Resin composition, electronic component device, method for manufacturing an electronic component device, and method for manufacturing a resin composition

Abstract

To provide a resin composition which can achieve good toughness by a method other than use of an additive, an electronic component device obtained by using the resin composition, a method for manufacturing an electronic component device using the resin composition, and a method for producing a resin composition which is excellent in toughness of a cured product.SOLUTION: A resin composition contains an epoxy resin, a curing agent and a curing accelerator, wherein when a peak corresponding to a reaction product of the epoxy resin and the curing accelerator is represented by a peak A, and a peak corresponding to an internal standard substance is represented by a peak B, in measurement by a MALDI-TOF / MS method, an intensity ratio (A / B) of the peak A to the peak B is 0.0005 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a resin composition, an electronic component device, a method for manufacturing an electronic component device, and a method for manufacturing a resin composition.

Background Art

[0002] Resin compositions containing thermosetting resins such as epoxy resins are widely used as encapsulating materials for protecting the surroundings of electronic component devices such as semiconductor packages (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In order to cope with diversification of the structure of electronic component devices and reduction of manufacturing costs, it has been considered to reduce the volume ratio of the encapsulating material in the electronic component device. However, when the volume ratio of the encapsulating material is decreased, the risk of cracks due to stress concentration increases. As a method for alleviating stress concentration, the use of additives such as flexible materials is conceivable, but there is a limit to the amount of additives used in consideration of the balance of the properties of the encapsulating material. An object of the present disclosure is to provide a resin composition in which good toughness is achieved by a method other than the use of additives, an electronic component device obtained by using this resin composition, and a method for manufacturing an electronic component device using this resin composition. Another object of the present disclosure is to provide a method for manufacturing a resin composition having excellent toughness of the cured product.

Means for Solving the Problems

[0005] Specific means for solving the above problems include the following aspects. <1> It contains epoxy resin, a hardener, and a curing accelerator. A resin composition in which, in measurement by the MALDI-TOF / MS method, when the peak corresponding to the reaction product of the epoxy resin and the curing accelerator is defined as peak A and the peak corresponding to the internal standard substance is defined as peak B, the intensity ratio of peak A to peak B (A / B) is 0.0005 or less. <2> The curing accelerator does not contain a functional group that reacts with the epoxy group. <1> The resin composition described above. <3> The epoxy resin comprises at least one selected from the group consisting of triphenylmethane-type epoxy resin, biphenylaralkyl-type epoxy resin, naphthalenearalkyl-type epoxy resin, and novolac-type epoxy resin. <1> or <2> The resin composition described above. <4> The curing agent comprises at least one selected from the group consisting of triphenylmethane-type phenolic resin, biphenylaralkyl-type phenolic resin, naphthalenearalkyl-type phenolic resin, and novolac-type phenolic resin. <1> ~ <3> A resin composition according to any one of the items. <5> For use as a sealing material for electronic component devices in which the volume ratio of the sealing material to the total volume of the electronic component device is 50% or less, <1> ~ <4> A resin composition according to any one of the items. <6> A support member, an element placed on the support member, and an element arranged around the element <1> ~ <5> An electronic component device comprising a cured product of a resin composition according to any one of the items. <7> A step of placing the element on a support member, and the element <1> ~ <5> A method for manufacturing an electronic component device, comprising the step of sealing with a resin composition described in any one of the items. <8> A method for producing a resin composition containing an epoxy resin, a curing agent, and a curing accelerator, comprising calculating the intensity ratio (A / B) of peak A to peak B, where peak A is defined as the reaction product of the epoxy resin and the curing accelerator, and peak B is defined as the internal standard, in a measurement by MALDI-TOF / MS method. [Effects of the Invention]

[0006] This disclosure provides a resin composition in which good toughness is achieved by means other than the use of additives, an electronic component device obtained using this resin composition, and a method for manufacturing an electronic component device using this resin composition. This disclosure also provides a method for manufacturing a resin composition in which the cured product has excellent toughness. [Modes for carrying out the invention]

[0007] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, each component may contain multiple types of particles. If multiple types of particles corresponding to each component are present in the composition, the particle size of each component refers to the value for a mixture of such multiple types of particles present in the composition, unless otherwise specified.

[0008] <Resin composition> The resin composition disclosed herein contains an epoxy resin, a curing agent, and a curing accelerator. In measurements using the MALDI-TOF / MS method, when the peak corresponding to the reaction product of the epoxy resin and the curing accelerator is defined as peak A, and the peak corresponding to the internal standard substance is defined as peak B, the intensity ratio of peak A to peak B (A / B) is 0.0005 or less.

