Curable resin composition and electronic component device

Abstract

The first curable resin composition includes a triphenylmethane epoxy resin having at least one selected from the group consisting of an alkyl group and an alkoxy group. The second curable resin composition includes a triphenylmethane type epoxy resin having at least one selected from the group consisting of an alkyl group and an alkoxy group, and a polysiloxane-based stress relaxation agent. The third curable resin composition has an elastic coefficient of 400 MPa or less at 260 DEG C when made into a cured product, a linear expansion coefficient of 32 ppm / DEG C or more at 180-200 DEG C when made into a cured product, and an adhesive strength of 0.45 MPa or more with respect to Ag (silver) after treatment at 85 DEG C and 85% RH.

Description

Technical Field

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

[0002] In recent years, the high-density mounting of semiconductor components has been developing. With this, resin-sealed semiconductor devices have become mainstream in surface-mounted packages compared to existing pin-insertion packages. Surface-mounted integrated circuits (ICs) and large-scale integrated circuits (LSIs) have become thin and small packages in order to increase mounting density and reduce mounting height. As a result, the area occupied by the components relative to the package becomes larger, and the thickness of the package becomes very thin.

[0003] Furthermore, the mounting method of these packages is different from that of pin insertion type packages. That is, the pin insertion type packages are structured as follows: after the pins are inserted into the wiring board, soldering is performed from the back side of the wiring board, so the package is not directly exposed to high temperature.

[0004] However, surface mounted ICs are temporarily fixed on the surface of a wiring board and processed using a solder bath, reflow device, etc., so the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture absorbed vaporizes during reflow, and the resulting vapor pressure acts as a peeling stress, causing peeling between the supporting members such as components and lead frames and the sealing material, which causes the generation of package cracks and poor electrical properties. Therefore, it is desirable to develop a sealing material that has excellent adhesion to the supporting member and, in turn, excellent solder heat resistance (reflow resistance).

[0005] As a sealing material having excellent reflow resistance, Patent Document 1 proposes 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.

[0006] In order to improve the reflow resistance, for example, the surface of the lead frame is roughened before the plating process to improve the adhesion with the sealing material.

[0007] [Prior art literature]

[0008] [Patent Document]

[0009] Patent Document 1: Japanese Patent Application Publication No. 2008-111101 Summary of the invention

[0010] [Problems to be solved by the invention]

[0011] It is desired to develop a sealing material whose peeling from the lead frame is suppressed even under more severe moisture absorption conditions.

[0012] The present disclosure has been made in view of the above circumstances and aims to provide a curable resin composition which suppresses peeling from a lead frame even when the cured product absorbs moisture under the conditions of 85° C. and 85% RH, and an electronic component device including an element sealed with the curable resin composition.

[0013] [Technical means to solve the problem]

[0014] <1> A curable resin composition comprising a triphenylmethane epoxy resin having at least one selected from the group consisting of an alkyl group and an alkoxy group.

[0015] <2> The curable resin composition according to <1>, wherein the benzene ring contained in the triphenylmethane epoxy resin has two or more alkyl groups.

[0016] <3> The curable resin composition according to <1> or <2>, wherein the benzene ring contained in the main chain of the triphenylmethane epoxy resin has two or more alkyl groups.

[0017] <4> The curable resin composition according to any one of <1> to <3>, wherein the alkyl group includes a tert-butyl group.

[0018] <5> The curable resin composition according to any one of <1> to <4>, further comprising a polysiloxane-based stress relaxant.

[0019] <6> The curable resin composition according to <5>, wherein the polysiloxane-based stress relaxant comprises a branched polysiloxane having the following structural units (a) and (b), and the terminal is selected from R 1 At least one functional group selected from the group consisting of hydroxyl and alkoxy, and the epoxy equivalent is 500g / eq to 4000g / eq.

[0020] [Chemistry 1]

[0021]

[0022] 〔R 1 represents an unsubstituted alkyl, alkenyl, aryl, or aralkyl group having 1 to 12 carbon atoms, and a plurality of R 1 In the case of multiple R 1They may be the same or different. X represents 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidyloxyethyl, 3-glycidyloxypropyl, 4-glycidyloxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, or 3-(3,4-epoxycyclohexyl)propyl]

[0023] <7> A curable resin composition having an elastic modulus of 400 MPa or less at 260°C when formed into a cured product, a linear expansion coefficient of 32 ppm / °C or more at 180°C to 200°C when formed into a cured product, and an adhesive strength of the cured product to Ag (silver) of 0.45 MPa or more after treatment at 85°C and 85% RH.

[0024] <8> The curable resin composition according to <7>, wherein the spiral flow according to EMMI (Epoxy Molding Material Institute)-1-66 is 100 cm or more.

[0025] <9> The curable resin composition according to <7> or <8>, which has a hot hardness of 56 or more when cured.

[0026] <10> The curable resin composition according to any one of <7> to <9>, wherein the hot strength of the cured product is 3 MN / m 2 above.

[0027] <11> An electronic component device comprising: a device; and a cured product of the curable resin composition according to any one of <1> to <10>, wherein the device is sealed.

[0028] <12> The electronic component device according to <11>, comprising a lead frame having the element mounted on one surface thereof.

[0029] <13> The electronic component device according to <12>, wherein the lead frame contains Ag.

[0030] [Effects of the Invention]

[0031] The present disclosure provides a curable resin composition that suppresses peeling from a lead frame even when the cured product absorbs moisture under the conditions of 85° C. and 85% RH, and an electronic component device including an element sealed with the curable resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] none DETAILED DESCRIPTION

[0033] Hereinafter, the form for implementing the present disclosure is described in detail. Among them, the present disclosure is not limited to the following embodiments. In the following embodiments, except for the cases clearly indicated, the structural components (including component steps, etc.) are not necessary. The numerical values ​​and their ranges are also the same and do not limit the present disclosure.

[0034] In the present disclosure, in a numerical range expressed using “to”, the numerical values ​​described before and after including “to” are regarded as the minimum value and the maximum value, respectively.

[0035] In the numerical range recorded in stages in the present disclosure, the upper limit or lower limit recorded in one numerical range may also be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in the present disclosure, the upper limit or lower limit of the numerical range may also be replaced by the value shown in the synthesis example.

[0036] In the present disclosure, each component may include a plurality of corresponding compounds. When a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the content rate or content of each component refers to the total content rate or content of the plurality of substances present in the composition.

[0037] In the present disclosure, multiple types of particles corresponding to each component may be included. When multiple types of particles corresponding to each component are present in the composition, unless otherwise specified, the particle size of each component refers to a value related to a mixture of the multiple types of particles present in the composition.

[0038] In the present disclosure, the term "stacked" means stacking layers, and two or more layers may be combined or two or more layers may be detachable.

[0039] In the description of the group (atomic group) in the present disclosure, the description not recording whether it is substituted or unsubstituted includes both the group having no substituent and the group having a substituent.

[0040] In the present disclosure, the number of structural units indicates an integer value for a single molecule and indicates a rational number which is an average value for a collection of a plurality of molecules.

[0041] In the present disclosure, the carbon number refers to the total number of carbon atoms contained in a certain group as a whole. When the group has no substituent, it means the number of carbon atoms forming the skeleton of the group. When the group has a substituent, it means the total number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent.

[0042] In the present disclosure, the weight average molecular weight (Mw) is a value obtained by measuring under the following measurement conditions using the following gel permeation chromatography (GPC) measuring device and converting using a calibration curve of standard polystyrene. In particular, for compounds whose Mw cannot be accurately measured by GPC due to their small molecular weight, the molecular weight obtained based on the chemical structure of the compound is used as the Mw, Mn or degree of polymerization of the compound.

[0043] An example of the measuring apparatus is as follows. In the preparation of the calibration curve, five sample sets ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation) can be used as standard polystyrene.

[0044] (GPC measurement device)

[0045] GPC equipment: High-speed GPC equipment "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Co., Ltd.

[0046] Column: TSKgel Super Multipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation

[0047] (Measurement conditions)

[0048] Solvent: tetrahydrofuran (THF)

[0049] Measurement temperature: 40℃

[0050] Flow rate: 0.35mL / min

[0051] Sample concentration: 10mg / THF 5mL

[0052] Injection volume: 20 μL

[0053] <Curing resin composition>

[0054] The first curable resin composition of the present disclosure includes a triphenylmethane epoxy resin having at least one selected from the group consisting of an alkyl group and an alkoxy group. Hereinafter, the “triphenylmethane epoxy resin having at least one selected from the group consisting of an alkyl group and an alkoxy group” is also referred to as a “specific triphenylmethane epoxy resin”.

[0055] The first curable resin composition of the present disclosure suppresses peeling from the lead frame even when the curing agent is allowed to absorb moisture under the conditions of 85° C. and 85% RH. The reason why the first curable resin composition of the present disclosure exhibits the above effect is not clear, but is presumed as follows.

