Curable resin composition and electronic component device

Abstract

A curable resin composition, wherein the epoxy resin and the phenolic curing agent are contained in an equivalent ratio of phenolic hydroxyl groups of the phenolic curing agent to epoxy groups of the epoxy resin of 0.5 or more but less than 1.0.

Description

Technical Field

[0001] This disclosure relates to a curable resin composition and an electronic component device. Prior Technology

[0002] In recent years, the high-density mounting of semiconductor devices has been continuously developing. Along with this, surface-mount packaging has become mainstream, replacing the previous through-hole packaging with resin-sealed semiconductor devices. Surface-mount integrated circuits (ICs) and large-scale integrated circuits (LSIs) have become thin and small packages to increase mounting density and reduce mounting height. Therefore, the area occupied by the device relative to the package has increased, and the package thickness has become very thin.

[0003] Furthermore, the mounting method for these packages differs from that of through-hole packages. Specifically, through-hole packages involve inserting the pins into the patch panel and then soldering them from the back of the patch panel, thus preventing the package from being directly exposed to high temperatures. However, surface-mount ICs are temporarily fixed to the surface of a wiring board and processed using solder baths and reflow equipment, thus exposing the package directly to soldering temperatures (reflow temperatures). As a result, if the package absorbs moisture, the moisture vaporizes during reflow, and the resulting vapor pressure acts as peel stress, causing delamination between the component, lead frame, and other supporting components and the sealing material. This leads to package cracking and poor electrical characteristics. Therefore, it is desirable to develop a sealing material with excellent adhesion to supporting components and, consequently, excellent solder heat resistance (reflow resistance).

[0004] As a sealing material, curable resin compositions containing epoxy resin and phenolic curing agents are known. Summary of the Invention

[0005] [The problem that the invention aims to solve] There is room for further improvement in the reflow resistance of the curable resin composition proposed in Patent Document 1. This disclosure is made in view of the aforementioned situation, and the problem to be solved by this disclosure is to provide a curing resin composition with excellent reflow resistance and an electronic component device including elements sealed by the curing resin composition. [Methods for solving problems]

[0006] The specific methods used to achieve the stated objectives are as follows. <1> A curable resin composition, wherein the epoxy resin and the phenolic curing agent are contained in an equivalent ratio of phenolic hydroxyl groups of the phenolic curing agent to epoxy groups of the epoxy resin of 0.5 or more but less than 1.0. <2> As described <1> The described curable resin composition, wherein the epoxy resin comprises a copolymeric epoxy resin having structural units derived from alkylphenol and structural units derived from alkoxynaphthalene. <3> As described <2> The described curable resin composition, wherein the copolymerized epoxy resin accounts for 50% to 90% of the total mass of the epoxy resin. <4> As described <1> to <3> The curable resin composition described in any one of the following, wherein the epoxy resin comprises a biphenyl-type epoxy resin. <5> As described <1> to <4> The curable resin composition described in any one of the following, wherein the phenolic curing agent comprises one or more phenolic curing agents selected from the group consisting of aryl phenolic resins and phenolic varnish phenolic resins. <6> As described <1> to <5> The curable resin composition described in any one of the following, wherein the phenolic curing agent comprises an aralkyl-type phenolic resin, and The content of the aryl phenolic resin relative to the total mass of the phenolic hardener is 60% to 95% by mass. <7> As described <1> to <6> The curing resin composition described in any one of the claims further contains a curing accelerator, said curing accelerator comprising an adduct of a third phosphine compound and a quinone compound. <8> An electronic component device includes an element and a seal for sealing the element as described above. <1> to <7> A resin-cured product of any of the curing resin compositions described in the preceding items. <9> As described <8> The described electronic component device further includes a support member on one side of which the component is mounted. [The effects of the invention]

[0007] This disclosure provides a curable resin composition with excellent reflow resistance and an electronic component device including elements sealed by the curable resin composition. Implementation

[0008] The following is a detailed description of the forms used to implement this disclosure. However, this disclosure is not limited to the following embodiments. In the following embodiments, unless specifically stated otherwise, structural elements (including element steps, etc.) are not essential. The numerical values ​​and their ranges are also the same and do not limit this disclosure.

[0009] In this disclosure, the values ​​recorded before and after "~" in the numerical range represented by "~" are respectively the minimum and maximum values. Within the numerical ranges described in this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in this disclosure. Furthermore, within the numerical ranges described in this disclosure, the upper or lower limit of that range may also be replaced by the value shown in the synthetic example. This disclosure may contain multiple compounds equivalent to each component. Where multiple substances equivalent to each component are present in the composition, unless otherwise specified, the content or percentage of each component refers to the total content or percentage of the multiple substances present in the composition. In this disclosure, there may be multiple particles corresponding to each component. In the case where multiple 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 the mixture of the multiple particles present in the composition. In this disclosure, the term "layering" refers to stacking layers, which can combine two or more layers, or allow two or more layers to be assembled and disassembled. In the description of the base (atomic group) disclosed herein, the descriptions of unsubstituted and unsubstituted groups include those without substituents and those with substituents. In this disclosure, the number of structural units is represented as an integer value for a single molecule, and as a rational number representing the average value for a collection of multiple molecules. In this disclosure, the so-called carbon number refers to the total number of carbon atoms contained in a base as a whole. When the base does not have substituents, it represents the number of carbon atoms forming the skeleton of the base. When the base has substituents, it represents the total number of carbon atoms forming the skeleton of the base plus the number of carbon atoms in the substituents.

[0010] In this disclosure, the equivalent ratio of phenolic hydroxyl groups (active hydrogens) of the phenolic curing agent to the epoxy groups of the epoxy resin (moles of active hydrogens in the phenolic curing agent / moles of epoxy groups in the epoxy resin) can be determined as follows: The curing resin composition is measured by 1H-Nuclear Magnetic Resonance (1H-NMR), and the result is determined based on the integral ratio of protons in the epoxy groups to protons in the phenolic hydroxyl groups. Furthermore, the 1H-NMR of the curing resin composition is measured under the following conditions. (Measurement conditions) • Measuring apparatus: Bruker AVANCE3 HD 400 Nanobay • Determination solvent: Dimethyl sulfoxide (DMSO)-d6 (0.7 ml) • Measurement temperature: 25℃ • 1H resonant frequency: 400 MHz • Measurement mode: NPROTON Total number of times: 16 • Softening time: 1 second

[0011] In this disclosure, the dynamic viscoelasticity determination of resin-cured compositions of curable resins can be performed using a dynamic viscoelasticity measuring device (e.g., PerkinElmer DMA8000). For example, dynamic viscoelasticity determination can be performed on a rectangular resin-cured composition with a short side of 5 mm × a long side of 50 mm × a thickness of 2 mm under the following conditions: test mode: 3-point bending mode; test temperature: 25°C to 330°C; heating rate: 10°C / min; test frequency: 1 Hz. The stored viscoelasticity value, peak value of tanδ, glass transition temperature, etc., can be determined based on the obtained graph (vertical axis: tanδ, horizontal axis: temperature). Furthermore, the resin curing material is produced by the following method: the curable resin composition is formed using a transfer molding machine at a mold temperature of 175°C, a molding pressure of 8.3 MPa, and a curing time of 120 seconds, and then post-cured at 175°C for 5 hours.

[0012] In this disclosure, the coefficient of thermal expansion (CTE) of the cured resin composition is determined, for example, for a φ4 mm × 20 mm cured resin composition, using a thermomechanical analysis apparatus. Furthermore, the fabrication of the cured resin composition is as described above. The test conditions were set as follows: load 15 g, test temperature -50℃ to 220℃, and heating rate 5℃ / minute. As a thermomechanical analysis apparatus, the TMA / SS6100 manufactured by Seiko Instruments Co., Ltd. can be used.

[0013] In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined under the following conditions using the gel permeation chromatography (GPC) apparatus described below, and converted using a calibration curve of standard polystyrene. Furthermore, in the preparation of the calibration curve, five sample groups ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation) were used as the standard polystyrene. For compounds whose molecular weight is too small to be accurately determined by GPC, the molecular weight determined based on the chemical structure of the compound is used as the Mw or Mn of the compound. (GPC measuring device) GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation. Tube String: TSKgel Super Multipore HZ-H (tube length: 15 cm, tube inner diameter: 4.6 mm), manufactured by Tosoh Corporation. (Measurement conditions) Solvent: tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35 mL / min Sample concentration: 10 mg / THF 5 mL Injection volume: 20 μL

[0014] <Curing Resin Composition> The curable resin composition disclosed herein contains epoxy resin and phenolic curing agent in an equivalent ratio of phenolic hydroxyl groups of phenolic curing agent to epoxy groups of epoxy resin of 0.5 or more but less than 1.0.

[0015] The disclosed curable resin composition exhibits excellent reflow resistance.

[0016] The reason why the described effect is achieved by the hardening resin composition disclosed herein is not clear, but it is speculated as follows. The disclosed curable resin composition contains epoxy resin and phenolic curing agent in an equivalent ratio of phenolic hydroxyl groups of the phenolic curing agent to epoxy groups of the epoxy resin of 0.5 or more but less than 1.0. This results in an increased tanδ value near the reflow temperature and a tendency to alleviate internal stress in the cured resin during reflow. Consequently, the adhesion between the cured resin and the support member is improved, thus suggesting excellent reflow resistance. As a test used to evaluate reflow resistance, the Moisture Sensitive Level (MSL) test is known as a standard of the Joint Electron Device Engineers Council (JEDEC). The curable resin composition disclosed herein exhibits surprisingly excellent reflow resistance even after heating and humidifying at a temperature of 85°C and a relative humidity of 85% for 168 hours (equivalent to MSL grade 1).