[0009] In this disclosure, the intensity ratio of peak A to peak B (A / B) may be simply referred to as the "peak intensity ratio."

[0010] In this disclosure, MALDI is an abbreviation for Matrix Assisted Laser Desorption / Ionization, and TOF / MS is an abbreviation for Time of Flight Mass Spectrometry.

[0011] A small intensity ratio (A / B) of peak A to peak B indicates that the reaction between the epoxy resin and the curing accelerator in the resin composition is suppressed. Our investigations have shown that resin compositions in which the reaction between epoxy resin and curing accelerator is suppressed maintain good toughness of the cured product. Therefore, when the resin composition is used, for example, as a encapsulant for electronic components, cracking of the encapsulant can be effectively suppressed.

[0012] The reason why the toughness of the cured product of a resin composition in which the reaction between the epoxy resin and the curing accelerator is suppressed is not entirely clear, but it is presumed to be as follows. When a portion of the curing accelerator contained in the resin composition reacts with a portion of the epoxy resin, the cured product obtained by curing the resin composition contains a mixture of different polymer networks: one formed by the reaction between the epoxy resin and the curing accelerator, and another formed by the reaction between the epoxy resin and the curing agent. When the reaction between the curing accelerator and the epoxy group contained in the resin composition is suppressed, the coexistence of the different polymer networks described above in the cured product is suppressed. As a result, it is considered that the resin structure of the cured product becomes dense and good toughness is maintained.

[0013] The MALDI-TOF / MS method is one of the mass spectrometry methods. Specifically, a mixture containing a resin component to be measured, an internal standard substance, a matrix, and an ionizing agent is irradiated with a laser to ionize the components contained in the mixture, and mass spectrometry is performed based on the flight time of the obtained ionized products.

[0014] The peak corresponding to the reaction product of the epoxy resin and the curing accelerator is specifically considered to be the peak detected at the m / z of the value obtained by adding 1 to the sum of the molecular weight of the epoxy resin and the molecular weight of the curing accelerator (that is, the state in which a proton is added to the reaction product of the molecule of the epoxy resin and the molecule of the curing accelerator). When the reaction product of the molecule of the epoxy resin and the molecule of the curing accelerator consists of two molecules of the epoxy resin and one molecule of the curing accelerator, the peak detected at the m / z of the value obtained by adding 1 to the sum of twice the molecular weight of the epoxy resin and the molecular weight of the curing accelerator is considered to be the peak corresponding to the reaction product of the epoxy resin and the curing accelerator.

[0015] When there are two or more peaks corresponding to the reaction product of the epoxy resin and the curing accelerator, the peak intensity ratio is calculated with the peak having the maximum intensity as peak A.

[0016] As the internal standard substance used for measuring the peak intensity, it is preferable to use a substance having no functional group that reacts with the epoxy group. From the viewpoints of suppressing phase separation with other components contained in the mixture, ionization efficiency, and safety, it is preferable to use a crown ether having no functional group that reacts with the epoxy group as the internal standard substance.

[0017] Examples of crown ethers that do not have functional groups that react with epoxy groups include dibenzo-24-crown-8 and 4,4'(5')-di-t-butyldibenzo-18-crown-6.

[0018] Matrix materials used for measuring peak intensity include dithranol and trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile.

[0019] Sodium trifluoroacetate is an example of an ionization aid used for measuring peak intensity.

[0020] The mixture used for measurement may contain all the components of the resin composition, or it may contain only some of the components of the resin composition. If the mixture does not contain some of the components included in the resin composition, the mixture includes at least an epoxy resin, a curing agent, and a curing accelerator.

[0021] The mixing ratio of the above components contained in the mixture is not particularly limited and can be set within the scope of common technical knowledge in the field. For example, it is preferable to use 1 part by mass of resin composition (excluding components other than epoxy resin, curing agent, and curing accelerator if any) per 10 parts by mass of matrix, 1 part by mass of ionization aid, and 0.01 parts by mass of internal standard substance.

[0022] The concentrations of the above components contained in the mixture are not particularly limited and can be set within the range of common technical knowledge in the field. For example, it is preferable that the total concentration of the matrix, resin composition (excluding components other than epoxy resin, curing agent, and curing accelerator if any) contained in the mixture be between 5 mg / mL and 20 mg / mL.