[0056] If the triphenylmethane epoxy resin has at least one selected from the group consisting of an alkyl group and an alkoxy group, the monomer volume increases, and the molecular weight of the monomer increases, and after polymerization, it becomes a polymer with a low crosslinking density and an enlarged intermolecular distance. Therefore, the number of molecules per unit volume decreases, and the molecules are easily decomposed when tensile stress is applied, so it is expected that the elastic coefficient of the cured product of the curable resin composition will decrease and the linear expansion coefficient will increase. As a result, the stress (combination of strain, elastic coefficient, linear expansion difference and temperature difference) generated by the linear expansion difference between the supporting members is reduced and can be reduced to less than the adhesion of the resin, so the peeling of the cured product of the curable resin composition from the supporting member is suppressed. It is also estimated that the reflow resistance is also improved.

[0057] The second curable resin composition of the present disclosure includes a triphenylmethane epoxy resin having at least one selected from the group consisting of an alkyl group and an alkoxy group, and a polysiloxane-based stress relaxant.

[0058] The second curable resin composition of the present disclosure suppresses peeling from the lead frame even when the curing agent is allowed to absorb moisture under the conditions of 85° C. and 85% RH. The reason why the second curable resin composition of the present disclosure exhibits the above effect is not clear, but is presumed as follows.

[0059] The effects estimated when using the specific triphenylmethane epoxy resin are as described in the first curable resin composition. Furthermore, by including a polysiloxane-based stress relaxant, the occurrence of warpage and cracks when the curable resin composition is cured can be reduced, thereby effectively suppressing the peeling of the cured product from the supporting member.

[0060] The third curable resin composition of the present disclosure has an elastic modulus of 400 MPa or less at 260° C. when formed into a cured product, a linear expansion coefficient of 32 ppm / ° C. or more at 180° C. to 200° C. when formed into a cured product, and an adhesive strength of the cured product to Ag (silver) of 0.45 MPa or more after treatment at 85° C. and 85% RH.

[0061] The third curable resin composition of the present disclosure suppresses peeling from the lead frame even when the curing agent is allowed to absorb moisture under the conditions of 85° C. and 85% RH. The reason why the third curable resin composition of the present disclosure exhibits the above effect is not clear, but is presumed as follows.

[0062] When the elastic modulus at 260° C. of the cured product is 400 MPa or less, the strain stress between the lead frame and the cured product is reduced during the reflow process, and peeling from the lead frame is suppressed.

[0063] In addition, it was previously believed that the smaller the linear expansion coefficient, the more the peeling from the lead frame was suppressed. However, experiments have found that in the third curable resin composition of the present disclosure, a linear expansion coefficient of the cured product at 180°C to 200°C of 32 ppm / °C or more is effective in suppressing peeling from the lead frame.

[0064] Furthermore, by setting the adhesive strength of the hardened material to Ag (silver) after treatment at 85°C and 85% RH to be greater than 0.45 MPa on the basis of setting the elastic coefficient and linear expansion coefficient within the above range, peeling from the lead frame is suppressed even when moisture is absorbed under the conditions of 85°C and 85% RH.

[0065] The elastic modulus of the cured product of the third curable resin composition at 260° C. is 400 MPa or less, preferably 390 MPa or less, and more preferably 380 MPa or less.

[0066] From the viewpoint of protecting the chip from external forces, the elastic modulus at 260° C. is preferably 80 MPa or more, more preferably 100 MPa or more, further preferably 120 MPa or more, and particularly preferably 170 MPa or more.

[0067] The elastic coefficient of the cured product of the curable resin composition is determined by using a viscoelasticity measuring device (e.g., RSAIII manufactured by TA Instruments) under the conditions of a span of 40 mm and a frequency of 1 Hz, and by a three-point bending method, the temperature is raised from 20°C to 300°C at 5°C / min, and the elastic coefficient at 260°C is obtained. In addition, the cured product is prepared by the method described in terms of the linear expansion coefficient. The cured product is a rectangular product having a short side of 5.1 mm, a long side of 20 mm, and a thickness of 2 mm.

[0068] The linear expansion coefficient of the cured product of the third curable resin composition at 180°C to 200°C is 32 ppm / °C or more, preferably 34 ppm / °C or more, and more preferably 36 ppm / °C or more. From the viewpoint of being close to 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, further preferably 50 ppm / °C or less, and particularly preferably 42 ppm / °C or less.

[0069] In the present disclosure, the linear expansion coefficient is based on Japanese Industrial Standards (JIS) K 7197: 2012 and is the slope of the tangent line at 180°C to 200°C when the strain of the hardened material is plotted against the temperature by thermomechanical analysis (TMA). In addition, the test load is set to 5g and the heating rate is set to 5°C / min for measurement. The linear expansion coefficient can be measured using a thermomechanical analyzer (for example, TMA / SS6100 manufactured by Seiko Instruments Co., Ltd.).

[0070] The cured product was prepared by molding the curable resin composition using a transfer molding machine at a mold temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and then post-curing at 175° C. for 5 hours. The cured product had a rectangular shape with a short side of 5.1 mm, a long side of 20 mm, and a thickness of 2 mm.

[0071] The cured product of the third curable resin composition has an adhesive strength to Ag (silver) of 0.45 MPa or more, preferably 0.50 MPa or more, and more preferably 0.55 MPa or more. The upper limit of the adhesive strength is not particularly limited.

[0072] In the present disclosure, in the measurement of the adhesive strength of the cured product of the curable resin composition to Ag (silver), first, the curable resin composition is applied to an Ag substrate, and after curing at 175° C. and a curing time of 120 seconds, a post-curing is performed at 175° C. for 5 hours to prepare a sample. The cured product of the sample has a shape of 3.0 mm in short side, 3.5 mm in long side, and 2.9 mm in thickness. The sample is heated at 85° C. and 85% RH for 168 hours, and then a shear strength test is performed at 260° C. using an adhesive strength tester (e.g., manufactured by Nordson, product name 4000 Optima) in which the tool of the device touches the cured product for measurement.

[0073] Hereinafter, various materials that can be contained in the first to third curable resin compositions will be described. In addition, the first to third curable resin compositions are also collectively referred to as curable resin compositions of the present disclosure.

[0074] (Epoxy resin)

[0075] The first curable resin composition and the second curable resin composition of the present disclosure contain a specific triphenylmethane epoxy resin.

[0076] The third curable resin composition preferably contains an epoxy resin. One epoxy resin may be used alone or two or more epoxy resins may be used in combination. At least one epoxy resin is preferably a specific triphenylmethane epoxy resin.

[0077] The specific triphenylmethane epoxy resin has at least one selected from the group consisting of an alkyl group and an alkoxy group, and preferably has an alkyl group. The specific triphenylmethane epoxy resin may be used alone or in combination of two or more.

[0078] The alkyl group of the specific triphenylmethane epoxy resin preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic, but at least one alkyl group is preferably branched and preferably contains a tert-butyl group.

[0079] The alkoxy group of the specific triphenylmethane epoxy resin preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkoxy group may be linear, branched, or cyclic.

[0080] It is preferred that the benzene ring contained in the specific triphenylmethane type epoxy resin has two or more alkyl groups, and it is more preferred 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 contained in the benzene ring is preferably a branched alkyl group, and the branched alkyl group is preferably arranged at an ortho position relative to the glycidyloxy group.

[0081] The specific triphenylmethane epoxy resin may be an epoxy resin represented by the following formula (1).

[0082] [Chemistry 2]

[0083]

[0084] In formula (1), R each independently represents an alkyl group or an alkoxy group, i each independently represents an integer of 1 to 3, and k each independently represents an integer of 0 to 4. n is an average value and represents a number of 0 to 10.

[0085] Examples of the alkyl group and alkoxy group represented by R include the groups explained above.

[0086] i represents an integer of 1 to 3, preferably 2 or 3, more preferably 2. When i is 2, R represented by the subscript i is preferably at least one branched alkyl group, more preferably a combination of a branched alkyl group and a linear alkyl group, for example, a combination of a tert-butyl group and a methyl group. The tert-butyl group and the methyl group may be arranged at any position on the benzene ring, but the tert-butyl group is preferably arranged at the ortho position relative to the glycidyloxy group. In addition, the arrangement relationship between the tert-butyl group and the methyl group may be any one, and may be arranged at any one of the ortho position, meta position and para position.

[0087] k each independently represents an integer of 0 to 4, and 0 is preferred.

[0088] Specific examples of the specific triphenylmethane epoxy resin include epoxy resins represented by the following formula (2): In the formula (2), t-Bu represents a tert-butyl group.

[0089] [Chemistry 3]

[0090]

[0091] n is the average value, which represents a number from 0 to 10.

[0092] The curable resin composition of the present disclosure may contain other epoxy resins other than the specific triphenylmethane type epoxy resin.

[0093] As other epoxy resins, there is no particular limitation on the type thereof as long as it has two or more epoxy groups in one molecule. Specific examples of other epoxy resins are described below, but the present invention is not limited to these.