[0017] In a graph obtained by performing dynamic viscoelasticity measurements on the cured resin composition of the disclosed invention, with tanδ as the vertical axis and temperature as the horizontal axis, the temperature at which tanδ reaches its maximum (the so-called glass transition temperature) is preferably less than 120°C, and more preferably less than 110°C. By keeping the glass transition temperature below 120°C, there is a tendency to improve the solder reflow resistance of the cured resin composition of the disclosed invention. The lower limit of the glass transition temperature is not particularly limited; for example, it can be set to 50°C or higher.

[0018] From the viewpoint of the solderability resistance of the curable resin composition disclosed herein, the tanδ at the glass transition temperature is preferably greater than 0.400, more preferably greater than 0.410. There is no particular limitation on the upper limit of tanδ at the glass transition temperature; for example, it may be set to 1.0 or less.

[0019] From the viewpoint of the solder reflow resistance of the curable resin composition disclosed herein, when the tanδ value at the glass transition temperature is set to 100, the tanδ value at at least one temperature of glass transition temperature -10°C is preferably greater than 60, more preferably greater than 63, and even more preferably greater than 65.

[0020] From the viewpoint of the solder reflow resistance of the curable resin composition disclosed herein, the sum of tanδ values ​​at temperatures of 220°C, 230°C, 240°C, and 250°C is preferably greater than 0.400. There is no particular upper limit to the sum of tanδ values ​​at temperatures of 220°C, 230°C, 240°C, and 250°C, for example, it can be set to 2.0 or less.

[0021] From the viewpoint of the solder reflow resistance of the curable resin composition disclosed herein, the sum of tanδ values ​​at temperatures of 70°C, 80°C, and 90°C is preferably greater than 0.600, and more preferably greater than 0.700. There is no particular upper limit to the sum of tanδ values ​​at temperatures of 70°C, 80°C, and 90°C, for example, it may be set to 2.0 or less.

[0022] From the perspective of reflow resistance, the storage viscoelasticity at 260°C, determined by dynamic viscoelasticity measurement of the cured resin of the curing resin composition, is preferably 450 MPa or less, more preferably 435 MPa or less, and even more preferably 420 MPa or less. There is no particular limit to the lower limit of the storage elasticity coefficient; for example, it can be set to 150 MPa or higher.

[0023] From the perspective of the conformability of the supporting components, the coefficient of thermal expansion (CTE1) of the cured resin composition of the disclosed material at a temperature below the glass transition temperature, as determined by thermomechanical analysis, is preferably 15 ppm / ℃ or less, more preferably 13 ppm / ℃ or less, and even more preferably 10 ppm / ℃ or less. The lower limit of the coefficient of thermal expansion is not particularly limited; for example, it can be set to 3 ppm / ℃. From the viewpoint of adhesion to the supporting member, the coefficient of thermal expansion (CTE2) at temperatures above the glass transition temperature is preferably 10 ppm / ℃ to 45 ppm / ℃, more preferably 12 ppm / ℃ to 40 ppm / ℃, and even more preferably 15 ppm / ℃ to 38 ppm / ℃.

[0024] The following describes the various materials that may be contained in curable resin compositions.

[0025] (Epoxy resin) The curable resin composition disclosed herein contains epoxy resin. There is no particular limitation on the type of epoxy resin, as long as it has two or more epoxy groups per molecule. Furthermore, in this disclosure, the linear polysiloxane compound is provided not to be contained in the epoxy resin. The following are specific examples of epoxy resins, but are not limited to these.

[0026] Specifically, examples include: 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, and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthol, with aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a phenolic varnish resin, and then epoxidizing the phenolic varnish resin to obtain a phenolic varnish-type epoxy resin (phenolic varnish-type epoxy resin, o-cresol varnish-type epoxy resin, etc.); condensing or co-condensing the phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst to obtain a triphenylmethane-type phenolic resin, and then epoxidizing the triphenylmethane-type phenolic resin. The obtained triphenylmethane type epoxy resin; phenolic varnish resin obtained by co-condensing the phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst, and then epoxidizing the phenolic varnish resin to obtain a copolymer type epoxy resin; diphenylmethane type epoxy resin as diglycidyl ether of bisphenol A, bisphenol F, etc.; biphenyl type epoxy resin as diglycidyl ether of alkyl-substituted or unsubstituted biphenyl phenol; stilbene type epoxy resin as diglycidyl ether of stilbene phenolic compounds; sulfur-containing atom type epoxy resin as diglycidyl ether of bisphenol S, etc.; epoxy resin as glycidyl ether of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; as phthalic acid, isophthalic acid... Glycidyl ester type epoxy resins of polycarboxylic acid compounds such as formic acid and tetrahydrophthalic acid; glycidyl amine type epoxy resins obtained by replacing the active hydrogen atom of nitrogen atoms in aniline, diaminodiphenylmethane, isocyanuric acid, etc. with glycidyl groups; dicyclopentadiene type epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and phenol compounds; alicyclic epoxy resins such as diepoxyvinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylates, and 2-(3,4-epoxy)cyclohexyl-5,5-spirocyclic (3,4-epoxy)cyclohexane-m-dioxane, obtained by epoxidizing the olefin bonds within the molecule; and glycidyl esters used as p-xylene-modified phenolic resins. p-Xylene-modified epoxy resin as an ether; glycidyl ether-modified epoxy resin as a m-xylene-modified phenolic resin; glycidyl ether-modified terpene epoxy resin as a terpene-modified phenolic resin; glycidyl ether-modified epoxy resin as a dicyclopentadiene-modified phenolic resin; glycidyl ether-modified epoxy resin as a cyclopentadiene-modified phenolic resin; glycidyl ether-modified epoxy resin as a polycyclic aromatic ring-modified phenolic resin; naphthalene-type epoxy resin as a naphthalene-containing phenolic resin; halogenated phenolic varnish-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;Aryl alkyl type epoxy resins are obtained by epoxidation of aryl alkyl type phenol resins such as phenol aryl alkyl resins and naphthol aryl alkyl resins. Furthermore, glycidyl ethers of aminophenol, i.e., aminophenol type epoxy resins, can also be used as epoxy resins. These epoxy resins can be used alone or in combination of two or more.

[0027] There are no particular limitations on biphenyl-type epoxy resins as long as they have a biphenyl backbone. For example, epoxy resins represented by the following general formula (II) are preferred.

[0028] [Chemistry 1]

[0029] In formula (II), R8 represents a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, or an aromatic group with 4 to 18 carbon atoms, which may all be the same or different. n is the average value and represents an integer from 0 to 10.

[0030] There are no particular limitations on stilbene-type epoxy resins as long as they have a stilbene backbone. For example, epoxy resins represented by the following general formula (III) are preferred.

[0031] [Chemistry 2]

[0032] In formula (III), R9 and R10 represent hydrogen atoms or monovalent organic groups with 1 to 18 carbon atoms, which may be the same or different. n is the average value and represents an integer from 0 to 10.

[0033] Diphenylmethane-type epoxy resins are not particularly limited as long as they have a diphenylmethane backbone. For example, epoxy resins represented by the following general formula (IV) are preferred.

[0034] [Chemistry 3]

[0035] In formula (IV), R11 and R12 represent hydrogen atoms or monovalent organic groups with 1 to 18 carbon atoms, which may be the same or different. n is the average value and represents an integer from 0 to 10.

[0036] There are no particular limitations on epoxy resins containing sulfur atoms, as long as they contain sulfur atoms. For example, epoxy resins represented by the following general formula (V) can be listed.

[0037] [Chemistry 4]

[0038] In formula (V), R13 represents a hydrogen atom or a monovalent organic group with 1 to 18 carbon atoms, which can be the same or different. n is the average value and represents an integer from 0 to 10.

[0039] There are no particular limitations on phenolic varnish-type epoxy resins as long as they are obtained by epoxidizing phenolic varnish-type phenolic resins.

[0040] [Chemistry 5]

[0041] In formula (VI), R14 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, which may all be the same or different. R15 represents a monovalent organic group having 1 to 18 carbon atoms, which may all be the same or different. i independently represents an integer from 0 to 3. n is the average value and represents an integer from 0 to 10.

[0042] Dicyclopentadiene-type epoxy resins are not particularly limited as long as they are epoxy resins obtained by epoxidation of compounds with a dicyclopentadiene skeleton as raw materials.

[0043] [Chemistry 6]

[0044] In equation (VII), R16 represents a monovalent organic group with 1 to 18 carbon atoms, which can be the same or different. i represents an integer from 0 to 3 independently. n is the average value and represents an integer from 0 to 10.

[0045] There are no particular restrictions on triphenylmethane-type epoxy resins as long as they are epoxy resins made from compounds with a triphenylmethane skeleton.

[0046] [Chemistry 7]

[0047] In equation (VIII), R17 and R18 represent monovalent organic groups with carbon numbers 1 to 18, which may be the same or different. i independently represents an integer from 0 to 3, and k independently represents an integer from 0 to 4. n is the average value and represents an integer from 0 to 10.