[0023] The irradiation conditions for the laser used to measure peak intensity are not particularly limited and can be set within the scope of common technical knowledge in the field. For example, it is preferable to use a laser with a wavelength of 337 nm and set the irradiation conditions so that the intensity (au) of peak B, which corresponds to the internal standard material, is in the range of 1,000 to 100,000.

[0024] The method for controlling the peak intensity ratio of the resin composition is not particularly limited. Examples include using a curing accelerator that does not contain functional groups that react with epoxy groups, or using a curing accelerator that functions as a catalyst when heated to near the curing temperature (e.g., a latent or encapsulated curing accelerator).

[0025] The resin composition of this disclosure preferably has a glass transition temperature of 150°C or higher. When the glass transition temperature of the cured product is 150°C or higher, when the resin composition is used as a encapsulant for electronic components, warping of the substrate caused by volume changes of the cured product due to temperature changes is effectively suppressed. From the viewpoint of suppressing substrate warping, the glass transition temperature of the cured resin composition is more preferably 160°C or higher, even more preferably 170°C or higher, and particularly preferably 180°C or higher. From the viewpoint of maintaining good toughness, the glass transition temperature of the cured resin composition is preferably 230°C or lower, more preferably 220°C or lower, and even more preferably 210°C or lower.

[0026] In this disclosure, the glass transition temperature of the cured resin composition is measured by the method described in the examples.

[0027] From the viewpoint of suppressing substrate warping, the CTE1 (coefficient of linear expansion in the glass region) of the resin composition is preferably 8 ppm / °C or higher, more preferably 10 ppm / °C or higher, and even more preferably 12 ppm / °C or higher. From the standpoint of package reliability, the CTE1 of the resin composition is preferably 21 ppm / °C or less, more preferably 19 ppm / °C or less, and even more preferably 17 ppm / °C or less.

[0028] From the viewpoint of suppressing substrate warping, the CTE2 (coefficient of linear expansion in the rubber region) of the resin composition is preferably 35 ppm / °C or higher, more preferably 45 ppm / °C or higher, and even more preferably 50 ppm / °C or higher. From the standpoint of package reliability, the CTE2 of the resin composition is preferably 75 ppm / °C or less, more preferably 70 ppm / °C or less, and even more preferably 65 ppm / °C or less.

[0029] In this disclosure, the CTE1 and CTE2 of the cured resin composition are measured by the method described in the examples.

[0030] From the viewpoint of suppressing warping of the substrate, the flexural modulus of the cured resin composition at 25°C is preferably 14 GPa or higher, more preferably 15 GPa or higher, and even more preferably 17 GPa or higher. From the viewpoint of package reliability, the flexural modulus of the cured resin composition at 25°C is preferably 26 GPa or less, more preferably 24 GPa or less, and even more preferably 20 GPa or less.

[0031] From the viewpoint of controlling the warping of the substrate, the flexural modulus of the cured resin composition at 260°C is preferably 0.4 GPa or higher, more preferably 0.7 GPa or higher, and even more preferably 1.0 GPa or higher. From the viewpoint of package reliability, the flexural modulus of the cured resin composition at 260°C is preferably 2.5 GPa or less, more preferably 2.0 GPa or less, and even more preferably 1.5 GPa or less.

[0032] In this disclosure, the flexural modulus of the cured resin composition is measured by the method described in the examples.

[0033] The following describes each component that makes up the resin composition.

[0034] (Epoxy resin)Specifically, the epoxy resins include: novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing a novolac resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing a novolac resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound (benzaldehyde, salicylaldehyde, etc.) under an acidic catalyst; triphenylmethane-type epoxy resins obtained by condensing or co-condensing a triphenylmethane-type phenolic resin (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound (benzaldehyde, salicylaldehyde, etc.) under an acidic catalyst; and novolac resins obtained by co-condensing the above phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst. Copolymer epoxy resins that are epoxidized from; diphenylmethane type epoxy resins that are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; sulfur atom-containing epoxy resins that are diglycidyl ethers of bisphenol S, etc.; epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester type epoxy resins that are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine type epoxy resins in which the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is replaced with a glycidyl group; dicyclopentadiene type epoxy resins that are epoxidized from a copolymer resin of dicyclopentadiene and a phenol compound;Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which have epoxidized olefin bonds within the molecule; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenol resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenol resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenol resins; dicyclopentadiene-modified epoxy resins, which are glycidyl ethers of dicyclopentadiene-modified phenol resins; Examples of epoxy resins include: cyclopentadiene-modified epoxy resins, which are glycidyl ethers of chloropentadiene-modified phenol resins; polycyclic aromatic ring-modified epoxy resins, which are glycidyl ethers of polycyclic aromatic ring-modified phenol resins; naphthalene-type epoxy resins, which are glycidyl ethers of naphthalene ring-containing phenol resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; and aralkyl-type epoxy resins, which are epoxidized aralkyl-type phenol resins such as phenol aralkyl-type phenol resins, biphenyl aralkyl-type phenol resins, and naphthol aralkyl-type phenol resins. Furthermore, epoxidized acrylic resins can also be cited as epoxy resins. These epoxy resins may be used individually or in combination of two or more types.