[0094] Specifically, there can be mentioned: a novolac-type epoxy resin (phenol novolac-type epoxy resin, o-cresol novolac-type epoxy resin, etc.) 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, 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 to obtain a novolac resin, and then epoxidizing the novolac resin; a triphenylmethane-type phenol resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst, and then epoxidizing the triphenylmethane-type phenol resin Triphenylmethane epoxy resin (except for specific triphenylmethane epoxy resin); copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained by co-condensing the phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; diphenylmethane epoxy resin as a diglycidyl ether of bisphenol A, bisphenol F, etc.; biphenyl epoxy resin as a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; stilbene epoxy resin as a diglycidyl ether of a stilbene-based phenol compound; sulfur-containing epoxy resin as a diglycidyl ether of bisphenol S, etc.; epoxy resin as a glycidyl ether of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; Glycidyl ester epoxy resins of glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine epoxy resins obtained by replacing the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. with a glycidyl group; dicyclopentadiene epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; alicyclic epoxy resins such as diepoxy vinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane obtained by epoxidizing an olefin bond in the molecule; p-xylene-modified phenol resins p-xylene modified epoxy resin as the glycidyl ether of meta-xylene modified phenol resin; meta-xylene modified epoxy resin as the glycidyl ether of meta-xylene modified phenol resin; terpene modified epoxy resin as the glycidyl ether of terpene modified phenol resin; dicyclopentadiene modified epoxy resin as the glycidyl ether of dicyclopentadiene modified phenol resin; cyclopentadiene modified epoxy resin as the glycidyl ether of cyclopentadiene modified phenol resin; polycyclic aromatic ring modified epoxy resin as the glycidyl ether of polycyclic aromatic ring modified phenol resin; naphthalene type epoxy resin as the glycidyl ether of phenol resin containing naphthalene ring; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bonds using peracids such as peracetic acid;Aralkyl epoxy resins obtained by epoxidizing aralkyl phenol resins such as phenol aralkyl resins and naphthol aralkyl resins. Furthermore, aminophenol glycidyl ethers, i.e., aminophenol epoxy resins, etc. can also be cited as epoxy resins. These epoxy resins can be used alone or in combination of two or more. ;

[0095] Among the epoxy resins, it is preferred that a biphenyl type epoxy resin be included from the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to the lead frame and the viewpoint of the balance between heat resistance and fluidity.

[0096] The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, and is preferably an epoxy resin represented by the following general formula (II).

[0097] [Chemistry 4]

[0098]

[0099] 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 they may be the same or different. n is an average value and represents a number of 0 to 10.

[0100] The stilbene-type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, and is preferably an epoxy resin represented by the following general formula (III).

[0101] [Chemistry 5]

[0102]

[0103] In formula (III), R 9 and R 10 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be the same or different. n is an average value and represents a number of 0 to 10.

[0104] The diphenylmethane epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, and is preferably an epoxy resin represented by the following general formula (IV).

[0105] [Chemistry 6]

[0106]

[0107] In formula (IV), R 11 and R 12 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be the same or different. n is an average value and represents a number of 0 to 10.

[0108] 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).

[0109] [Chemistry 7]

[0110]

[0111] In formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be the same or different. n is an average value and represents a number of 0 to 10.

[0112] The novolac-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac-type phenol resin. For example, an epoxy resin represented by the following general formula (VI) can be mentioned.

[0113] [Chemistry 8]

[0114]

[0115] In formula (VI), R 14 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. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0116] 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.

[0117] [Chemistry 9]

[0118]

[0119] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and 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.

[0120] As other triphenylmethane type epoxy resins other than the specific triphenylmethane type epoxy resin, a triphenylmethane type epoxy resin having no alkyl group and no alkoxy group can be mentioned.

[0121] The copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound and 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.

[0122] [Chemistry 10]

[0123]

[0124] In formula (IX), R 19 ~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i represents an integer of 0 to 3, j represents an integer of 0 to 2, and k represents an integer of 0 to 4. l and m are average values, which are numbers from 0 to 10, and (l+m) represents a number from 0 to 10. The end of the epoxy resin represented by formula (IX) is any 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 the same as those of R in formula (IX) 19 ~R 21 , i, j and k are the same as those defined above. n is 1 (when bonded via a methylene group) or 0 (when bonded not via a methylene group).

[0125] [Chemistry 11]

[0126]

[0127] Examples of the epoxy resin represented by the general formula (IX) include random copolymers randomly including one structural unit and m structural units, alternating copolymers alternately including one structural unit and m structural units, copolymers regularly including one structural unit and m structural units, block copolymers including one structural unit and m structural units in a block form, etc. Any of these may be used alone, or two or more thereof may be used in combination.

[0128] As the copolymerized epoxy resin, a methoxynaphthalene-cresol formaldehyde co-condensed epoxy resin, namely Epiclon HP-5000 (DIC Corporation, trade name), which contains the following two structural units in a random, alternating or block order is also preferred. For example, epoxy resins represented by the following general formula can be cited. In the following general formula, n and m are respectively average values, which are numbers from 0 to 10, and (n+m) represents a number from 0 to 10. Preferably, n and m are respectively average values, which are numbers from 1 to 9, and (n+m) represents a number from 2 to 10.

[0129] [Chemistry 12]

[0130]

[0131] The aralkyl epoxy resin is not particularly limited as long as it is an epoxy resin prepared from a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof as a raw material. For example, an epoxy resin obtained by glycidyl etherifying a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof is preferred, and an epoxy resin represented by the following general formula (X) and general formula (XI) is more preferred.

[0132] [Chemistry 13]

[0133]

[0134] In formula (X) and formula (XI), R 38 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, which may be the same or different. i is an integer of 0 to 3, j is an integer of 0 to 2, k is an integer of 0 to 4, and l is an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0135] Regarding R in the above-mentioned general formulae (II) to (VII) and (IX) to (XI): 8 ~R 21 and R 37 ~R 41 , the term "may be the same or different" means, for example, that 8 to 88 R in formula (II) 8 They may be the same or different. 9 ~R 21 and R 37 ~R 41 , which also means that the numbers of each contained in the formula may be the same or different. 8 ~R 21 and R 37 ~R 41 They may be the same or different. For example, R 9 With R 10 They may be the same or different.

[0136] In addition, the monovalent organic group having 1 to 18 carbon atoms in the general formulae (III) to (VII) and (IX) to (XI) is preferably an alkyl group or an aryl group.

[0137] In the general formulae (II) to (VII) and (IX) to (XI), n is an average value and is preferably independently in the range of 0 to 10. If n is 10 or less, the melt viscosity of the resin component will not be too high, the viscosity of the curable resin composition during melt molding will be reduced, and the occurrence of poor filling and deformation of the bonding wire (metal wire connecting the element and the lead) will tend to be suppressed. It is more preferable that n is set in the range of 0 to 4.

[0138] The epoxy equivalent of other epoxy resins is not particularly limited. From the viewpoint of balancing various properties such as moldability, heat resistance and electrical reliability, the epoxy equivalent of other epoxy resins 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.

[0139] The epoxy equivalent of other epoxy resins is set as the value measured by the method based on JIS K 7236:2009.

[0140] The other 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 other epoxy resin is preferably 40°C to 180°C. In addition, from the viewpoint of operability 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.

[0141] In the present disclosure, the softening point refers to a value measured by the ring and ball method of JIS K 7234:1986.

[0142] In the present disclosure, the melting point refers to a value measured by a visual method in accordance with JIS K 0064:1992.

[0143] From the viewpoint of the balance between moldability and heat resistance, the Mw of the other epoxy resin is preferably 550 to 1050, and more preferably 650 to 950.

[0144] The ratio of the specific triphenylmethane type epoxy resin in the curable resin composition to 100 parts by mass of the total amount of the epoxy resin is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more. The upper limit of the ratio is not particularly limited, and may be 95 parts by mass or less, 90 parts by mass or less, or 85 parts by mass or less.

[0145] From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the total content of the epoxy resin in the curable resin composition is preferably 0.5 to 60 mass %, more preferably 2 to 50 mass %, and further preferably 3 to 45 mass %.

[0146] (Hardener)

[0147] The curable 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 curing agents commonly used as components of curable resin compositions. The curing agent can be used alone or in combination of two or more.

[0148] In the present disclosure, as long as the curing agent has a structure that can react with the epoxy resin contained in the curable resin composition to cure the curable resin composition, even a compound with a small content and little contribution to the curing reaction of the curable resin composition is included in the curing agent.

[0149] Examples of the curing agent include phenolic curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents.

[0150] Among these, the curing agent is preferably a phenolic curing agent or an amine curing agent from the viewpoint of heat resistance. In addition, from the viewpoint of adhesion of the curable resin composition of the present disclosure to the lead frame and the viewpoint of heat resistance, the curing agent is preferably a phenolic curing agent.