[0048] There are no particular limitations on the copolymerized epoxy resin obtained by epoxidizing phenolic varnish resins obtained from naphthol compounds, phenol compounds, and aldehyde compounds, as long as the epoxy resin uses compounds with naphthol skeletons and compounds with phenol skeletons as raw materials. For example, it is preferably an epoxy resin obtained by glycidyl etherification of a phenolic varnish-type phenolic resin having a naphthol skeleton and a phenol skeleton, and more preferably an epoxy resin represented by the following general formula (IX).

[0049] [Chemistry 8]

[0050] In formula (IX), R19~R21 represent monovalent organic groups with 1~18 carbon atoms, which may be the same or different. i independently represents an integer from 0 to 3, j independently represents an integer from 0 to 2, and k independently represents an integer from 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 epoxy resin represented by formula (IX) ends in either formula (IX-1) or formula (IX-2). In formulas (IX-1) and (IX-2), the definitions of R19~R21, i, j, and k are the same as those in formula (IX). n is 1 (in the case of bonding via methylene) or 0 (in the case of bonding without methylene).

[0051] [Chemistry 9]

[0052] Examples of epoxy resins represented by the general formula (IX) include: random copolymers having 1 and m structural units randomly; alternating copolymers having 1 and m structural units alternately; copolymers having 1 and m structural units regularly; and block copolymers having 1 and m structural units in a block form. Any of these can be used alone or in combination.

[0053] Aryl alkyl type epoxy resins are not particularly limited as long as they are epoxy resins synthesized from phenolic resins synthesized from at least one of the group consisting of phenolic compounds such as phenol and cresol, and naphthol, dimethylnaphthol, etc., with dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, or derivatives thereof. For example, it is more preferably an epoxy resin obtained by glycidyl etherification of a phenolic resin synthesized from at least one of the group consisting of phenolic compounds such as phenol and cresol, and naphthol, dimethylnaphthol, etc., with dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, or derivatives thereof, and more preferably epoxy resins represented by the following general formulas (X) and (XI).

[0054] [Chemistry 10]

[0055] In formulas (X) and (XI), R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, which may all be the same or different. R 37, R 39 to R 41 represent monovalent organic groups having 1 to 18 carbon atoms, which may all be the same or different. i is an independent integer from 0 to 3, j is an independent integer from 0 to 2, k is an independent integer from 0 to 4, and l is an independent integer from 0 to 4. n is the average value, and each is an independent integer from 0 to 10.

[0056] Regarding R8~R21 and R37~R41 in general formulas (II) to (XI), the phrase "may all be the same or different" means, for example, that the 8 to 88 R8s in formula (II) may all be the same or different. Similarly, regarding R9~R21 and R37~R41, it also means that the number of each in the formula may all be the same or different. Furthermore, R8~R21 and R37~R41 may each be the same or different. For example, R9 and R10 may all be the same or different. In addition, the monovalent organic groups with 1 to 18 carbon atoms in general formulas (III) to (XI) are preferably alkyl or aryl.

[0057] In formulas (II) to (XI), n is an average value, preferably an independent value of 0 to 10. If n is less than 10, the melt viscosity of the resin component will not be too high, and the viscosity of the curing resin composition during melt molding will be reduced, which can suppress the tendency for poor filling, deformation of the bonding line (metal wire connecting the element and the lead wire), etc. n is more preferably set to a range of 0 to 4.

[0058] From the viewpoint of the solder reflow resistance of the curable resin composition disclosed herein, the epoxy resin is preferably a copolymerizable epoxy resin comprising structural units derived from alkylphenol and structural units derived from alkoxynaphthalene (hereinafter referred to as a specific copolymerizable epoxy resin). Examples of structural units derived from alkylphenol include the following structural unit (a).

[0059] [Chemistry 11]

[0060] In the structural unit, RA independently represents a monovalent alkyl group having 1 to 18 carbon atoms, preferably a monovalent alkyl group having 1 to 6 carbon atoms. X represents an integer from 1 to 3.

[0061] The following structural unit (b) can be listed as a structural unit derived from alkoxynaphthalene.

[0062] [Chemistry 12]

[0063] In the structural unit, RB independently represents a monovalent alkoxy group having 1 to 18 carbon atoms, preferably a monovalent alkoxy group having 1 to 6 carbon atoms. y represents an integer from 1 to 6. Furthermore, the two bonding sites in the structural unit (b) can exist on the same ring of the naphthalene ring, or they can exist on two separate rings of the naphthalene ring.

[0064] Certain copolymerized epoxy resins may have the following structural unit (c). In the following structural units, n is an integer from 1 to 10, preferably an integer from 2 to 8. Furthermore, the two bonding sites of the naphthalene ring in the structural unit (c) can exist on the same ring of the naphthalene ring, or they can exist on two separate rings of the naphthalene ring.

[0065] [Chemistry 13]

[0066] As a structural unit that satisfies the structural unit (c), the following structural unit (d) can be listed as an example.

[0067] [Chemistry 14]

[0068] In the epoxy resin, from the viewpoint of the solder reflow resistance of the curing resin composition disclosed herein, the epoxy resin is preferably an epoxy resin comprising a specific copolymer type. In addition, from the viewpoint of solder reflow resistance, epoxy resins containing biphenyl are preferred.

[0069] There is no particular limitation on the epoxy equivalent of epoxy resin. From the perspective of balancing various properties such as formability, heat resistance and electrical reliability, the epoxy equivalent of epoxy resin is preferably 40 g / eq to 1000 g / eq, more preferably 45 g / eq to 500 g / eq, and even more preferably 50 g / eq to 350 g / eq. The epoxy equivalent of the epoxy resin is set as a value determined using the method according to Japanese Industrial Standards (JIS) K 7236:2009.

[0070] Epoxy resin can be either solid or liquid at 25°C. When epoxy resin is solid at 25°C, there are no particular limitations on its softening point or melting point. From the perspective of balancing formability and heat resistance, the softening point or melting point of epoxy resin is preferably 40°C to 180°C. Furthermore, from the perspective of workability during the manufacture of curable resin compositions, the softening point or melting point of epoxy resin is preferably 50°C to 130°C. In this disclosure, softening point refers to the value determined by the ring and ball method according to JIS K 7234:1986. In this disclosure, melting point refers to the value determined by the visual method according to JIS K 0064:1992.

[0071] In terms of solderability, formability, and heat resistance, the preferred Mw of epoxy resin is 550~1050, and more preferably 650~950. In addition, from the viewpoints of reflow resistance, formability, and heat resistance, the Mn of epoxy resin is preferably 250~800, and more preferably 350~600.

[0072] In terms of reflow resistance, strength, flowability, and formability, the content of epoxy resin relative to the total mass of the curing resin composition is preferably 0.5% to 60% by mass, more preferably 2% to 50% by mass, and even more preferably 3% to 45% by mass.

[0073] From the viewpoint of the solder reflow resistance of the curable resin composition disclosed herein, when the epoxy resin includes a specific copolymer epoxy resin, the content of the specific copolymer epoxy resin relative to the total mass of the epoxy resin is preferably 50% to 90% by mass, more preferably 55% to 80% by mass, and even more preferably 60% to 75% by mass.

[0074] From the viewpoint of the solderability resistance of the curable resin composition disclosed herein, when the epoxy resin includes biphenyl epoxy resin, the content of biphenyl epoxy resin relative to the total mass of the epoxy resin is preferably 5% to 40% by mass, more preferably 7% to 35% by mass, and even more preferably 10% to 30% by mass.

[0075] (Phenolic hardener) The disclosed curable resin composition contains a phenolic curing agent. There are no particular limitations on the type of phenolic curing agent; it can be selected from those commonly used as components in curable resin compositions. A single phenolic curing agent can be used, or two or more can be used in combination.

[0076] Examples of phenolic curing agents include phenolic resins and polyphenolic compounds having two or more phenolic hydroxyl groups in one molecule. The following are specific examples of phenolic hardeners, but are not limited to these. Examples of phenolic curing agents include: polyphenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; phenolic varnish-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthol with aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; aralkyl phenolic resins such as phenolic aralkyl resins and naphthol aralkyl resins synthesized from the aforementioned phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc.; and p-xylene-modified phenolic resins and... / or xylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization of the phenolic compound and dicyclopentadiene; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin; triphenylmethane-type phenolic resin obtained by condensing or co-condensing the phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; triazine-type phenolic resin such as 2-[4-[(2-hydroxy-3-(2'-ethylhexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; phenolic resin obtained by copolymerizing two or more of these, etc.

[0077] From the viewpoint of the solder reflow resistance of the disclosed curable resin composition, the phenolic curing agent is preferably one or more phenolic curing agents selected from the group consisting of aryl alkyl phenolic resins and phenolic varnish phenolic resins, and more preferably all of them. The phenolic curing agents will be described in more detail below, but are not limited to these.

[0078] Aryl alkyl phenolic resins are not particularly limited, but can be listed as phenolic resins synthesized from at least one of the group consisting of phenolic compounds and naphthol compounds, dimethoxy-p-xylene, bis(methoxymethyl)biphenyl or derivatives thereof. Specific examples of aryl phenolic resins include phenolic resins represented by the following general formulas (XII) to (XIV). In formulas (XII) to (XIV), R23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, which may all be the same or different. R22, R24, R25, and R28 represent monovalent organic groups having 1 to 18 carbon atoms, which may all be the same or different. R26 and R27 represent hydroxyl groups or monovalent organic groups having 1 to 18 carbon atoms, which may all be the same or different. i is an independent integer from 0 to 3, j is an independent integer from 0 to 2, k is an independent integer from 0 to 4, and p is an independent integer from 0 to 4. n is the average value, and each is an independent integer from 0 to 10. The phrase "may all be the same or may be different" as used in the general formula refers to, for example, that the i R 22 values ​​in general formula (XII) may all be the same or may be different from each other. Furthermore, R 22 to R 37 may each be the same or may be different. For example, R 22 and R 23 may both be the same or may be different.