[0035] From the viewpoint of increasing the glass transition temperature of the cured product, the epoxy resin is preferably a triphenylmethane type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthalene aralkyl type epoxy resin, or a novolac type epoxy resin.

[0036] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

[0037] The epoxy equivalent of the epoxy resin shall be the value measured according to the method conforming to JIS K 7236:2009.

[0038] When the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of ease of handling during the preparation of the resin composition, it is more preferably 50°C to 130°C.

[0039] The melting point or softening point of the epoxy resin shall be the value measured by differential scanning calorimetry (DSC) or by a method (ring-sphere method) in accordance with JIS K 7234:1986.

[0040] The epoxy resin content in the resin composition is preferably 0.5% to 50% by mass, and more preferably 2% to 30% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc.

[0041] (Hardening agent) The resin composition includes a curing agent. The type of curing agent is not particularly limited and can be selected according to the desired properties of the resin composition. Examples of curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymer captan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, and active ester compounds. The curing agent may be used alone or in combination of two or more types.

[0042] Specifically, as phenol curing agents, polyhydric phenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; phenol aralkyl-type phenolic resins, biphenyl aralkyl-type phenolic resins, and Examples include aralkyl phenolic resins such as phthol aralkyl phenolic resins; paraxylylene-modified phenolic resins, metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerizing two or more of these. These phenolic curing agents may be used individually or in combination of two or more.

[0043] From the viewpoint of increasing the glass transition temperature of the cured product, triphenylmethane-type phenolic resins, biphenyl aralkyl-type phenolic resins, naphthalene aralkyl-type phenolic resins, and novolac-type phenolic resins are preferred as curing agents.

[0044] If the curing agent is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of handling during the manufacture of the resin composition, it is more preferably 50°C to 130°C.

[0045] The melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0046] The equivalent ratio of epoxy resin to curing agent, i.e., the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in curing agent / number of functional groups in epoxy resin), is not particularly limited. From the viewpoint of minimizing unreacted components, it is preferable to set it in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is even more preferable to set it in the range of 0.8 to 1.2.

[0047] (Curing accelerator) From the viewpoint of suppressing the reaction between the epoxy resin and the curing accelerator in the resin composition, it is preferable that the curing accelerator does not contain functional groups that react with epoxy groups. The curing accelerator may be used alone or in combination of two or more types.

[0048] In this disclosure, "curing accelerator that does not contain functional groups that react with epoxy groups" means a curing accelerator that does not contain functional groups that have properties that react with epoxy groups, such as primary or secondary amino groups with active hydrogen or phenolic hydroxyl groups. Even tertiary amines that do not possess active hydrogen, such as 1,8-diazabicyclo[5.4.0]undecene-7, do not qualify as "curing accelerators that do not contain functional groups that react with epoxy groups" if they produce a primary amino group through hydrolysis.

[0049] Examples of curing accelerators that do not contain functional groups that react with epoxy groups include phosphorus-containing compounds that do not contain functional groups that react with epoxy groups, and nitrogen-containing compounds that do not contain functional groups that react with epoxy groups.

[0050] Examples of phosphorus atom-containing compounds that do not contain functional groups that react with epoxy groups include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tetra-n-butylphosphonium tetraphenylborate, riphenylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, tetra-n-butylphosphonium bromide, and tetraphenylphosphonium bromide. Examples of nitrogen atom-containing compounds that do not contain functional groups that react with epoxy groups include benzyldimethylamine and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole.

[0051] The amount of curing accelerator contained in the resin composition is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). When the amount of curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the resin component, it tends to cure well in a short time. When the amount of curing accelerator is 30 parts by mass or less per 100 parts by mass of the resin component, it tends to result in a good molded product with a curing speed that is not too fast. From the viewpoint of suppressing the reaction with epoxy resin in the resin composition, it is preferable that all of the curing accelerators contained in the resin composition do not contain functional groups that react with epoxy groups.