[0151] Examples of phenolic curing agents include phenol resins and polyphenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; benzene resins synthesized from the phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, and the like; Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins; p-xylene-modified phenol resins and / or m-xylene-modified phenol resins; melamine-modified phenol resins; terpene-modified phenol resins; dicyclopentadiene-type phenol resins and dicyclopentadiene-type naphthol resins synthesized by copolymerizing the above-mentioned phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins; biphenyl-type phenol resins; triphenylmethane-type phenol resins obtained by condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; phenol resins obtained by copolymerizing two or more of these, etc. These phenolic hardeners may be used alone or in combination of two or more.

[0152] As the aralkyl phenol resin, phenol aralkyl resins and naphthol aralkyl resins synthesized from phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc. can be cited. The aralkyl phenol resin can also be copolymerized with other phenol resins. As the copolymerized aralkyl phenol resins, the copolymerized phenol resins of triphenylmethane phenol resin and aralkyl phenol resin, the copolymerized phenol resins of salicylaldehyde phenol resin and aralkyl phenol resin, the copolymerized phenol resins of novolac phenol resin and aralkyl phenol resin, etc. can be cited.

[0153] 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 dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof. For example, the phenol resins represented by the following general formulas (XII) to (XIV) are preferred.

[0154] [Chemistry 14]

[0155]

[0156] In formula (XII) to formula (XIV), R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 22 , R24 , R 25 and R 28 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. i is an integer of 0 to 3, j is an integer of 0 to 2, k is an integer of 0 to 4, and p is an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0157] From the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to the lead frame and the viewpoint of heat resistance, the aralkyl-type phenol resin is preferably a phenol resin represented by the general formula (XIII).

[0158] From the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to the lead frame and the viewpoint of heat resistance, in the general formula (XIII), both i and k are preferably 0.

[0159] The dicyclopentadiene-type phenol resin is not particularly limited as long as it is a phenol resin obtained using a compound having a dicyclopentadiene skeleton as a raw material. For example, the phenol resin represented by the following general formula (XV) can be mentioned.

[0160] [Chemistry 15]

[0161]

[0162] In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and 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.

[0163] The triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained using an aromatic aldehyde compound as a raw material, and is preferably a phenol resin represented by the following general formula (XVI).

[0164] [Chemistry 16]

[0165]

[0166] In formula (XVI), R 30 and R 31 The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i is an integer of 0 to 3, and k is an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0167] The copolymerized phenol resin of triphenylmethane type phenol resin and aralkyl type phenol resin is not particularly limited as long as it is a copolymerized phenol resin obtained from a compound having a benzaldehyde skeleton as a raw material and an aralkyl type phenol resin. For example, a phenol resin represented by the following general formula (XVII) is preferred.

[0168] [Chemistry 17]

[0169]

[0170] In formula (XVII), R 32 ~R 34 The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i is an integer of 0 to 3, k is an integer of 0 to 4, and q is an integer of 0 to 5. l and m are average values ​​and are numbers of 1 to 11.

[0171] The novolac-type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. For example, a phenol resin represented by the following general formula (XVIII) is preferred.

[0172] [Chemistry 18]

[0173]

[0174] In formula (XVIII), R 35 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. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0175] Regarding R in the general formulae (XII) to (XVIII) 22 ~R 36 The phrase "may be the same or different" means, for example, that i R in formula (XII) 22 They may be the same or different from each other. 23 ~R 36 , which also means that the numbers of each contained in the formula may be the same or different. 22 ~R 36 They may be the same or different. 22 and R 23 Can be the same or different, R 30 and R 31 They may be the same or different.

[0176] The n in the general formula (XII) to the general formula (XVIII) is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity of the curable resin composition during melt molding will also be low, which will not easily cause filling defects and deformation of bonding wires (metal wires connecting components and leads). The average n in one molecule is preferably set in the range of 0 to 4.

[0177] Specific examples of the amine-based curing agent include: aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, and 2-methylaniline; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole; imidazoline compounds such as imidazoline, 2-methylimidazoline, and 2-ethylimidazoline; and the like.

[0178] The functional group equivalent of the curing agent (hydroxyl equivalent in the case of a phenolic curing agent, active hydrogen equivalent in the case of an amine curing agent) is not particularly limited. From the viewpoint of balancing 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.

[0179] The hydroxyl equivalent in the case of a phenolic curing agent is a value calculated based on the hydroxyl value measured in accordance with JIS K 0070: 1992. The active hydrogen equivalent in the case of an amine curing agent is a value calculated based on the amine value measured in accordance with JIS K 7237:1995.

[0180] When the curing agent is solid at 25° C., the softening point or melting point thereof is not particularly limited. From the viewpoint of moldability and heat resistance, the softening point or melting point of the curing agent is preferably 40° C. to 180° C. From the viewpoint of operability during the production of the curable resin composition, the softening point or melting point of the curing agent is preferably 50° C. to 130° C.

[0181] 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 may be, for example, 0.5 to 1.2, 0.5 to 1.0, 0.55 to 0.9, or 0.6 to 0.8.

[0182] When the equivalent ratio is set to 0.5 or more and less than 1.0, the adhesion between the cured product of the curable resin composition and the supporting member tends to be improved. The reason is not clear, but the value of tanδ near the reflow temperature tends to be increased, and the internal stress of the cured resin during reflow tends to be relaxed.

[0183] When the hardener includes a phenolic hardener, from the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to the lead frame, the content of the phenolic hardener relative to the total mass of the hardener 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.

[0184] When the phenolic curing agent includes an aralkylphenol resin, the content of the aralkylphenol resin relative to the total mass of the phenolic curing agent is more preferably 60 to 100 mass %, and further preferably 70 to 100 mass %, from the viewpoint of the adhesion of the curable resin composition of the present disclosure to the lead frame.

[0185] (Inorganic filler)

[0186] The curable resin composition of the present disclosure may also contain an inorganic filler. When the curable resin composition contains an inorganic filler, 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 semiconductor packaging, it is preferably contained in an inorganic filler.

[0187] The inorganic material constituting the inorganic filler is not particularly limited. Specifically, the inorganic material includes spherical silica, crystalline silica, glass, aluminum oxide, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, aluminum nitride, diaspore, beryllium oxide, magnesium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, mica, titanate, etc.

[0188] Inorganic fillers containing inorganic materials having flame retardant effects may also be used. Examples of inorganic materials having flame retardant effects include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.

[0189] The inorganic filler may be used alone or in combination of two or more.

[0190] The shape of the inorganic filler is not particularly limited, and examples thereof include powder, spherical, and fibrous shapes, etc. A spherical shape is preferred from the viewpoint of fluidity during molding of the curable resin composition and mold wear resistance.

[0191] The average particle size of the inorganic filler is not particularly limited. From the viewpoint of balancing the viscosity and filling properties of the curable resin composition, the volume average particle size 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.

[0192] The volume average particle size of the inorganic filler can be measured as a volume average particle size (D50) using a laser diffraction scattering particle size distribution analyzer.

[0193] The particle size of the inorganic filler may be cut to 100 μm or less, 75 μm or less, or 53 μm or less.

[0194] The top cut particle size can be determined from the particle size distribution when the volume average particle size (D50) is measured.

[0195] When the curable resin composition contains an inorganic filler, the content of the inorganic filler is not particularly limited. The content of the inorganic filler relative 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.

[0196] If the content of the inorganic filler is 30% by mass or more of the curable resin composition as a whole, the thermal expansion coefficient, thermal conductivity, elastic modulus and other properties of the cured product tend to be further improved. If the content of the inorganic filler is 90% by mass or less of the curable resin composition as a whole, the increase in the viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the moldability tends to be further improved.

[0197] The content of the inorganic filler relative to the entire curable resin composition is preferably 68 to 86 volume %, more preferably 70 to 84 volume %, and even more preferably 72 to 82 volume %.

[0198] When the content of the inorganic filler is 68% by volume or more of the curable resin composition as a whole, the thermal expansion coefficient, thermal conductivity, elastic modulus, and other properties of the cured product tend to be further improved. When the content of the inorganic filler is 86% by volume or less of the curable resin composition as a whole, the viscosity increase of the curable resin composition is suppressed, the fluidity is further improved, and the moldability tends to be further improved.

[0199] (hardening accelerator)

[0200] The curable resin composition of the present disclosure may also include 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 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 to these.