[0079] From the viewpoint of the solderability of the curable resin composition disclosed herein, aralkyl-type phenolic resins are preferably phenolic resins represented by general formula (XIII). From the viewpoint of the solder reflow resistance of the hardened resin composition disclosed herein, in addition, in general formula (XIII), i and k are preferably both 0.

[0080] [Chemistry 15]

[0081] Aryl phenolic resins can also be copolymerized phenolic resins with other phenolic resins. Examples of copolymerized phenolic resins include: copolymerized phenolic resins of triphenylmethane type and aryl phenolic resins, copolymerized phenolic resins of salicylaldehyde type and aryl phenolic resins, and copolymerized phenolic resins of phenolic varnish type and aryl phenolic resins.

[0082] Dicyclopentadiene-type phenolic resins are not particularly limited as long as they are phenolic resins obtained from compounds having a dicyclopentadiene skeleton as raw materials. For example, phenolic resins represented by the following general formula (XV) are preferred.

[0083] [Chemistry 16]

[0084] In equation (XV), R 29 represents monovalent organic groups with 1 to 18 carbon atoms, which can be the same or different. i represents an integer from 0 to 3 independently. n is the average value and represents an integer from 0 to 10.

[0085] Triphenylmethane-type phenolic resins are not particularly limited as long as they are phenolic resins obtained from aromatic aldehyde compounds as raw materials. For example, phenolic resins represented by the following general formula (XVI) are preferred.

[0086] [Chemistry 17]

[0087] In equation (XVI), R30 and R31 represent monovalent organic groups with carbon numbers from 1 to 18, which may be the same or different. i is an independent integer from 0 to 3, and k is an independent integer from 0 to 4. n is the average value and is an integer from 0 to 10.

[0088] There is no particular limitation on the copolymerization of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin, as long as the phenolic resin obtained by using a compound having a benzaldehyde skeleton as a raw material is copolymerized with an aralkyl-type phenolic resin. For example, a phenolic resin represented by the following general formula (XVII) is preferred.

[0089] [Chemistry 18]

[0090] In equation (XVII), R32~R34 represent monovalent organic groups with 1 to 18 carbon atoms, which may be the same or different. i is an independent integer from 0 to 3, k is an independent integer from 0 to 4, and q is an independent integer from 0 to 5. l and m are average values, and are independent integers from 0 to 11. The sum of l and m is an integer from 1 to 11.

[0091] Phenolic resins of the varnish type are not particularly limited as long as they are phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. For example, phenolic resins represented by the following general formula (XVIII) are preferred.

[0092] [Chemistry 19]

[0093] In formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, which may all be the same or different. R 36 represents a monovalent organic group having 1 to 18 carbon atoms, which may all be the same or different. i independently represents an integer from 0 to 3. n is the average value and represents an integer from 0 to 10.

[0094] Regarding R22 to R36 in the general formulas (XII) to (XVIII), the phrase "may all be the same or may be different" means, for example, that the i R22s in formula (XII) may all be the same or may be different from each other. Similarly, regarding the other R23 to R36, it means that the number of each R22 in the formula may all be the same or may be different from each other. Furthermore, R22 to R36 may each be the same or different. For example, R22 and R23 may both be the same or different, and R30 and R31 may both be the same or different.

[0095] In the general formulas (XII) to (XVIII), n is preferably an integer from 0 to 10. If it is less than 10, 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 lower, making it less likely to cause poor filling, deformation of the bonding line (metal wire connecting the element and the lead wire), etc. The average n in one molecule is preferably set to the range of 0 to 4.

[0096] There is no particular limitation on the hydroxyl equivalent of phenolic hardeners. From the perspective of balancing various properties such as reflow resistance, formability, and electrical reliability, 10 g / eq to 1000 g / eq is preferred, and 30 g / eq to 500 g / eq is more preferred. Hydroxyl equivalent refers to the value calculated based on the hydroxyl value determined according to JIS K 0070:1992.

[0097] When the phenolic curing agent is solid at 25°C, there are no particular limitations on its softening point or melting point. From the viewpoint of formability and heat resistance, the softening point or melting point of the phenolic curing agent is preferably 40°C to 180°C. Furthermore, from the viewpoint of operability in the manufacture of curable resin compositions, the softening point or melting point of the phenolic curing agent is preferably 50°C to 130°C.

[0098] From the viewpoint of the solderability resistance of the curing resin composition disclosed herein, the content of phenolic curing agent relative to the total mass of the curing resin composition is preferably 0.5% to 40% by mass, more preferably 1% to 30% by mass, and even more preferably 2% to 20% by mass.

[0099] From the viewpoint of the solderability resistance of the curing resin composition disclosed herein, when the phenolic curing agent includes aralkyl-type phenolic resin, the content of aralkyl-type phenolic resin relative to the total mass of the phenolic curing agent is preferably 60% to 95% by mass, and more preferably 65% ​​to 90% by mass.

[0100] From the viewpoint of the solder reflow resistance of the disclosed curing resin composition, when the phenolic curing agent includes phenolic varnish-type phenolic resin, the content of phenolic varnish-type phenolic resin relative to the total mass of the phenolic curing agent is preferably 5% to 40% by mass, and more preferably 10% to 30% by mass.

[0101] (Various additives) In addition to the components described above, the curable resin composition disclosed herein may also contain various additives such as curing accelerators, inorganic fillers, coupling agents, stress relievers, release agents, colorants, flame retardants, ion exchangers, resins other than epoxy resins, and curing agents other than phenolic curing agents. Besides the additives exemplified below, the curable resin composition may also contain various additives well-known in the art, as needed.

[0102] (hardening accelerator) The curable resin composition disclosed herein may also contain a curing accelerator. There are no particular limitations on the type of curing accelerator; it can be selected based on the type of epoxy resin, the desired properties of the curable resin composition, etc.

[0103] From the perspective of curing properties and flowability, curing accelerators are preferably those containing phosphonium compounds. Specifically, examples of phosphorus compounds include: triphenylphosphine, diphenyl(p-toluene)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkyl-alkoxyphenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine, tri(tetraalkylphenyl)phosphine, tri(dialkoxyphenyl)phosphine, tri(trialkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and other tertiary phosphines; maleic anhydride, 1,4-benzoquinone, 2,5-toluenequinone, 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; and diazonylphenylmethane and other compounds with π bonds that form intramolecularly polarized compounds. Compounds; tertiary phosphine reacts 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, and 4-chloro-1-naphthol Compounds with intramolecular polarization obtained by reacting halogenated phenolic compounds such as 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl with dehydrohalogenation; salts of tetrasubstituted phosphonium such as tetraphenylphosphonium and tetrasubstituted borate esters such as tetra-p-tolueneboronic acid ester; salts of tetrasubstituted phosphonium with anions of phenolic compounds after deprotonation; salts of tetrasubstituted phosphonium with anions of carboxylic acid compounds after deprotonation, etc.

[0104] The phosphonium compound is preferably a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific hardening accelerator).

[0105] [Chemistry 20]

[0106] In formula (I-1), R1 to R3 are each independently a hydrocarbon group with 1 to 18 carbon atoms, and two or more of R1 to R3 can bond together to form a ring structure. R4 to R7 are each independently a hydrogen atom, a hydroxyl group, or an organic group with 1 to 18 carbon atoms, and two or more of R4 to R7 can bond together to form a ring structure.

[0107] The "hydrocarbon group with 1 to 18 carbons" described in R1 to R3 of general formula (I-1) includes aliphatic hydrocarbon groups with 1 to 18 carbons and aromatic hydrocarbon groups with 6 to 18 carbons.

[0108] From a fluidity perspective, aliphatic hydrocarbon groups with 1 to 18 carbon atoms are preferably 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms.

[0109] The aliphatic hydrocarbon group having 1 to 18 carbon atoms can be a straight-chain or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. From the viewpoint of ease of manufacture, a straight-chain or branched aliphatic hydrocarbon group is preferred.

[0110] The aliphatic hydrocarbon group, which has 1 to 18 carbon atoms, can be either straight-chain or branched. Specifically, examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, pentyl, hexyl, octyl, decyl, dodecyl, and other alkyl groups, allyl, vinyl, etc. The straight-chain or branched aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include: methoxy, ethoxy, n-butoxy, tributoxy, and other alkoxy groups; phenyl, naphthyl, and other aryl groups; hydroxyl, amino groups; halogen atoms, etc. The straight-chain or branched aliphatic hydrocarbon group may have two or more substituents, which may be the same or different. When the straight-chain or branched aliphatic hydrocarbon group has substituents, the total number of carbon atoms in the aliphatic hydrocarbon group and the substituents is preferably 1 to 18. From the viewpoint of curability, unsubstituted alkyl groups are preferred, more preferably unsubstituted alkyl groups having 1 to 8 carbon atoms, and even more preferably n-butyl, isobutyl, n-pentyl, n-hexyl, and n-octyl.