[0052] (filling material) The resin composition may contain fillers. The type of filler is not particularly limited. Specifically, examples include inorganic materials such as fused silica, crystalline silica, glass, alumina, talc, clay, and mica. Inorganic fillers with flame retardant properties may also be used. Examples of inorganic fillers with flame retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium-zinc composite hydroxides, and zinc borate.

[0053] Among inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing the coefficient of thermal expansion, and alumina is preferred from the viewpoint of high thermal conductivity. One type of inorganic filler may be used alone, or two or more types may be used in combination. Examples of inorganic filler forms include powder, beads formed from spherical powder, and fibers.

[0054] From the viewpoint of filling performance, the volume-average particle size of the filler contained in the resin composition is preferably 10 μm or less, preferably 1 μm to 8 μm, and more preferably 2 μm to 6 μm.

[0055] From the viewpoint of filling performance, the maximum particle size of the filler contained in the resin composition is preferably 50 μm or less, and more preferably 30 μm or less.

[0056] In this disclosure, the volume-average particle diameter of the filler is the particle diameter (D50) at which the cumulative amount from the smaller diameter side reaches 50% in the volume-based particle size distribution obtained using a laser diffraction / scattering particle size distribution analyzer (e.g., LA920, Horiba, Ltd.). If the filler is contained in the resin composition, the resin components contained in the resin composition may be removed by methods such as thermal decomposition or dissolution before measuring the volume-average particle size.

[0057] The filler content in the resin composition is not particularly limited, but from the viewpoint of fluidity and strength, it is preferably 30% to 90% by volume of the total resin composition, more preferably 35% to 80% by volume, and even more preferably 50% to 80% by volume. When the filler content is 30% or more by volume of the total resin composition, the properties of the cured product, such as the coefficient of thermal expansion, thermal conductivity, and elastic modulus, tend to improve. When the filler content is 90% or less by volume of the total resin composition, the increase in viscosity of the resin composition is suppressed, fluidity improves, and moldability tends to be better.

[0058] In addition to the components described above, the resin composition may also contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, silicone oils, and silicone particles, as exemplified below. The resin composition may also contain, as necessary, various additives well known in the art, in addition to those exemplified below.

[0059] (Coupling agent) The resin composition may contain a coupling agent. From the viewpoint of improving the adhesion between the resin component and the inorganic filler, it is preferable that the resin composition contains a coupling agent. Examples of known coupling agents include silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and disilazane, as well as titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0060] When the resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass, per 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more per 100 parts by mass of the inorganic filler, the adhesion to the frame tends to improve further. When the amount of the coupling agent is 10 parts by mass or less per 100 parts by mass of the inorganic filler, the moldability of the package tends to improve further.

[0061] (Ion exchanger) The resin composition may contain an ion exchanger. It is preferable that the resin composition contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of electronic component devices equipped with the sealed element. The ion exchanger is not particularly limited, and conventionally known ion exchangers can be used. Specifically, examples include hydrotalcite compounds and hydrated oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchanger may be used individually or in combination of two or more. Among these, hydrotalcite represented by the following general formula (A) is preferred.

[0062] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0 < X ≤ 0.5, m is a positive number)

[0063] When the resin composition contains an ion exchanger, its content is not particularly limited as long as it is sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass, based on 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

[0064] (Release agent) The resin composition may contain a release agent from the viewpoint of obtaining good mold release properties with the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, examples include higher fatty acids such as carnauba wax, montanic acid, and stearic acid, metal salts of higher fatty acids, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more.

[0065] When the resin composition contains a release agent, its amount is preferably 0.01 part by mass to 10 parts by mass, and more preferably 0.1 part by mass to 5 parts by mass, based on 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). When the amount of the release agent is 0.01 part by mass or more based on 100 parts by mass of the resin component, mold release properties tend to be sufficiently obtained. When it is 10 parts by mass or less, better adhesion properties tend to be obtained.

[0066] (Flame retardant) The resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specifically, examples include organic or inorganic compounds containing a halogen atom, antimony atom, nitrogen atom, or phosphorus atom, metal hydroxides, etc. The flame retardant may be used alone or in combination of two or more.