[0201] Examples of the curing accelerator include diazabicycloolefins such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and 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 Compounds with intramolecular polarization formed by adding maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 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 other quinone compounds, compounds having π bonds such as diazonium methane; cyclic amidinium compounds such as tetraphenylborate of DBU, tetraphenylborate of DBN, tetraphenylborate of 2-ethyl-4-methylimidazole, tetraphenylborate of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine amine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and other tertiary amine compounds; 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, and tetrapropylammonium hydroxide; primary phosphines such as ethylphosphine and phenylphosphine, secondary phosphines such as dimethylphosphine and diphenylphosphine, triphenylphosphine, diphenyl (p-tolyl) phosphine, tri (alkylphenyl) phosphine, tri (alkoxyphenyl) phosphine, tri (alkylalkoxyphenyl) phosphine, tri (dialkylphenyl) phosphine, tri (trialkylphenyl) phosphine, tri (tetraalkylphenyl) phosphine, tri (dialkoxyphenyl) phosphine, tri (trialkoxyphenyl) phosphine , tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tri(benzyl)phosphine and other tertiary phosphine and other organic phosphine; phosphine compounds such as complexes of the organic phosphine and organic boron; compounds with intramolecular polarization formed by the addition of the organic phosphine or the phosphine compound with maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 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 and other quinone compounds, and compounds having π bonds such as diazonophenylmethane;The organic phosphine or the phosphine compound is reacted with 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-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, Compounds with intramolecular polarization obtained by reacting halogenated phenol compounds such as 6-bromo-2-naphthol and 4-bromo-4'-hydroxybiphenyl and then undergoing a dehydrohalogenation process; tetrasubstituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborates of tetrasubstituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetrasubstituted phosphonium and phenol compounds; phosphobetaine compounds; adducts of phosphonium compounds and silane compounds, etc.;

[0202] Examples of suitable hardening accelerators include triphenylphosphine and quinone compound adducts of triphenylphosphine.

[0203] When the curable resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.1% to 8% by mass, more preferably 0.3% to 7% by mass, and further preferably 0.5% to 6% 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 curable resin composition of the present disclosure becomes an appropriate value, and the production of the molded article becomes easy.

[0204] (Stress Relief Agent)

[0205] The second curable resin composition of the present disclosure contains a polysiloxane-based stress relaxant.

[0206] The polysiloxane stress relaxant may be used alone or in combination of two or more. The polysiloxane stress relaxant may be in any form such as solid, liquid, or rubber particles at 25° C. In addition, as long as the polysiloxane stress relaxant contains a polysiloxane skeleton, it may contain a polymer part other than the polysiloxane skeleton, such as a methyl methacrylate-silicone copolymer.

[0207] Examples of the polysiloxane stress relaxant include polysiloxane stress relaxants having a methyl group and a phenyl group, polysiloxane stress relaxants having an epoxy group, polysiloxane stress relaxants having an amino group, and polysiloxane stress relaxants obtained by polyether-modifying these.

[0208] The polysiloxane-based stress relaxant is more preferably polysiloxane having an epoxy group, polyether polysiloxane, etc. Among them, polyether polysiloxane is preferred from the viewpoint of suppressing the peeling of the cured product from the lead frame.

[0209] The polyether polysiloxane is not particularly limited as long as it is a compound in which a polyether group is introduced into silicone, which is a polymer compound having a main skeleton based on a siloxane bond.

[0210] The polyether polysiloxane may be a side chain modified polyether polysiloxane or a terminal modified polyether polysiloxane. Of these, the polyether polysiloxane is preferably a side chain modified polyether polysiloxane from the viewpoint of suppressing poor appearance of the cured product.

[0211] An example of the polyether polysiloxane is epoxy-polyether polysiloxane. The epoxy-polyether polysiloxane is not particularly limited as long as it is a compound in which a polyether group and an epoxy group are introduced into silicone, which is a polymer compound having a main skeleton based on a siloxane bond.

[0212] The epoxy-polyether polysiloxane may be a side chain modified epoxy-polyether polysiloxane, a terminal modified epoxy-polyether polysiloxane, or a side chain and terminal modified epoxy-polyether polysiloxane. As the main skeleton of the epoxy-polyether polysiloxane, polydimethylsiloxane is preferred. As the polyether group, a polyether group formed by polymerization of one or both of ethylene oxide and propylene oxide is preferred.

[0213] The epoxy-polyether polysiloxane is preferably a side chain-modified epoxy-polyether polysiloxane in which a polyether group (preferably a polyether group obtained by polymerization of one or both of ethylene oxide and propylene oxide) and an epoxy group are respectively present in the side chain of silicone (preferably polydimethylsiloxane).

[0214] The polysiloxane-based stress relaxant may include a branched polysiloxane having the following structural units (a) and (b), and the terminal is selected from R 1 , hydroxyl and alkoxy groups, and the epoxy equivalent is 500 g / eq to 4000 g / eq. 1 A branched polysiloxane having at least one functional group selected from the group consisting of a hydroxyl group and an alkoxy group and an epoxy equivalent of 500 g / eq to 4000 g / eq is also referred to as a “specific branched polysiloxane”.

[0215] [Chemistry 19]

[0216]

[0217] R 1 represents an unsubstituted alkyl, alkenyl, aryl, or aralkyl group having 1 to 12 carbon atoms, and a plurality of R 1 In the case of multiple R1 They may be the same or different. X represents a 2,3-epoxypropyl group, a 3,4-epoxybutyl group, a 4,5-epoxypentyl group, a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group, a 4-glycidyloxybutyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, or a 3-(3,4-epoxycyclohexyl)propyl group.

[0218] R 1 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.

[0219] As R 1 Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl.

[0220] As R 1 Examples of the alkenyl group include an alkyl group, a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.

[0221] As R 1 Examples of the aryl group include phenyl, tolyl, xylyl, naphthyl, and biphenyl.

[0222] As R 1 Examples of the aralkyl group include benzyl and phenethyl.

[0223] Among them, as R 1 , preferably methyl or phenyl.

[0224] X represents a 2,3-epoxypropyl group, a 3,4-epoxybutyl group, a 4,5-epoxypentyl group, a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group, a 4-glycidyloxybutyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, or a 3-(3,4-epoxycyclohexyl)propyl group, and among these, a 3-glycidyloxypropyl group is preferred.

[0225] In addition, from the viewpoint of storage stability of the polymer, the terminal of the specific branched polysiloxane is selected from the group consisting of R 1 , at least one functional group selected from the group consisting of hydroxyl and alkoxy.

[0226] The epoxy equivalent of the specific branched polysiloxane is in the range of 500 g / eq to 4000 g / eq, preferably 1000 g / eq to 2500 g / eq. When the epoxy equivalent of the specific branched polysiloxane is 500 g / eq or more, the fluidity of the curable resin composition tends to be improved, and when the epoxy equivalent of the specific branched polysiloxane is 4000 g / eq or less, the oozing out to the surface when the cured product is formed tends to be suppressed, and the moldability tends to be excellent.

[0227] From the viewpoint of the fluidity of the curable resin composition and the low warpage property when the cured product is obtained, the specific branched polysiloxane preferably further has the following structural unit (c).

[0228] [Chemistry 20]

[0229]

[0230] R in structural unit (c) 1 is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and has a plurality of R 1 They may be the same or different. 1 Examples of the hydrocarbon group represented by include R as the structural unit (a) and the structural unit (b): 1 And the base listed.

[0231] The specific branched polysiloxane may be a block copolymer or a random copolymer, and is preferably a random copolymer.

[0232] The softening point of the specific branched polysiloxane is preferably 40° C. to 120° C., and more preferably 50° C. to 100° C. When the softening point of the specific branched polysiloxane is 40° C. or higher, the mechanical strength of the curable resin composition when the cured product is obtained tends to be improved, and when the softening point of the specific branched polysiloxane is 120° C. or lower, the dispersibility of the specific branched polysiloxane in the curable resin composition tends to be excellent.

[0233] As a method for adjusting the softening point of a specific branched polysiloxane, examples include appropriately setting the molecular weight of the specific branched polysiloxane, the content ratio of the structural unit (a) to the structural unit (c), the type of silicon-bonded organic group, etc. From the perspective of the dispersibility of the specific branched polysiloxane in the curable resin composition and the fluidity of the curable resin composition, the adjustment of the softening point is preferably to adjust the content of the aryl group in the specific branched polysiloxane. At this time, the aryl group can include phenyl, tolyl, xylyl, naphthyl, biphenyl, etc., and phenyl is more preferred. The content of the phenyl group in the monovalent organic group bonded to the silicon atom in the specific branched polysiloxane is preferably set to 60 mol% to 99 mol%, and more preferably set to 70 mol% to 85 mol%.

[0234] The weight average molecular weight (Mw) of the specific branched polysiloxane is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and still more preferably 3,000 to 10,000, as measured by gel permeation chromatography (GPC) and calculated using a standard polystyrene calibration curve.

[0235] The specific branched polysiloxane can be obtained by the production method shown below, or can be obtained as a commercial product.

[0236] The method for producing the specific branched polysiloxane is not particularly limited and can be produced by a known method. For example, the organochlorosilane, organoalkoxysilane, siloxane or their partially hydrolyzed condensates that can form the (a) to (c) units by hydrolysis condensation reaction can be mixed into a mixed solution of an organic solvent capable of dissolving the raw materials and the reaction product and water in an amount that can hydrolyze all the hydrolyzable groups of the raw materials, and subjected to a hydrolysis condensation reaction to obtain the same. At this time, in order to reduce the amount of chlorine contained as an impurity in the curable resin composition, it is preferred to use organoalkoxysilane and / or siloxane as a raw material. In this case, as a catalyst to promote the reaction, it is preferred to add an acid, a base or an organometallic compound.