[0111] Alicyclic hydrocarbon groups with 3 to 18 carbon atoms can specifically include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, and cycloalkenyl groups such as cyclopentenyl and cyclohexenyl. Alicyclic hydrocarbon groups may or may not have substituents. Substituents can include alkyl groups such as methyl, ethyl, n-butyl, and tributyl, alkoxy groups such as methoxy, ethoxy, n-butoxy, and tributoxy, aryl groups such as phenyl and naphthyl, hydroxyl groups, amino groups, and halogen atoms. Alicyclic hydrocarbon groups may have two or more substituents, which may be the same or different. When an alicyclic hydrocarbon group has substituents, the total number of carbon atoms in the alicyclic hydrocarbon group and the substituents is preferably 3 to 18. The position of the substituents is not particularly limited when the alicyclic hydrocarbon group has substituents. From the viewpoint of curability, unsubstituted cycloalkyl groups are preferred, more preferably unsubstituted cycloalkyl groups with 4 to 10 carbon atoms, and even more preferably cyclohexyl, cyclopentyl, and cycloheptyl.

[0112] The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may or may not have substituents. Examples of substituents include: alkyl groups such as methyl, ethyl, n-butyl, and tributyl; alkoxy groups such as methoxy, ethoxy, n-butoxy, and tributoxy; aryl groups such as phenyl and naphthyl; hydroxyl groups; amino groups; and halogen atoms. The aromatic hydrocarbon group may have two or more substituents, which may be the same or different. When the aromatic hydrocarbon group has substituents, the total number of carbon atoms in the aromatic hydrocarbon group and the substituents is preferably 6 to 18. When the aromatic hydrocarbon group has substituents, the position of the substituents is not particularly limited.

[0113] Aromatic hydrocarbon groups having 6 to 18 carbon atoms include, specifically: phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl, tributylphenyl, methoxyphenyl, ethoxyphenyl, n-butoxyphenyl, and tributoxyphenyl. The substituents in these aromatic hydrocarbon groups can be located at the ortho, meta, or para positions. From a flowability perspective, unsubstituted aryl groups having 6 to 12 carbon atoms or containing substituents having 6 to 12 carbon atoms are preferred; more preferably, unsubstituted aryl groups having 6 to 10 carbon atoms or containing substituents having 6 to 10 carbon atoms are preferred; and even more preferably, phenyl, p-tolyl, and p-methoxyphenyl are preferred.

[0114] The term "two or more of R1 to R3 that can bond together to form a cyclic structure" as described in general formula (I-1) refers to the case where two or three bonds in R1 to R3 together form a divalent or trivalent hydrocarbon group. Examples of R1 to R3 in this case include: alkyl groups such as ethyl, propyl, butyl, pentyl, and hexyl that can bond with phosphorus atoms to form a cyclic structure; alkenyl groups such as ethynyl, propynyl, and butynyl; aryl groups such as methylene phenyl; arylyl, naphthyl, and anthraceneyl; and substituents that can bond with phosphorus atoms to form a cyclic structure. These substituents can also be further substituted with alkyl, alkoxy, aryl, aryloxy, amino, hydroxyl, or halogen atoms.

[0115] The "organic group having 1 to 18 carbon atoms" described in R 4 to R 7 of the general formula (I-1) refers to an aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbon oxy group, aromatic hydrocarbon oxy group, acetyl group, hydrocarbon oxy carbonyl group, and acetyloxy group that have 1 to 18 carbon atoms and may be substituted or unsubstituted.

[0116] Examples of the aliphatic and aromatic hydrocarbon groups described above can be cited as examples of aliphatic and aromatic hydrocarbon groups represented by R1 to R3.

[0117] Examples of aliphatic hydrocarbon oxy groups include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tributoxy, cyclopropoxy, cyclohexyloxy, cyclopentoxy, allyloxy, ethyleneoxy, and other oxy groups with oxygen atoms bonded to the aliphatic hydrocarbon group; these aliphatic hydrocarbon oxy groups are further substituted by alkyl, alkoxy, aryl, aryloxy, amino, hydroxyl, halogen atoms, etc.

[0118] Examples of aromatic hydrocarbon oxy groups include: phenoxy, methylphenoxy, ethylphenoxy, methoxyphenoxy, butoxyphenoxy, phenoxy, etc., in which an oxygen atom is bonded to the aromatic hydrocarbon group; and groups in which these aromatic hydrocarbon oxy groups are further substituted by alkyl, alkoxy, aryl, aryloxy, amino, halogen, etc.

[0119] Examples of such acetyl groups include: methyl, acetyl, ethyl carbonyl, butyl, cyclohexyl carbonyl, allyl carbonyl, and other aliphatic hydrocarbon carbonyl groups; phenyl carbonyl, methyl phenyl carbonyl, and other aromatic hydrocarbon carbonyl groups; and these aliphatic hydrocarbon carbonyl or aromatic hydrocarbon carbonyl groups may be further substituted by alkyl, alkoxy, aryl, aryloxy, amino, halogen, or other groups.

[0120] Examples of the aforementioned hydrocarbon carbonyl groups include: aliphatic hydrocarbon carbonyl groups such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, allyloxycarbonyl, and cyclohexyloxycarbonyl; aromatic hydrocarbon carbonyl groups such as phenoxycarbonyl and methylphenoxycarbonyl; and groups in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted by alkyl, alkoxy, aryl, aryloxy, amino, or halogen atoms.

[0121] Examples of hydroxyl groups include: aliphatic hydrocarbon carbonyl groups such as methyl carbonyl group, ethyl carbonyl group, butyl carbonyl group, allyl carbonyl group, and cyclohexyl carbonyl group; aromatic hydrocarbon carbonyl groups such as phenyl carbonyl group and methyl phenyl carbonyl group; and groups in which these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc.

[0122] The term "two or more of R4 to R7 that can bond together to form a cyclic structure" as described in the general formula (I-1) refers to 2 to 4 R4 to R7 bonds that, as a whole, can form a divalent to tetravalent organic group. Examples of R4 to R7 in this case include: alkyl groups such as ethyl, propyl, butyl, pentyl, and hexyl; alkenyl groups such as ethynyl, propynyl, and butynyl; arylyl groups such as methylene phenyl; arylyl, naphthyl, and anthraceneyl; and other substituents that can form a cyclic structure, as well as their oxygen or dioxy groups. These substituents can also be further substituted with alkyl, alkoxy, aryl, aryloxy, amino, hydroxyl, or halogen atoms.

[0123] R4 to R7 of the general formula (I-1) are not particularly limited. For example, they are preferably each independently selected from hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, or substituted or unsubstituted aryloxy group. From the viewpoint of ease of obtaining the raw materials, hydrogen atom, hydroxyl group, unsubstituted or at least one substituted aryl group selected from the group consisting of alkyl and alkoxy groups, or chain or cyclic alkyl groups are preferred. Examples of unsubstituted or at least one substituted aryl group selected from the group consisting of alkyl and alkoxy groups include: phenyl, p-tolyl, m-tolyl, o-tolyl, p-methoxyphenyl, etc. Examples of chain or cyclic alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tributyl, octyl, cyclohexyl, etc. From the viewpoint of hardening properties, it is preferable that all R4 to R7 are hydrogen atoms, or that at least one of R4 to R7 is a hydroxyl group and the rest are all hydrogen atoms.

[0124] In general formula (I-1), preferably, two or more of R1 to R3 are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, R4 to R7 are all hydrogen atoms or at least one is a hydroxyl group, and the rest are all hydrogen atoms. More preferably, all of R1 to R3 are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, R4 to R7 are all hydrogen atoms or at least one is a hydroxyl group, and the rest are all hydrogen atoms.

[0125] From the viewpoint of rapid curing, a particular curing accelerator is preferably a compound comprising the general formula (I-2) below.

[0126] [Chemistry 21]

[0127] In formula (I-2), R1 to R3 are each independently a hydrocarbon group with 1 to 18 carbon atoms, and two or more of R1 to R3 can bond together to form a ring structure. R4 to R6 are each independently a hydrogen atom or an organic group with 1 to 18 carbon atoms, and two or more of R4 to R6 can bond together to form a ring structure.

[0128] The specific examples of R1 to R6 in general formula (I-2) are the same as those of R1 to R6 in general formula (I-1), and the preferred ranges are also the same.

[0129] Certain hardening accelerators can be obtained, for example, as adducts of third phosphine compounds and quinone compounds. Specifically, examples of third phosphine compounds include: triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tri(4-methylphenyl)phosphine, tri(4-ethylphenyl)phosphine, tri(4-n-propylphenyl)phosphine, tri(4-n-butylphenyl)phosphine, tri(isopropylphenyl)phosphine, tri(tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, and tri(4-ethoxyphenyl)phosphine. From the viewpoint of formability, triphenylphosphine and tributylphosphine are preferred.

[0130] As quinone compounds, specific examples include 1,2-benzoquinone, 1,4-benzoquinone, biphenylquinone, 1,4-naphthoquinone, and anthraquinone. From the viewpoint of moisture resistance and storage stability, 1,4-benzoquinone is preferred.

[0131] Specific examples of specific hardening accelerators include: the addition reaction product of triphenylphosphine and 1,4-benzoquinone, the addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, the addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, the addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, the addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, the addition reaction product of triisobutylphosphine and 1,4-benzoquinone, and the addition reaction product of tricyclopentylphosphine and 1,4-benzoquinone, etc.