[0067] If the resin composition contains a flame retardant, the amount is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

[0068] (Coloring agent) The resin composition may contain a coloring agent. Examples of known coloring agents include carbon black, organic dyes, organic pigments, titanium dioxide, red lead, and red iron oxide. The amount of coloring agent can be appropriately selected depending on the purpose. One coloring agent may be used alone, or two or more may be used in combination.

[0069] (Silicone particles) The resin composition may contain silicone particles. The silicone particles may have a core-shell structure. Examples of silicone particles having a core-shell structure include silicone rubber particles coated with silicone resin (silicone-based core-shell rubber particles). The volume-average particle size of the silicone particles may be in the range of 100 nm to 10 μm.

[0070] (Method for preparing resin composition) The method for preparing the resin composition is not particularly limited. A common method involves thoroughly mixing predetermined amounts of components using a mixer or the like, then melt-kneading them using a mixing roll, extruder, or the like, followed by cooling and pulverization. More specifically, for example, a method involves uniformly stirring and mixing predetermined amounts of the above-mentioned components, then kneading them using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, followed by cooling and pulverization.

[0071] The resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25°C and atmospheric pressure). The shape of the solid resin composition is not particularly limited and can be in the form of powder, granules, or tablets. When the resin composition is in tablet form, the dimensions and mass should be such that they are suitable for the packaging molding conditions, from the viewpoint of ease of handling.

[0072] <Electronic Components and Devices> The electronic component device of this disclosure comprises a support member, an element disposed on the support member, and a cured product of the above-mentioned resin composition disposed around the element.

[0073] Examples of electronic component devices include those in which elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) are mounted on support members such as lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates, and the resulting element section is sealed with a resin composition. More specifically, common resin-encapsulated ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) have a structure in which elements are fixed on a lead frame, the terminal parts of the elements such as bonding pads are connected to the lead parts by wire bonding, bumps, etc., and then sealed using a resin composition by transfer molding, etc.; TCP (Tape Carrier Package) has a structure in which elements connected to a tape carrier by bumps are sealed with a resin composition; and COB (Chip On) has a structure in which elements connected to wiring formed on a support member by wire bonding, flip-chip bonding, solder, etc., are sealed with a resin composition. Examples of board modules, hybrid ICs, multi-chip modules, etc.; BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), etc., have a structure in which elements are mounted on the surface of a support member having terminals for connecting to a wiring board formed on the back surface, the elements and wiring formed on the support member are connected by bump or wire bonding, and then the elements are sealed with a resin composition. Resin compositions can also be suitably used in printed wiring boards.

[0074] The resin composition of this disclosure effectively suppresses substrate warping even when used as a encapsulant for electronic component devices in which the volume ratio of the encapsulant to the overall electronic component device is small (for example, the volume ratio of the encapsulant is 50% or less).

[0075] <Manufacturing method for electronic component devices> A method for manufacturing an electronic component device according to the present disclosure includes the steps of arranging an element on a support member and sealing the element with a resin composition according to the present disclosure.

[0076] The method for carrying out each of the above steps is not particularly limited and can be carried out using general methods. Furthermore, the types of support members and elements used in the manufacture of electronic component devices are not particularly limited and can be those commonly used in the manufacture of electronic component devices.

[0077] Methods for encapsulating the element using the resin composition of this disclosure include low-pressure transfer molding, injection molding, and compression molding.

[0078] <Method for producing resin compositions> The present disclosure is a method for producing a resin composition comprising an epoxy resin, a curing agent, and a curing accelerator. The measurement by the MALDI-TOF / MS method includes calculating the intensity ratio (A / B) of peak A to peak B, where peak A is defined as the reaction product of the epoxy resin and the curing accelerator, and peak B is defined as the internal standard substance.

[0079] According to the above method, a resin composition with excellent toughness of the cured product can be obtained. Specifically, by selecting materials based on the peak intensity ratio value calculated by measurement using the MALDI-TOF / MS method, a resin composition with excellent toughness of the cured product can be obtained. In the above method, the details of the measurement by the MALDI-TOF / MS method are the same as those described above. [Examples]

[0080] The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0081] <Preparation of resin composition> The resin compositions for the examples and comparative examples were prepared by mixing the components shown below in the proportions (parts by mass) shown in Table 1.