[0237] Examples of the organoalkoxysilane and / or siloxane as a raw material for the specific branched polysiloxane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxysilane, diphenyldiethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, and the like. Oxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl(methyl)dimethoxysilane, 3-glycidoxypropyl(methyl)diethoxysilane, 3-glycidoxypropyl(phenyl)dimethoxysilane, 3-glycidoxypropyl(phenyl)diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(phenyl)dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(phenyl)diethoxysilane, and hydrolysis condensates thereof.

[0238] The total content of the polysiloxane stress relaxant is preferably 3 to 50 parts by mass, more preferably 4 to 45 parts by mass, and even more preferably 5 to 40 parts by mass, based on 100 parts by mass of the resin component (the total amount of the epoxy resin and the hardener).

[0239] The second curable resin composition disclosed in the present invention may also include other stress relaxers other than polysiloxane stress relaxers. As other stress relaxers, there can be listed: thermoplastic elastomers such as styrene, olefin, urethane, polyester, polyether, polyamide, polybutadiene, natural rubber (NR), acrylonitrile-butadiene copolymer (NBR), acrylic rubber, urethane rubber, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-butyl acrylate copolymer, triphenylphosphine, coumarone resin, etc., which use these rubber particles forming a core-shell structure. Other stress relaxers can be used alone or in combination of two or more.

[0240] The stress relaxer may be a commercial product or a synthetic stress relaxer. Examples of commercial products include polysiloxane-based stress relaxers and specific branched polysiloxane-based stress relaxers, such as 217 Flake, 233 Flake, 249 Flake, 220 Flake, SH6018, AY42-119 (all from Dow-Toray Co., Ltd.), KR-480 (Shin-Etsu Chemical Co., Ltd.), and SRK-200A (Mitsubishi Chemical Co., Ltd.).

[0241] Examples of butadiene-based and acrylic-based stress relaxants include U POWDER (Unitika Co., Ltd.), CTBN1008SP and CTBN1009SP (UBE Co., Ltd.), JP200 (Nippon Soda Co., Ltd.), and BTA-751 (Dow Chemical Co., Ltd.).

[0242] Examples of the polyether-based stress relaxant include FZ-3711, FZ-3720, and FZ-3730 (all from The Dow Chemical Company).

[0243] The content of the polysiloxane stress relaxant relative to the total content of the stress relaxant is preferably 10% by mass or more, preferably 15% by mass or more, and preferably 20% by mass or more.

[0244] The first curable resin composition and the third curable resin composition disclosed herein may also include stress relaxants such as silicone oil and silicone rubber particles. By including a stress relaxant in the curable resin composition, the warping deformation of the package and the generation of package cracks can be further reduced. As a stress relaxant, commonly used known stress relaxants (flexible agents) can be cited. Specifically, as a stress relaxant, thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, polybutadiene, natural rubber (NR), acrylonitrile-butadiene copolymer (NBR), acrylic rubber, urethane rubber, silicone powder, etc., rubber particles, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. have core-shell structures. Rubber particles. The stress relaxant can be used alone or in combination of two or more. Among them, silicone stress relaxants are preferably used. Examples of the silicone-based stress relaxant include silicone-based stress relaxants having an epoxy group, silicone-based stress relaxants having an amino group, silicone-based stress relaxants obtained by polyether-modifying these, etc. Examples of the silicone-based stress relaxants that can be used in the first curable resin composition and the third curable resin composition include the silicone-based stress relaxants contained in the second curable resin composition.

[0245] When the first curable resin composition and the third curable resin composition contain a stress relaxant, the content thereof is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, based on 100 parts by mass of the epoxy resin contained in the curable resin composition.

[0246] (Various additives)

[0247] The curable resin composition of the present disclosure may contain various additives such as coupling agents, mold release agents, colorants, flame retardants, and ion exchangers in addition to the above components. In addition, the curable resin composition of the present disclosure may also contain a siloxane compound having a structural unit containing an epoxy group and an alkoxy group and having a polymerization degree of 2. In addition to the additives exemplified below, the curable resin composition may contain various additives well known in the above technical field as needed.

[0248] (Coupling agent)

[0249] The curable resin composition of the present disclosure may also contain a coupling agent. The type of the coupling agent is not particularly limited, and a known coupling agent can be used. Examples of the coupling agent include silane coupling agents, titanium coupling agents, and the like. The coupling agent may be used alone or in combination of two or more.

[0250] 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.

[0251] Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tri(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(di-tridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylate isostearyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearyl diacrylate titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0252] When the curable resin composition contains a coupling agent, from the viewpoint of the adhesiveness of the interface between the epoxy resin and the inorganic filler, the content of the coupling agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the inorganic filler contained in the curable resin composition.

[0253] (Release Agent)

[0254] In the case of using a mold during molding, the curable resin composition of the present disclosure may also contain a release agent from the viewpoint of mold release from the mold. The release agent is not particularly limited, and a known release agent can be used. Examples of the release agent include: carnauba wax, higher fatty acids such as octadecanoic acid and stearic acid, higher fatty acid metal salts, ester waxes such as octadecanoic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. The release agent may be used alone or in combination of two or more.

[0255] When the curable 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 curable resin composition. If the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency that sufficient releasability can be obtained. If it is 15 parts by mass or less, there is a tendency that better releasability can be obtained.

[0256] (Colorant)

[0257] The curable resin composition of the present disclosure may also contain a colorant. Examples of the colorant include carbon black, organic dyes, organic pigments, titanium oxide, red lead, iron oxide and other known colorants. The content of the colorant may be appropriately selected according to the purpose, etc. The colorant may be used alone or in combination of two or more.

[0258] When the curable resin composition contains a colorant, the content of the colorant is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 4% by mass.

[0259] (Flame Retardant)

[0260] The curable resin composition of the present disclosure may also contain a flame retardant. The flame retardant is not particularly limited, and a conventionally known flame retardant may be used. Examples of the flame retardant include organic compounds or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardant may be used alone or in combination of two or more.

[0261] When the curable resin composition of the present disclosure contains a flame retardant, the content of the flame retardant is not particularly limited as long as it is a sufficient amount to obtain the desired flame retardant effect. The content of the flame retardant is preferably 1 to 300 parts by mass, more preferably 2 to 150 parts by mass, relative to 100 parts by mass of the epoxy resin contained in the curable resin composition.

[0262] (Ion Exchanger)

[0263] The curable resin composition of the present disclosure may also contain an ion exchanger. When the curable resin composition is used as a sealing material for a semiconductor package, it is preferred to contain an inorganic ion exchanger from the viewpoint of improving the moisture resistance and high temperature storage characteristics of an electronic component device including the sealed element.

[0264] The ion exchanger is not particularly limited, and any known ion exchanger can be used. Specifically, hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth can be listed. One type of ion exchanger can be used alone, or two or more types can be used in combination. Specifically, as the ion exchanger, hydrotalcite represented by the following general formula (A) can be listed.

[0265] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O…(A)

[0266] (0<X≦0.5, m is a positive number)

[0267] When the curable resin composition of the present disclosure contains an ion exchanger, the content of the ion exchanger 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 to 30 parts by mass, more preferably 1 to 6 parts by mass, relative to 100 parts by mass of the epoxy resin contained in the curable resin composition.

[0268] (Physical Properties of Curable Resin Composition)

[0269] From the viewpoint of fluidity, the spiral flow of the curable resin composition of the present disclosure obtained by the following method is preferably 100 cm or more, more preferably 120 cm or more, further preferably 140 cm or more, and particularly preferably 160 cm or more. The upper limit of the spiral flow is not particularly limited, and may be, for example, 170 cm or less.

[0270] The spiral flow was measured using a spiral flow measurement mold in accordance with EMMI-1-66, and the flow distance when the curable resin composition was 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 was determined.

[0271] From the viewpoint 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 further 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 further preferably 44 seconds or less.

[0272] The gel time is measured from the time 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 preferred to heat the resin while periodically stirring it with a spatula. The so-called "loss of viscosity of the resin" refers to the phenomenon that the resin breaks or is destroyed when the resin is kneaded with a spatula.

[0273] The viscosity of the curable 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, further preferably 1 Pa·s to 50 Pa·s, and particularly preferably 1 Pa·s to 20 Pa·s. The viscosity of the curable resin composition at 175° C. is measured using a flow tester viscometer at a pressure of 1 MPa, a nozzle diameter of 1 mm, and a length of 10 mm.

[0274] From the viewpoint of heat resistance, the glass transition temperature (Tg) of the cured product of the curable resin composition is preferably 80° C. or higher, more preferably 85° C. or higher, and further preferably 90° C. or higher. The upper limit of Tg is not particularly limited and may be 200° C. or lower, or 180° C. or lower.

[0275] In the present disclosure, the glass transition temperature of the cured product is defined as the temperature of the intersection of a tangent line at 10° C. to 30° C. and a tangent line at 200° C. to 220° C. obtained by the measurement of the linear expansion coefficient.

[0276] From the viewpoints of moldability and handleability of the curable resin composition, the hot hardness of the cured product is preferably 56 or more, more preferably 58 or more, and further preferably 60 or more. The upper limit of the hot hardness is not particularly limited, and may be 90 or less, 88 or less, 85 or less, 83 or less, or 80 or less.