[0132] Curing resin compositions may also contain curing accelerators other than phosphonium compounds. As curing accelerators other than phosphonium compounds, specifically examples include: diazabicyclo[4.3.0]nonene-5 (DBN), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and other diazabicycloolefins; cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of said cyclic amidine compounds; phenolic varnish salts of said cyclic amidine compounds or their derivatives; and the addition of maleic anhydride, 1,4-benzoquinone, 2,5-toluenequinone, 1,4-naphthoquinone, and 2,3-dimethyl... Compounds with intramolecular polarization formed from quinone compounds such as benzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone; compounds with π bonds such as diazonylmethane; cyclic amidine compounds such as tetraphenylborate of DBU, tetraphenylborate of DBN, tetraphenylborate of 2-ethyl-4-methylimidazolium, and tetraphenylborate of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the aforementioned tertiary amine compounds; and ammonium salt compounds such as tetrabutylammonium acetate, tetrabutylammonium phosphate, tetraethylammonium acetate, tetrahexylammonium benzoate, and tetrapropylammonium hydroxide.

[0133] When the curable resin composition contains a specific curing accelerator as a curing accelerator, the content of the specific curing accelerator relative to the total mass of the curing accelerator is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0134] When a curing resin composition contains a curing accelerator, the content of the curing accelerator relative to the total mass of the resin component is preferably 0.1% to 30% by mass, more preferably 1% to 15% by mass. If the content of the curing accelerator relative to the total mass of the resin component is 0.1% by mass or more, the curing resin composition tends to cure well in a short time. If the content of the curing accelerator relative to the total mass of the resin component is 30% by mass or less, the curing speed of the curing resin composition tends to be not too fast, and good molded products can be obtained.

[0135] (Inorganic filler material) The curable resin composition disclosed herein may also contain inorganic fillers. By containing inorganic fillers, the hygroscopicity of the curable resin composition tends to decrease, and its strength in the cured state tends to increase. When the curable resin composition is used as a sealing material for semiconductor packaging, it is preferable to contain inorganic fillers.

[0136] There are no particular restrictions on the types of inorganic fillers. Specifically, examples include: spherical silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zircon, zircon, forsterite, blocky talc, spinel, aluminum-rich andalusite, titanium oxide, talc, clay, mica, and other inorganic materials. Inorganic fillers with flame-retardant properties can also be used. Examples of flame-retardant inorganic fillers include: aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium and zinc hydroxides, zinc borate, etc. From the viewpoint of reducing the coefficient of linear expansion, spherical silica is preferred; from the viewpoint of high thermal conductivity, alumina is preferred. One type of inorganic filler can be used alone, or two or more can be combined. Examples of the states of inorganic fillers include: powder, spheroidized powder particles, fibers, etc. Inorganic fillers can be used alone or in combination of two or more.

[0137] There are no particular limitations on the shape of inorganic fillers; examples include powder, spheres, and fibers. However, spherical shapes are preferred in terms of flowability during molding of the curable resin composition and mold abrasion resistance.

[0138] There are no particular limitations on the average particle size of inorganic fillers. From the viewpoint of balancing the viscosity, filling properties, etc. of the curable resin composition, the volume average particle size of inorganic fillers is preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 30 μm, and even more preferably 0.5 μm to 25 μm. The average particle size of inorganic fillers can be determined as the volume average particle size (D50) using a laser diffraction particle size distribution measuring device. The volume average particle size can be determined using known methods. For example, an inorganic filler can be extracted from a self-curing resin composition or cured resin using organic solvents, nitric acid, aqua regia, etc., and then thoroughly dispersed using an ultrasonic disperser to prepare a dispersion. This dispersion can be used to determine the volume average particle size of the inorganic filler based on the particle size distribution measured using a laser diffraction particle size distribution measuring device. Alternatively, the cured resin can be embedded in a transparent epoxy resin, etc., and ground to obtain a cross-section. The volume average particle size of the inorganic filler can be determined based on the particle size distribution obtained from the cross-section observed using a scanning electron microscope. Furthermore, it can also be determined by continuously observing two-dimensional cross-sections of the cured resin using a focused ion beam (FIB) device (Scanning Electron Microscope, SEM) and performing three-dimensional structural analysis.

[0139] When the curable resin composition contains inorganic fillers, there is no particular limitation on the content of the inorganic fillers. The content of inorganic fillers relative to the total mass of the 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. If the content of inorganic filler relative to the total mass of the curable resin composition is more than 30% by mass, there is a tendency for the thermal expansion coefficient, thermal conductivity, elastic modulus and other properties of the cured resin to be further improved. If the content of inorganic filler relative to the total mass of the curing resin composition is less than 90% by mass, the increase in viscosity of the curing resin composition is suppressed, the fluidity is further improved, and the formability becomes better.

[0140] (Coupling agent) The curable resin composition disclosed herein may also contain a coupling agent. There are no particular restrictions on the type of coupling agent; known coupling agents may be used. Examples of coupling agents include silane coupling agents and titanium coupling agents. A single coupling agent may be used, or two or more may be used in combination.

[0141] The silane coupling agent is not particularly limited as long as it is a compound other than the aforementioned linear polysiloxane compound, and examples include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 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-ureopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, etc.

[0142] Examples of titanium coupling agents include: isopropyl triisostearyl titanate, isopropyl tri(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(di-tetrazyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tetrazyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate) ethyl titanate, isopropyl trioctyl titanate, isopropyl dimethacrylate isostearyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearyl diacrylate titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate, etc.

[0143] In terms of solder reflow resistance, the disclosed curable resin composition is preferably one containing at least one of 3-aminopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.

[0144] When the curing resin composition contains a coupling agent, from the viewpoint of the adhesion of the epoxy resin to the inorganic filler interface, the content of the coupling agent relative to the total mass of the inorganic filler contained in the curing resin composition is preferably 0.001% to 10% by mass, more preferably 0.01% to 8% by mass, and even more preferably 0.05% to 5% by mass.

[0145] (Stress reliever) The disclosed curable resin composition may also contain stress-relieving agents such as silicone oil and silicone rubber particles. By containing stress-relieving agents in the curable resin composition, the warpage and cracking of the encapsulation can be further reduced. Commonly used and known stress-relieving agents (flexible agents) can be listed as stress-relieving agents. Specifically, examples of stress-relieving agents include: thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers; rubber particles such as natural rubber (NR), acrylonitrile butadiene rubber (NBR), acrylic rubber, urethane rubber, and silicone powder; and rubber particles with core-shell structures such as methyl methacrylate butadiene styrene (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. Stress relievers can be used alone or in combination of two or more. Silicone-based stress relievers are preferred. Examples of silicone-based stress relievers include those with epoxy groups, those with amine groups, and those modified with polyethers.

[0146] When the curing resin composition contains a stress reliever, the content of the stress reliever relative to the total mass of epoxy resin contained in the curing resin composition is preferably 0.1% to 30% by mass, and more preferably 1% to 5% by mass.

[0147] (Mold release agent) When using a mold for molding, the disclosed curable resin composition may also contain a release agent from the viewpoint of mold release properties. There are no particular limitations on the release agent; previously known agents may be used. Examples of release agents include: carnauba wax, higher fatty acids such as octacoate and stearic acid, metal salts of higher fatty acids, ester waxes such as octacoate esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. A single release agent may be used, or two or more may be used in combination.

[0148] When the curable resin composition disclosed herein contains a release agent, the content of the release agent relative to the total mass of epoxy resin contained in the curable resin composition is preferably 0.01% to 15% by mass, more preferably 0.1% to 10% by mass. If the content of the release agent relative to the total mass of epoxy resin contained in the curable resin composition is 0.01% by mass or more, there is a tendency to obtain sufficient release properties. If the content of the release agent relative to the total mass of epoxy resin contained in the curable resin composition is 15% by mass or less, there is a tendency to obtain even better release properties.

[0149] (Coloring agent) The curable resin composition disclosed herein may also contain colorants. Examples of colorants include: carbon black, organic dyes, organic pigments, titanium dioxide, red lead, iron oxide, and other known colorants. The content of the colorant can be appropriately selected according to the purpose, etc. A single colorant may be used, or two or more may be used in combination.

[0150] When the curable resin composition contains a colorant, the content of the colorant relative to the total mass of the curable resin composition is preferably 0.01% to 5% by mass, more preferably 0.05% to 3% by mass, and even more preferably 0.01% to 1% by mass.

[0151] (Flame retardant) The cured resin composition disclosed herein may also contain flame retardants. There are no particular limitations on the flame retardant; previously known flame retardants may be used. Examples of flame retardants include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, as well as metal hydroxides. A single flame retardant may be used, or two or more may be used in combination.

[0152] When the curable resin composition disclosed herein contains a flame retardant, there is no particular limitation on the content of the flame retardant, provided that it is sufficient to obtain the desired flame retardant effect. The content of the flame retardant relative to the total mass of epoxy resin contained in the curable resin composition is preferably 1% to 300% by mass, more preferably 2% to 150% by mass.

[0153] (ion exchanger) The curable resin composition disclosed herein may also contain ion exchangers. When the curable resin composition is used as a sealing material for semiconductor packaging, it is preferable to contain ion exchangers from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of electronic components including the sealed elements. The ion exchanger is not particularly limited, and those previously known can be used. Specifically, hydrotalcite compounds, hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth, etc. can be cited. The ion exchanger can be used alone or in combination of two or more kinds. Specifically, as the ion exchanger, hydrotalcite represented by the following general formula (A) can be cited.