[0082] • Epoxy resin 1: Triphenylmethane type epoxy resin with epoxy equivalent weight of 169 g / eq and a softening point of 60°C. • Epoxy resin 2: Biphenyl aralkyl type epoxy resin with epoxy equivalent weight of 272 g / eq and a softening point of 58°C. • Hardener 1: Triphenylmethane-type phenolic resin with a hydroxyl group equivalent of 104 g / eq and a softening point of 85°C. • Hardener 2: Biphenyl aralkyl type phenolic resin with a hydroxyl group equivalent of 203 g / eq and a softening point of 67°C. • Curing accelerator 1: Tetraphenylphosphonium tetraphenylborate • Curing accelerator 2: 2-ethyl-4-methylimidazole • Curing accelerator 3: Additive of tributylphosphine and 1,4-benzoquinone • Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane • Coupling agent 2: 3-glycidoxypropyltrimethoxysilane • Coloring agent: Carbon black • Silicone particles: Silicone-based core-shell rubber particles (volume average particle diameter 100nm~300nm) • Filling material: Silica particles, volume average particle size 6.9 μm • Filling material: Silica particles, volume average particle size 0.5 μm

[0083] (1) Measurement of peak intensity ratio Solutions containing dithranol as a matrix, a resin composition, dibenzo-24-crown-8 as an internal standard, and sodium trifluoroacetate as an ionizing agent were prepared using tetrahydrofuran as the solvent. The concentrations of the components in each solution were set as follows: matrix concentration of 10 mg / mL, resin composition (excluding components insoluble in the solvent) concentration of 10 mg / mL, ionization aid concentration of 10 mg / mL, and internal standard concentration of 0.1 mg / mL. The resin composition solution was subjected to centrifugal separation for 5 minutes (rotation speed 6200 r / min) using a small microcentrifuge (Tommy Industries Co., Ltd., PMC-060t) to settle solvent-insoluble components such as silica particles, and the resulting supernatant was used. The obtained solution was mixed so that the volume ratio of matrix solution, resin composition solution, ionization aid solution, and internal standard solution was 10:1:1:1 to obtain a mixture for peak intensity ratio measurement. The resulting mixture was subjected to mass spectrometry using the MALDI-TOF / MS method. A BRUKER AutoFlex LRF was used as the measurement instrument. The mixture was spread onto a sample plate and dried in a fume hood at room temperature (25°C). The amount of mixture applied per sample was 0.6 μL. The sample plate was placed in the apparatus and vacuumed to a measurable level. Then, measurements were taken at 10 locations, with 50 cumulative measurements per location, for a total of 500 cumulative measurements. The measurements were performed by irradiating the plate with a 337 nm wavelength laser at a laser power (30%) that resulted in a detection intensity (au) of the peak corresponding to the internal standard in the range of 10,000 to 50,000.

[0084] Peak A was defined as the peak corresponding to the reaction product between the epoxy resin and the curing accelerator contained in the resin composition (if there are two or more peaks, the peak with the highest intensity was selected), and Peak B was defined as the peak corresponding to the internal standard substance (the peak detected at m / z value equal to the molecular weight of dibenzo-24-crown-8 plus 23, which is the mass of the sodium ion that becomes the adduct ion). The ratio of the intensity of Peak A to the intensity of Peak B (A / B) was calculated. The results are shown in Table 1.

[0085] (2) Glass transition temperature and CTE A resin composition was injected and molded at a mold temperature of 175°C for 150 seconds to obtain a test specimen measuring 20 mm × 4 mm × 4 mm. The change in the longitudinal dimension (coefficient of linear expansion) of the test specimen was measured using a thermomechanical analyzer (TAS-1000S) manufactured by Rigaku Denki under a heating rate of 5°C / min. The temperature corresponding to the inflection point of the obtained thermal expansion curve was defined as the glass transition temperature Tg (°C). The slope of the line connecting two points on the thermal expansion curve at 50°C and 70°C was defined as the thermal expansion coefficient (CTE1) for temperatures below Tg (glass region), and the slope of the line connecting two points on the thermal expansion curve at 220°C and 230°C was defined as the thermal expansion coefficient (CTE2) for temperatures above Tg (rubber region).

[0086] (3) Static fracture toughness test (K IC test) A resin composition was injected and molded at a mold temperature of 175°C for 150 seconds to obtain a test specimen measuring 80 mm × 10 mm × 4 mm. Next, the obtained test specimen was post-cured at 175°C for 5 hours, and then a 1.75 mm notch and a 0.1 mm crack were made in the center of the test specimen. With the side of the test specimen with the notch and crack facing downwards, a three-point support bending test was performed using TENSILON (manufactured by A&D) with a span (distance between supports) of 64 mm, in accordance with JIS-K-6911. Substitute the maximum load at fracture of the specimen obtained from the measurement (F, in N), the width of the specimen obtained from the actual measurement (W, in m), the thickness (T, in m), the sum of the notch size and crack size (a, in m), and the span (S, in m) into the following formula, and K 1C Calculate the value, and the obtained value is in units of MPam 0.5 It was converted to [this]. The TENSILON head speed was set to 2.0 mm / min, and the test was conducted at 25°C.

