin, is 0.8 or less.

3. The curable resin composition according to claim 1, wherein the glass transition temperature of the cured product is higher than 110°C.

4. The curable resin composition according to claim 1, wherein the thermal expansion coefficient α2 measured at 180°C to 200°C is 32.0 ppm / °C or more.

5. The curable resin composition according to claim 1, wherein the epoxy resin contains at least one selected from the group consisting of a triphenylmethane type epoxy resin containing a t-Bu group and a biphenyl type epoxy resin.

6. The curable resin composition according to claim 1, further containing an inorganic filler.

7. An element, A cured product of the curable resin composition according to any one of claims 1 to 6 for encapsulating the element, An electronic component device comprising:

8. The electronic component device according to claim 7, comprising a lead frame on which the element is mounted on one surface.

9. The electronic component device according to claim 8, wherein the lead frame contains Ag.

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