[0154] Mg (1-X)AlX(OH) 2(CO 3) X / 2·mH 2O ･･･(A) (0<X≦0.5, m is a positive number)

[0155] 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 a sufficient amount for capturing ions such as halogen ions. The content rate of the ion exchanger relative to the total mass of the epoxy resin contained in the curable resin composition is preferably 0.1% by mass to 30% by mass, more preferably 1% by mass to 5% by mass.

[0156] (Resin other than epoxy resin) [[ID=ID=18]]The curable resin composition of the present disclosure may also contain a resin other than an epoxy resin. The type of the resin other than the epoxy resin is not particularly limited, and it can be selected from those usually used as components of curable resin compositions. The resin other than the epoxy resin can be used alone or in combination of two or more kinds.

[0157] Specific examples of the resin other than the epoxy resin are described below, but are not limited thereto. As the resin other than the epoxy resin, the following can be cited: thiol resin, urea resin, melamine resin, urethane resin, silicone resin, maleimide resin, unsaturated polyester resin, etc.

[0158] (Hardener other than phenolic hardener) The curable resin composition of the present disclosure may also contain a hardener other than a phenolic hardener. The type of the hardener other than the phenolic hardener is not particularly limited, and it can be selected from those usually used as components of curable resin compositions. The hardener other than the phenolic hardener can be used alone or in combination of two or more kinds.

[0159] Specific examples of the hardener other than the phenolic hardener are described below, but are not limited thereto. Other types of curing agents besides phenolic curing agents include: amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamine curing agents, isocyanate curing agents, and block isocyanate curing agents.

[0160] When the hardener, other than phenolic hardener, includes amine hardener, there is no particular limitation on the active hydrogen equivalent of the amine hardener. From the viewpoint of balancing various properties such as reflow resistance, formability, and electrical reliability, a value of 10 g / eq to 1000 g / eq is preferred, and 30 g / eq to 500 g / eq is more preferred. The active hydrogen equivalent of amine-based curing agents refers to the value calculated based on the amine value determined according to JIS K 7237:1995.

[0161] When the curable resin composition disclosed herein contains curing agents other than phenolic curing agents, the content of curing agents other than phenolic curing agents relative to the total mass of the curable resin composition is not particularly limited, but is preferably 2% to 35% by mass, more preferably 5% to 30% by mass.

[0162] (Method for manufacturing curable resin composition) There are no particular limitations on the manufacturing method of the curable resin composition. A common method includes: thoroughly mixing a specified amount of the components using a mixer or similar equipment, then melt-kneading using a mixing roller, extruder, or similar equipment, followed by cooling and pulverization. More specifically, a method may include: uniformly stirring and mixing a specified amount of the components, kneading using a kneader, roller, extruder, or similar equipment preheated to 70°C to 140°C, cooling, and pulverizing.

[0163] The curable resin composition is preferably solid at 25°C. When the curable resin composition is solid at 25°C, its shape is not particularly limited, and examples include powder, granules, and small flakes. From an operational point of view, the size and weight of the curable resin composition in small flake form are preferably consistent with the molding conditions for encapsulation.

[0164] (Uses of curable resin compositions) The applications of the disclosed curable resin composition are not particularly limited; for example, it can be used as a sealant for electronic components in various mounting technologies. Furthermore, the disclosed curable resin composition is ideally suited for various applications, including resin molded bodies for modules, resin molded bodies for motors, resin molded bodies for automotive applications, and sealants for protective materials in electronic circuits, exhibiting good flowability and curing properties.

[0165] <Electronic Components and Devices> The electronic component device disclosed herein includes an element and a cured form of the curable resin composition that seals the element.

[0166] Electronic component devices may further include support members for mounting the components. Examples of support components include: lead frames, wired carrier tapes, wiring boards, glass, silicon wafers, and organic substrates. Among these support components, a lead frame is preferred from the viewpoint of adhesion to the cured form of the curable resin composition.

[0167] The surface of the lead frame may be roughened or not. From the point of view of manufacturing cost, an unroughened lead frame is preferred, while from the point of view of adhesion, a roughened lead frame is preferred. There are no particular limitations on roughening methods, and examples include: alkali treatment, silane coupling treatment, sand pad treatment, plasma treatment, corona discharge treatment, etc.

[0168] The lead frame may include a plating layer comprising at least one of Au, Pd and Ni on at least a portion of its surface. Furthermore, the plating layer can be a single layer or multiple layers. Examples of multi-layer plating layers include a three-layer structure consisting of a Ni plating layer, a Pd plating layer, and an Au plating layer deposited from the lead frame side. As an example of the three-layer lead frame structure, a lead frame for which Ni-Pd-Au plating is applied to a copper lead frame known as PPF (Pre-plating Lead Flame) can be cited.

[0169] There is no particular limitation on the thickness of the coating, but it is preferably less than 5 μm, more preferably less than 4 μm, and even more preferably less than 3 μm.

[0170] Components included in electronic devices include, for example, active components such as silicon wafers, transistors, diodes, and thyristors; and passive components such as capacitors, resistors, and coils.

[0171] The following structures can be listed as specific structures for electronic components, but are not limited to these. (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) have a structure in which the component is fixed on the lead frame and the terminal and lead portions of the component are sealed with a curable resin composition after wire bonding, bumps, or other bonding pads are used to connect the components. (2) Tape Carrier Package (TCP), which has a structure that uses a curable resin composition to seal components connected to a carrier tape by bumps; (3) Chip On Board (COB) modules, hybrid ICs, polycrystalline modules, etc., which have a structure that uses a curable resin composition to seal components on wiring formed by wire bonding, flip chip bonding, solder, etc., connected to a support member; (4) Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), System in a Package (SiP), etc., which have components mounted on the surface of a support member on which wiring board connection terminals are formed on the back side, and the components are connected to the wiring formed on the support member by bumps or wire bonding, and the components are sealed with a curable resin composition.

[0172] There are no particular limitations on the method of sealing components using a curable resin composition; known methods can be used. For example, low-pressure transfer molding is commonly used, but spray molding, compression molding, and casting can also be employed. [Example]

[0173] The present disclosure will now be specifically described through examples, but the present disclosure is not limited to these examples. Furthermore, unless otherwise specified, the values ​​in the tables refer to "parts by mass".

[0174] (Examples 1-7 and Comparative Examples 1-3) After premixing (dry blending) the materials of the formulation shown in Table 1, knead them for about 15 minutes using a biaxial roller (roller surface temperature: about 80°C), cool and pulverize them to produce a powdered curable resin composition.

[0175] The details of the materials in Table 1 are as follows. Furthermore, the equivalent ratio of the phenolic hydroxyl groups of the phenolic curing agents to the epoxy groups of the epoxy resins in Table 1 was determined by the method described above.

[0176] • Epoxy Resin A: A copolymerizable epoxy resin having the following structural units: epoxy equivalent 250 g / eq, melt viscosity at 150°C 0.7 dPa·s, Mn 350~600

[0177] [Chemistry 22]

[0178] • Epoxy Resin B: Biphenyl-type epoxy resin, epoxy equivalent 196 g / eq, softening point 106℃, manufactured by Mitsubishi Chemical Corporation, trade name "YX-4000H", Mn 350 • Epoxy resin C: Biphenyl aryl type epoxy resin, epoxy equivalent 284 g / eq

[0179] Phenolic curing agent A: Aryl alkyl phenolic resin, hydroxyl equivalent 106 g / eq Phenolic curing agent B: Triphenylmethane-type phenolic resin, hydroxyl equivalent 95 g / eq • Phenolic curing agent C: Aryl alkyl phenolic resin, hydroxyl equivalent 203 g / eq Phenolic hardener D: Melamine-modified phenolic resin, hydroxyl equivalent 120 g / eq, softening point: 90℃ • Phenolic curing agent E: Triazine-type phenolic resin, 2-[4-[(2-hydroxy-3-(2'-ethylhexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, BASF, trade name "Tinuvin (registered trademark) 405" • Phenolic hardener F: Phenolic resin for varnish type, hydroxyl equivalent 223 g / eq • Phenolic hardener G: Phenolic resin for varnish type, hydroxyl equivalent 156 g / eq

[0180] • Hardening accelerator: The product of the addition reaction of triphenylphosphine and 1,4-benzoquinone

[0181] Coupling agent A: 3-aminopropyltrimethoxysilane Coupling agent B: 3-glycidoxypropyltrimethoxysilane Coupling agent C: linear polysiloxane, melting point: -70℃, epoxy equivalent 120 g / eq~150 g / eq Coupling agent D: Tetrathione di-triethoxysilane

[0182] Stress Relief Agent A: Epoxy-Modified Silicone Resin Stress reliever B: Indene-containing copolymer Stress reliever C: Phenyl-containing silicone resin

[0183] Inorganic filler A: Silicon dioxide filler with an average particle size of 19.4 μm. • Inorganic filler B: Silica filler with an average particle size of 0.6 μm Inorganic filler C: Silicon dioxide filler with an average particle size of less than 50 nm. • Inorganic filler D: A magnesium and zinc-containing metal hydroxide with an average particle size of 1.2 μm.