[0277] Regarding the hot hardness of the cured product, the hot hardness (175°C) was measured using a Shore D hardness tester (e.g., manufactured by Gaozheng Keji Co., Ltd.) for a rectangular hot hardness test piece of size: 4mm×80mm×10mm. The test piece was obtained by hardening and molding the curable resin composition under the conditions of 175°C, 120 seconds, and a pressure of 7MPa using a transfer molding machine and a circular plate mold. The measurement was performed in a press just after the test piece was made.

[0278] From the viewpoint of the moldability and workability of the curable resin composition, the hot strength of the cured product is preferably 3MN / m 2 More preferably 4MN / m 2 More than 5MN / m 2 In addition, the upper limit of the heat strength is not particularly limited and can be 20MN / m 2 Below, also 18MN / m 2 Below, also 16MN / m 2 the following.

[0279] The hot strength of the cured product was measured using a load tester (e.g., Aikoh Engineering Co., Ltd., table tester 1301K) for a rectangular hot strength test piece of size 4 mm × 80 mm × 10 mm. The test piece was obtained by curing and molding the curable resin composition at 175°C, 120 seconds, and a pressure of 7 MPa using a transfer molding machine and a circular plate mold.

[0280] From the viewpoint of the adhesion of the cured product to the lead frame, the elastic modulus at 260° C. of the cured product of the first curable resin composition or the second curable resin composition also depends on the filler amount, but is preferably 1000 MPa or less, more preferably 900 MPa or less, and even more preferably 800 MPa or less.

[0281] From the viewpoint of the adhesion of the cured product to the lead frame, the adhesive strength of the cured product of the first curable resin composition or the second curable resin composition to Ag (silver) is preferably 0.3 MPa or more, more preferably 0.35 MPa or more, and further preferably 0.4 MPa or more. In addition, the upper limit of the adhesive strength is not particularly limited.

[0282] From the viewpoint of suppressing the warping of the package of the cured product, the linear expansion coefficient of the cured product of the first curable resin composition or the second curable resin composition at 180°C to 200°C is preferably 25ppm / °C or more, more preferably 28ppm / °C or more, and further preferably 31ppm / °C or more. Previously, it was believed that the smaller the linear expansion coefficient, the more the peeling from the lead frame could be suppressed, but it was found that in the first curable resin composition or the second curable resin composition disclosed in the present invention, the linear expansion coefficient of the cured product at 180°C to 200°C was 31ppm / °C or more, which was effective in suppressing the peeling from the lead frame. Although the reason is not clear, it is speculated that it is the thermal stress reduction effect brought about by the suppression of warping caused by the difference in linear expansion coefficients between components. In particular, in the first curable resin composition or the second curable resin composition disclosed in the present invention, the glass transition temperature (Tg) can be lowered and the allowable range of the linear expansion coefficient can be expanded.

[0283] From the viewpoint of suppressing the generation of thermal stress with the packaging member, the upper limit of the linear expansion coefficient is preferably 60 ppm / °C or less, more preferably 55 ppm / °C or less, and still more preferably 50 ppm / °C or less.

[0284] (Method for producing curable resin composition)

[0285] The method for producing the curable resin composition is not particularly limited. As a common method, the following method can be cited: after the components of the prescribed amount are fully mixed by a mixer, etc., melt-kneading is performed by a mixing roll, an extruder, etc., and then cooled and crushed. More specifically, for example, the following method can be cited: the prescribed amount of the components is uniformly stirred and mixed, kneaded and cooled by a kneader, a roll, an extruder, etc. preheated to 70°C to 140°C, and then crushed.

[0286] 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 thereof include powder, granules, and flakes. From the viewpoint of workability, the size and mass of the curable resin composition in the form of flakes are preferably in accordance with the molding conditions of the package.

[0287] (Application of curable resin composition)

[0288] The application of the curable resin composition disclosed herein is not particularly limited, and it can be used, for example, as a sealant for electronic component devices and in various mounting technologies. In addition, the curable resin composition disclosed herein can be used for various applications where the resin composition preferably has good fluidity and curability, such as resin molded bodies for various modules, resin molded bodies for motors, resin molded bodies for vehicles, and sealants for electronic circuit protection materials.

[0289] <Electronic components and devices>

[0290] The electronic component device of the present disclosure includes a component and a cured product of the curable resin composition that seals the component.

[0291] The electronic component device may include a support member on which the components are mounted.

[0292] Examples of the supporting member include a lead frame, a wired carrier tape, a wiring board, glass, a silicon wafer, an organic substrate, etc. Among the supporting members, a lead frame is preferred from the viewpoint of adhesion with a cured product of the curable resin composition.

[0293] The surface of the lead frame may or may not be roughened. From the viewpoint of production cost, a lead frame is preferred, and from the viewpoint of adhesiveness, a roughened lead frame is preferred.

[0294] The roughening method is not particularly limited, and examples thereof include alkali treatment, silane coupling treatment, sand bedding treatment, plasma treatment, and corona discharge treatment.

[0295] The lead frame preferably contains Ag, and may further contain Cu or the like.

[0296] Examples of elements included in the electronic component device include active elements such as silicon chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils.

[0297] The following structures can be cited as specific structures of the electronic component device, but the present invention is not limited to these structures.

[0298] (1) Common resin-sealed ICs such as dual inline package (DIP), plastic leaded chip carrier (PLCC), quad flat package (QFP), small outline package (SOP), small outline J-lead package (SOJ), thin small outline package (TSOP), and thin quad flat package (TQFP), which have a structure in which a component is fixed to a lead frame and the terminal portion of the component such as a bonding pad and a lead portion are connected by wire bonding, bumps, etc., and then sealed with a curable resin composition;

[0299] (2) Tape Carrier Package (TCP), which has a structure in which a component connected to a carrier tape by bumps is sealed using a curable resin composition;

[0300] (3) Chip on Board (COB) modules, hybrid ICs, polycrystalline modules, etc., which have a structure in which a curable resin composition is used to seal components on wiring formed on a supporting member by wire bonding, flip chip bonding, soldering, etc.;

[0301] (4) Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), System in a Package (SiP), etc., which have a structure in which components are mounted on the surface of a support member having terminals for connecting to a wiring board formed on the back side, and the components are connected to wiring formed on the support member by bumps or wire bonding, and then the components are sealed with a curable resin composition.

[0302] The method of sealing the element using the curable resin composition is not particularly limited, and a known method can be applied. As a sealing method, for example, low-pressure transfer molding is generally used, and injection molding, compression molding, casting, etc. can also be used.

[0303] [Example]

[0304] Hereinafter, the present disclosure will be specifically described by way of examples, but the present disclosure is not limited to these examples. In addition, the numerical values ​​in the tables refer to "parts by mass" unless otherwise specified.

[0305] [Example 1A, Example 2A and Comparative Examples 1A to 5A]

[0306] The materials of the formulation shown in Table 1 were premixed (dry blended), kneaded for about 15 minutes using a biaxial roll (roll surface temperature: about 80° C.), cooled and pulverized to produce a powdered 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.

[0307] The details of the materials in Table 1 are as follows.

[0308] ·Epoxy resin A: biphenyl type, epoxy equivalent 192g / eq

[0309] ·Epoxy resin B: Sulfur-containing epoxy resin, epoxy equivalent 238g / eq~254g / eq, melting point 116℃~126℃

[0310] · Epoxy resin C: triphenylmethane type (without alkyl or alkoxy groups), epoxy equivalent 169 g / mol, softening point 60°C

[0311] Epoxy resin D: o-cresol type, epoxy equivalent 200g / eq

[0312] · Epoxy resin E: triphenylmethane type (without alkyl or alkoxy groups), epoxy equivalent 165 g / eq, melting point 104°C

[0313] Epoxy resin F: triphenylmethane type epoxy resin represented by the above formula (2), epoxy equivalent 214 g / eq, melting point 85°C

[0314] Hardener A: phenol resin, hydroxyl equivalent 175g / eq

[0315] Hardener B: triphenylmethane phenol resin, hydroxyl equivalent 104g / eq

[0316] Hardener C: Alkyl-modified phenolic resin, hydroxyl equivalent 224 g / eq

[0317] Hardener D: aminotriazine-modified phenolic resin, amine equivalent 120 g / eq

[0318] · Hardening accelerator: 1,4-benzoquinone adduct of triphenylphosphine

[0319] Inorganic filler: spherical silica particles with a top cut of 75 μm and a volume average particle size of 19 μm

[0320] · Coupling agent A: N-phenyl-3-aminopropyltrimethoxysilane

[0321] Coupling agent B: 3-glycidyloxypropyltrimethoxysilane

[0322] Coupling agent C: 3-mercaptopropyltrimethoxysilane

[0323] Release agent: ester wax such as dioctadecanoic acid ester

[0324] Colorant: Carbon black

[0325] Ion exchanger: hydrotalcite

[0326] Stress Relaxant A: Methyl / phenyl polysiloxane compound, solid at 25°C

[0327] Stress reliever B: triphenylphosphine oxide

[0328] Stress relaxant C: coumarone resin, softening point 100℃

[0329] Stress relaxant D: Specific branched polysiloxane with epoxy equivalent of 1660 and softening point of 80°C

[0330] <<Evaluation of curable resin composition>>

[0331] The properties of the curable resin compositions prepared in Examples and Comparative Examples were measured and evaluated by the following methods.