[0087]

number

[0088] (4) Dicing crack resistance A sealed substrate was fabricated by compression molding a layer (660 μm thick) of cured resin composition onto a silicon substrate (240 mm × 74 mm × 100 μm). The molding conditions were a molding temperature of 175°C and a molding time of 120 seconds, followed by post-curing in an oven at 175°C for 5 hours. The obtained encapsulated substrate was placed on the stage of a panel dicer (DISCO Corporation, DFD6310) with the cured material layer facing the stage. The encapsulated substrate was divided into region A and region B by a line that equally divided the 74mm side of the substrate, and only region A was adsorbed and fixed to the stage. In this state, the encapsulated substrate was cut along the boundary line between region A and region B. The cutting was performed using a blade with abrasive grit of #400 and a blade thickness of 0.2 mm, with a feed rate of 100 mm / s and a blade rotation speed of 20,000 rpm (revolutions / minute). The cut surface of region B of the cut encapsulated substrate was observed at 200x magnification using a digital microscope (Keyence Corporation, VHX-5000). Samples in which no cracks (chips or fractures) were observed across the entire cut surface were classified as "OK," and samples in which one or more cracks were observed were classified as "NG" to evaluate dicing crack resistance.

[0089] (5) Flexural modulus A resin composition was injected and molded at a mold temperature of 175°C for 150 seconds to obtain a test specimen measuring 80 mm × 10 mm × 4 mm. After post-curing the obtained test specimen at 175°C for 5 hours, a three-point support bending test was performed using TENSILON (manufactured by A&D) with a span (distance between support points) of 64 mm, in accordance with JIS-K-6911. The bending modulus of elasticity E (GPa) was calculated according to the following formula, and the obtained value was converted to the unit: GPa. The head speed of the TENSILON was set to 3.0 mm / min, and measurements were taken at two different temperatures: 25°C and 260°C. In the following equation, P is the load cell value (N), y is the displacement (mm), l is the span = 64 mm, w is the specimen width = 10 mm, and h is the specimen thickness = 4 mm.

[0090]

number

[0091] [Table 1]

[0092] As shown in Table 1, the resin compositions of Examples 1 to 5 (which do not contain functional groups that react with epoxy groups as a curing accelerator), which have a peak intensity ratio of 0.0005 or less, exhibit superior toughness of the cured product compared to the resin compositions of Comparative Examples 1 and 3 (which contain amino groups as functional groups that react with epoxy groups as a curing accelerator), and Comparative Example 2 (which contains phenolic hydroxyl groups as functional groups that react with epoxy groups as a curing accelerator), which have a peak intensity ratio greater than 0.0005.

Claims

1. A method for producing a resin composition containing an epoxy resin, a curing agent, and a curing accelerator, A method for producing a resin composition, comprising calculating the intensity ratio (A / B) of peak A to peak B, where peak A is defined as the reaction product of the epoxy resin and the curing accelerator, and peak B is defined as the internal standard substance, in a measurement by MALDI-TOF / MS method.

2. A method for producing the resin composition according to claim 1, wherein the curing accelerator does not contain a functional group that reacts with an epoxy group.

3. A method for producing the resin composition according to claim 1 or claim 2, wherein the epoxy resin comprises at least one selected from the group consisting of triphenylmethane type epoxy resin, biphenylaralkyl type epoxy resin, naphthalenearalkyl type epoxy resin, and novolac type epoxy resin.

4. A method for producing a resin composition according to any one of claims 1 to 3, wherein the curing agent comprises at least one selected from the group consisting of triphenylmethane-type phenolic resin, biphenylaralkyl-type phenolic resin, naphthalenearalkyl-type phenolic resin, and novolac-type phenolic resin.

5. A method for producing the resin composition according to any one of claims 1 to 4, for use as a sealing material for an electronic component device in which the volume ratio of the sealing material to the entire electronic component device is 50% or less.

6. A method for manufacturing an electronic component device, comprising the steps of: manufacturing a resin composition by the method for manufacturing a resin composition described in any one of Claims 1 to 5; arranging an element on a support member; and sealing the element with the resin composition.

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