[0184] <<Evaluation of Curable Resin Compositions>> The properties of the curable resin compositions manufactured in the Examples and Comparative Examples were evaluated by the following characteristic tests. The evaluation results are shown in Table 1. Furthermore, regarding the production of resin-cured products using curable resin compositions, unless explicitly stated otherwise, it is carried out in the following manner: after molding using a transfer molding machine at a mold temperature of 175°C, molding pressure of 8.3 MPa, and curing time of 120 seconds, post-curing is performed at 175°C for 5 hours.

[0185] <Reflow Resistance Evaluation> For a 28-pin Small Outline (SO) package with a silicon wafer of 3.2 mm × 2.2 mm × 0.37 mm mounted on a mold pad of 5.2 mm × 4.1 mm (lead frame material: copper alloy, Ni-Pd-Au plated product), it is molded using a curable resin composition, and then post-cured under the conditions of 175°C for 5 hours. It was visually confirmed that there were no cracks on the exterior of the obtained molded product, and it was confirmed by an ultrasonic flaw detector (manufactured by Hitachi, Ltd., FS-200) that there was no internal delamination. After drying the molded product at 125°C for 12 hours, it was humidified at a temperature of 85°C and a relative humidity of 85% for 168 hours. After that, according to the regulations of JEDEC, the temperature condition was set to 260°C, and three reflow processes were carried out at the same temperature. The exterior of the package was visually observed for cracks, and the interior of the package was observed by an ultrasonic flaw detector for delamination. The solder reflow resistance was evaluated by the ratio of the number of packages with either cracks or delamination to the number of test packages. The evaluation results are summarized in Table 1. (Evaluation Criteria) A: The occurrence of cracks and delamination is 0% B: The occurrence of cracks and delamination exceeds 0% and is less than 60% C: The occurrence of cracks and delamination is 60% or more and less than 100% D: The occurrence of cracks and delamination is 100%

[0186] (Measurement of tanδ and Storage Elastic Modulus) Based on the above conditions, resin cured products of the curable resin compositions obtained in the above Examples and Comparative Examples were produced. The resin cured products were rectangular resin cured products having a short side of 5 mm, a long side of 50 mm, and a thickness of 2 mm. For the resin cured products, dynamic viscoelasticity measurements were carried out under the conditions of test mode: three-point bending mode, measurement temperature: 25°C to 330°C, heating rate: 10°C / minute, test frequency: 1 Hz. The storage viscoelasticity values were obtained from the obtained chart (vertical axis: tanδ, horizontal axis: temperature) and are summarized in Table 1. In addition, based on the above charts, the following are calculated: (1) the temperature at which tanδ becomes the maximum (glass transition temperature), (2) the tanδ value at the glass transition temperature, (3) the tanδ value at a temperature 10 degrees lower than the glass transition temperature when the tanδ value at the glass transition temperature is set to 100 (recorded as tanδ ratio in Table 1), (4) the total tanδ values ​​at temperatures of 220℃, 230℃, 240℃ and 250℃ (recorded as tanδ total 1 in Table 1), and (5) the total tanδ values ​​at temperatures of 70℃, 80℃ and 90℃ (recorded as tanδ total 2 in Table 1), and summarized in Table 1.

[0187] <Determination of Coefficient of Thermal Expansion (CTE1)> Based on the aforementioned conditions, a resin-cured product of the curable resin composition obtained in the embodiments and comparative examples was prepared. The resin-cured product was set to have a diameter of φ4 mm × 20 mm. Subsequently, based on JIS K 7197:2012, the slope of the tangent line when plotting the strain of the cured resin relative to temperature was determined within the range of 10℃ to 30℃ using thermomechanical analysis. The measurement results are summarized in Table 1. Furthermore, the test load was set to 15 g, and the heating rate was set to 5℃ / minute for the measurement. In addition, the TMA high-precision two-sample thermal analysis apparatus (device name SS6100) manufactured by Seiko Instruments Co., Ltd. was used to determine the coefficient of linear expansion.

[0188] <Determination of water absorption rate> Based on the aforementioned conditions, a resin-cured product of the curable resin composition obtained in the embodiments and comparative examples was prepared. The resin-cured product was configured as a rectangular product having a short side of 5.1 mm, a long side of 20 mm, and a thickness of 2 mm. Subsequently, the resin-cured material was left to stand for 168 hours at a temperature of 85°C and a relative humidity of 85%. The mass (g) of the cured resin after standing was measured, and the increase rate (%) relative to the mass (g) of the cured resin before standing was calculated. The results are summarized in Table 1.

[0189] Liquidity Assessment (Spiral Flow) Using a auger for spiral flow measurement according to EMMI-1-66, the curable resin compositions obtained in the examples and comparative examples were molded under conditions of mold temperature 180°C, molding pressure 6.9 MPa, and curing time 90 seconds, and the flow distance (cm) was determined. The measurement results are summarized in Table 1.

[0190] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Epoxy resin A 70 70 70 70 70 70 70 - 70 70 B 30 30 30 30 30 30 30 70 30 30 C - - - - - - - 30 - - Phenolic hardeners A 47.3 39.5 47.3 41.5 41.5 41.5 41.5 - - - B - - - - - - - - 42.5 30.4 C - - - - - - - - - 13 D - 3 - 3 3 3 3 6 3 3 E - 10 - 10 10 10 10 10 - 10 F 8 8 8 5.5 5.5 5.5 5.5 33.6 - 7.8 G - - - - - - - 42.8 - - hardening accelerator 5 5 5 5 5 5 4.5 5 5.3 5.8 Coupling agent A 3 12 9 3 1 3 1 3 3.1 3 B 3 - - 4.5 1.5 4.5 1.5 4.5 3.1 4.5 C - - - - 5 - 5 - - - D - - - - - - - 1 - - Stress reliever A - - 20 20 - 20 20 - 20 - B - - - - - - - 10 - 30 C 20 20 - - - - - - - - Inorganic fillers A 1387 1462 1588 1619 1469 1367 1451 1686 1063 1657 B - - - - - 152 161 - - - C - - - - - - - 10 - - D - - - - - - - 6 - - Release agent (wax) 1 1 1 1 1 1 1 1 1 1 Colorant (carbon black) 3 3 3 4 4 3.5 3.5 3.1 3.3 4 Ion exchangers (hydrotalcite compounds) 3 3 3 3 3 3 3 3 3 3 The equivalent ratio of phenolic hydroxyl groups in phenolic curing agents to epoxy groups in epoxy resins. 0.7 0.7 0.7 0.7 0.7 0.7 0.7 1 1 1 Evaluation of reflow resistance A A A A B B B D D D Storage elasticity coefficient (MPa) 355 349 417 338 359 293 320 172 372 615 (1) Glass transfer temperature (°C) 105 98 102 86 86 86 83 102 112 125 (2) tanδ value at glass transfer temperature 0.413 0.477 0.417 0.639 0.603 0.623 0.609 0.379 0.677 0.408 (3) tanδ ratio 97 88 95 66 71 80 67 75 57 87 (4)tanδ total 1 0.401 0.428 0.422 0.488 0.473 0.446 0.433 0.427 0.302 0.527 (5) tanδ total 2 0.767 0.899 0.737 1.346 1.309 1.435 1.416 0.516 0.163 0.123 Measurement of coefficient of thermal expansion (CTE1) (ppm / ℃) 9 9 9 10 10 11 11 7 10 6 Determination of water absorption rate (%) 0.18 0.19 0.18 0.19 0.20 0.21 0.21 0.18 0.25 0.16 Liquidity assessment (cm) 97 84 66 65 61 74 56 91 137 64

[0191] Based on the results summarized in Table 1, it can be seen that the hardened resin composition obtained in the examples exhibits superior reflow resistance compared to the hardened resin composition obtained in the comparative examples.

[0192] The entire disclosure of Japanese Patent Application No. 2021-140408, filed on August 30, 2021, is incorporated herein by reference. All documents, patent applications, and technical specifications described in this specification are incorporated herein by reference to the same extent as those documents, patent applications, and technical specifications specifically described therein.

[0193] none

Claims

1. A curable resin composition comprising an epoxy resin and the phenolic curing agent in which the phenolic hydroxyl group of the phenolic curing agent is present in an equivalent ratio of 0.5 or more but less than 1.0 to the epoxy group of the epoxy resin, wherein the epoxy resin comprises a copolymeric epoxy resin having structural units derived from alkylphenol and structural units derived from alkoxynaphthalene, and a biphenyl-type epoxy resin, and the phenolic curing agent comprises one or more phenolic curing agents selected from the group consisting of arylalkyl-type phenolic resins and phenolic varnish-type phenolic resins.

2. The curable resin composition as claimed in claim 1, wherein, The copolymerized epoxy resin contains 50% to 90% by mass relative to the total mass of the epoxy resin.

3. The curable resin composition as described in claim 1 or claim 2, wherein, The phenolic curing agent comprises an aralkyl phenolic resin, and the aralkyl phenolic resin accounts for 60% to 95% of the total mass of the phenolic curing agent.

4. The curable resin composition as claimed in claim 1 or claim 2 further comprises a curing accelerator, said curing accelerator comprising an adduct of a third phosphine compound and a quinone compound.

5. An electronic component device comprising an element and a resin-cured form of a curable resin composition as described in claim 1 or claim 2, which seals the element.

6. The electronic component device as claimed in claim 5 further includes a support member on one side of which the element is mounted.