[0332] <Measurement of spiral flow>

[0333] The spiral flow of the curable resin composition is measured by the above method.

[0334] <Measurement of gel time>

[0335] The gel time of the curable resin composition is measured by the above method.

[0336] <Viscosity measurement>

[0337] The viscosity of the curable resin composition at 175° C. is measured by the above method.

[0338] <Measurement of linear expansion coefficient>

[0339] The thermal expansion coefficient of the cured product of the curable resin composition at 180° C. to 200° C. was measured by the above method. As a thermomechanical analyzer, TMA / SS6100 manufactured by Seiko Instruments Co., Ltd. was used.

[0340] <Glass transition temperature of cured product (Tg)>

[0341] The temperature of 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 linear expansion coefficient was defined as the glass transition temperature of the cured product.

[0342] <Measurement of elastic modulus>

[0343] The thermal expansion coefficient of the cured product of the curable resin composition at 260° C. was measured by the above method. As a viscoelasticity measuring apparatus, RSAIII manufactured by TA Instruments was used.

[0344] <Measurement of Adhesion Strength to Ag (Silver)>

[0345] The adhesive strength to Ag (silver) of the cured product of the curable resin composition was measured by the above method. As a measuring device, a product name 4000 Optima manufactured by Nordson was used.

[0346] <Determination of hot hardness>

[0347] The hardness of the cured product of the curable resin composition when heated was measured by the above method. As a measuring device, a Shore hardness meter type D manufactured by Kobun Keiki Co., Ltd. was used.

[0348] <Determination of hot strength>

[0349] The hot strength of the cured product of the curable resin composition was measured by the above method. A table tester 1301K manufactured by Aikoh Engineering Co., Ltd. was used as a measuring device.

[0350] <Evaluation of peeling properties during high temperature moisture absorption>

[0351] An 80-pin flat package (lead frame material: AgCu) having an outer dimension of 20 mm in length, 14 mm in width, and 2 mm in thickness and carrying a silicon chip (8 mm in length, 10 mm in width, and 0.4 mm in thickness) sealed with a cured product of the curable resin composition formed under the above conditions was produced.

[0352] The packages were heated under two conditions: 85° C., 85% RH for 168 hours (MSL1), and 85° C., 60% RH for 168 hours (MSL2).

[0353] After that, reflow treatment was performed at 260°C for 10 seconds, and the presence of peeling inside the package was observed using an ultrasonic flaw detector (HYE-FOCUS manufactured by Hitachi Construction Machinery Co., Ltd.). The peeling property was evaluated by the number of packages with peeling relative to the number of test packages (16).

[0354] [Table 1]

[0355]

[0356] [Table 2]

[0357]

[0358] As shown in Table 2, no difference in peelability was observed between the comparative example and the example under the moisture absorption conditions of 85°C and 60% RH. However, under the strict moisture absorption conditions of 85°C and 85% RH, the peeling of the example was significantly suppressed compared with the comparative example.

[0359] [Example 1B to Example 2B and Comparative Example 1B to Comparative Example 2B]

[0360] The materials of the formulation shown in Table 3 were pre-mixed (dry blended), kneaded for about 15 minutes using a biaxial roll (roll surface temperature: about 80° C.), cooled and pulverized to produce a powdered curable resin composition. In addition, 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.

[0361] The details of the materials in Table 3 are as follows.

[0362] ·Epoxy resin A: biphenyl type, epoxy equivalent 192g / eq

[0363] ·Epoxy resin B: Sulfur-containing epoxy resin, epoxy equivalent 238g / eq~254g / eq, melting point 116℃~126℃

[0364] · Epoxy resin C: triphenylmethane type (without alkyl or alkoxy groups), epoxy equivalent 169 g / mol, softening point 60°C

[0365] Epoxy resin D: o-cresol type, epoxy equivalent 200g / eq

[0366] Epoxy resin E: triphenylmethane type epoxy resin represented by the above formula (2), epoxy equivalent 214 g / eq, melting point 85°C

[0367] Hardener A: phenol resin, hydroxyl equivalent 175g / eq

[0368] Hardener B: triphenylmethane phenol resin, hydroxyl equivalent 104g / eq

[0369] Hardener C: Alkyl-modified phenolic resin, hydroxyl equivalent 224 g / eq

[0370] · Hardening accelerator: 1,4-benzoquinone adduct of triphenylphosphine

[0371] Inorganic filler: spherical silica particles with a top cut of 75 μm and a volume average particle size of 19 μm

[0372] · Coupling agent A: N-phenyl-3-aminopropyltrimethoxysilane

[0373] Coupling agent B: 3-glycidyloxypropyltrimethoxysilane

[0374] Coupling agent C: 3-mercaptopropyltrimethoxysilane

[0375] Release agent: ester wax such as dioctadecanoic acid ester

[0376] Colorant: Carbon black

[0377] Ion exchanger: hydrotalcite

[0378] Stress Relaxant A: Methyl / phenyl polysiloxane compound, solid at 25°C

[0379] Stress reliever B: triphenylphosphine oxide

[0380] Stress relaxant C: coumarone resin, softening point 100℃

[0381] <<Evaluation of curable resin composition>>

[0382] The properties of the curable resin compositions prepared in Examples and Comparative Examples were measured and evaluated by the above-mentioned methods. The evaluation results are shown in Table 4.

[0383] [Table 3]

[0384]

[0385] [Table 4]

[0386]

[0387] As shown in Table 4, under the hygroscopic conditions of 85°C and 60% RH (MSL2), there is no difference in peelability between the comparative example and the example, and the invention disclosed in the present disclosure cannot be easily thought of under normal hygroscopic conditions. In addition, it can be seen that under the strict hygroscopic conditions of 85°C and 85% RH (MSL1), the peeling of the example is significantly suppressed compared with the comparative example. In particular, Example 1B and Example 2B did not produce peeling packages under the strict hygroscopic conditions of MSL1, and a particularly excellent effect can be exerted.

[0388] The entire contents of the disclosures of Japanese Patent Application Nos. 2022-201454, 2022-201455, and 2022-201456 are incorporated into the present disclosure by reference.

[0389] All documents, patent applications, and technical specifications in the present disclosure are incorporated by reference into the present disclosure to the same extent as if each individual document, patent application, or technical specification was specifically and individually indicated to be incorporated by reference.

Claims

1. A curable resin composition comprising a triphenylmethane epoxy resin having at least one selected from the group consisting of an alkyl group and an alkoxy group.

2. The curable resin composition according to claim 1, wherein The benzene ring contained in the triphenylmethane epoxy resin has two or more alkyl groups.

3. The curable resin composition according to claim 1, wherein The benzene ring contained in the main chain of the triphenylmethane epoxy resin has two or more alkyl groups.

4. The curable resin composition according to claim 1, wherein The alkyl group includes a tert-butyl group. The curable resin composition according to claim 1 , further comprising a polysiloxane-based stress relaxant.

6. The curable resin composition according to claim 5, wherein The polysiloxane-based stress relaxer comprises a branched polysiloxane having the following structural units (a) and (b), and the terminal is selected from R 1 , at least one functional group selected from the group consisting of hydroxyl and alkoxy, with an epoxy equivalent of 500 g / eq to 4000 g / eq, [Chemistry 1] 〔R 1 represents an unsubstituted alkyl, alkenyl, aryl, or aralkyl group having 1 to 12 carbon atoms, and a plurality of R 1 In the case of multiple R 1 They may be the same or different; X represents 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidyloxyethyl, 3-glycidyloxypropyl, 4-glycidyloxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, or 3-(3,4-epoxycyclohexyl)propyl].

7. A curable resin composition, wherein the elastic modulus at 260°C when the cured product is formed is 400 MPa or less, the linear expansion coefficient at 180°C to 200°C when the cured product is formed is 32 ppm / °C or more, and the adhesive strength of the cured product after treatment at 85°C and 85% RH to Ag (silver) is 0.45 MPa or more.

8. The curable resin composition according to claim 7, wherein The spiral flow according to Epoxy Resin Molding Materials Association-1-66 is 100 cm or more.

9. The curable resin composition according to claim 7, wherein The hot hardness of the hardened material is 56 or more.

10. The curable resin composition according to claim 7, wherein The hot strength of the hardened product is 3MN / m 2 above.

11. An electronic component device comprising: element; and a cured product of the curable resin composition according to any one of claims 1 to 10, which seals the element. 12 . The electronic component device according to claim 11 , comprising a lead frame having the element mounted on one surface thereof.

13. The electronic component device according to claim 12, wherein: The lead frame includes Ag.

Images