TWI577730B - Liquid resin composition for electronic component, method of producing the same, and electronic component device - Google Patents

Description

Liquid resin composition for electronic component, method of manufacturing the same, and electronic component device

The present invention relates to a liquid resin composition for an electronic component, a method for producing the same, and an electronic component device.

In the field of component sealing for electronic components such as a transistor and an integrated circuit (IC), resin sealing has become mainstream in terms of protection performance, productivity, cost, and the like of electronic components. Epoxy resin compositions are widely used. The reason for this is that the epoxy resin has a balance of various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to an insert. For electronic devices such as chip on board (COB), chip on glass (COG), and tape carrier package (TCP), the semiconductor device is widely used. The resin composition is used as a sealing material.

For example, in a display such as a liquid crystal, a packaging method for driving a driving IC in a display is a package form (flip chip connection method) in which a semiconductor element is directly bump-connected to a wiring substrate, and a liquid material for an electronic component is used. Resin composition. The liquid resin composition for an electronic component used in the encapsulation method is known as an underfill material.

In the above-described semiconductor package method using a flip chip connection method, the underfill material is filled between the wiring substrate and the semiconductor element for sealing to maintain insulation between the bumps serving as the connection terminals and to maintain mechanical strength. In the space, a semiconductor device is formed. Therefore, the underfill The following conditions must be met: (1) a liquid of low viscosity at normal temperature; (2) in order to avoid bubbles (voids) during thermal hardening of the underfill after filling, and without solvent; (3) In order to avoid the increase of viscosity and the decrease of permeability, without solid components such as fillers, or to reduce the content thereof as much as possible; (4) in the case of containing solid components, properly formulated, that is, to maintain solids in the underfill The uniform dispersibility of the components is controlled without affecting the particle size distribution and the filling amount of viscosity, fluidity, permeability, and the like.

In the wiring board and the semiconductor device, the interval between the wirings tends to be narrow (fine pitch), and in the semiconductor device of the most advanced flip chip package type, the interval between the wirings is not less than 30 μm. Further, the ion migration phenomenon is a problem in that the ion mobility phenomenon is caused by a high voltage applied to the finely pitched wiring, which impairs the insulation reliability of the cured product of the liquid resin composition for an electronic component. One. In particular, under high temperature and high humidity, deterioration of the resin and the wiring metal is promoted, so that ion migration is likely to occur, and the risk of insulation failure in the semiconductor device tends to be further improved.

In order to avoid this insulation failure, measures for suppressing ion migration have been employed for the resin composition used in electronic components. For example, the following resin composition is known as a resin composition for use in a sealing material, an adhesive, or a prepreg, and a resin composition in which an inorganic ion exchanger is used as a metal ion scavenger (see, for example, Patent Document 1 to Patent Literature) 4); a resin composition containing benzotriazine, benzotriazole or the isocyanuric acid addition product (for example, refer to Patent Document 5 to Patent Document 10); and a borate containing a curing accelerator Resin composition of the compound (For example, refer to Patent Document 11); a resin composition having a cyclic acid anhydride having an acid anhydride equivalent of 200 or more (see, for example, Patent Document 12); and a resin composition containing an antioxidant (see, for example, Patent Document 13 to Patent Document 15) )Wait.

On the other hand, a method is known in which a particle having a core-shell structure is added to a resin composition to improve physical or mechanical properties, that is, to alleviate a mismatch due to a thermal expansion coefficient of a cured product of a resin composition and an adherend. The stress suppresses peeling and cracking, imparts flexibility, improves fracture toughness, and improves impact resistance (for example, see Patent Document 16).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-158492

[Patent Document 2] Japanese Patent Laid-Open No. Hei 9-314758

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-183470

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-63549

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2001-6769

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2001-203462

[Patent Document 7] Japanese Patent No. 3881286

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2005-72275

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2005-333085

[Patent Document 10] Japanese Patent No. 3634422

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2008-7577

[Patent Document 12] Japanese Patent No. 4775374

[Patent Document 13] Japanese Patent Laid-Open No. Hei 3-39320

[Patent Document 14] Japanese Patent Laid-Open No. Hei 10-279779

[Patent Document 15] Japanese Patent Laid-Open Publication No. 2010-254951

[Patent Document 16] Japanese Patent Laid-Open Publication No. 2010-138384

However, the fine pitch of the connection terminals of the semiconductor element and the fine wiring of the wiring board are progressing more, and the liquid resin composition for electronic components is required to achieve the following performance at an extremely high level: the filling is extremely narrow without a gap. The performance of the gap between the connection terminals or between the semiconductor element and the substrate, and the durability of the insulation. Accordingly, in the case of using only the above-described known countermeasures, it is difficult to sufficiently prevent insulation failure due to ion migration.

Further, the solid particles having particles having a core-shell structure are difficult to be applied to a liquid resin composition for an electronic component which requires the above properties. The reason for this is that the addition of solid particles may hinder the low viscosity of the liquid resin composition for electronic components, impair fluidity or filling performance, and may cause fatal insulation failure due to voids caused by poor filling; When a filter having a small pore size (for example, 10 μm) is filtered, pores of the filter are clogged, and it is difficult to selectively remove minute foreign matter or the like.

As described above, it is required to realize a liquid resin composition for an electronic component having the following properties: the performance of filling a narrow gap between the connection terminals or the gap between the semiconductor element and the substrate without gaps, and excellent insulation durability.

In view of the above, the present invention provides a liquid resin composition for an electronic component which is excellent in both the filling property and the ion mobility resistance after curing, a method for producing the same, and an electronic component device.

In order to solve the above problems, the inventors of the present invention have made an effort to achieve the above object, and have found that the liquid resin composition for an electronic component can be achieved by the following liquid resin composition for an electronic component. A cyclic anhydride containing epoxy resin, a liquid at 25 ° C, and a particle having a core-shell structure, and a viscosity at 25 ° C using an EMD type rotational viscometer is 1.2 Pa. s below.

The present invention relates to the following <1> to <14>.

<1> A liquid resin composition for an electronic component comprising an epoxy resin, a cyclic acid anhydride which is a liquid at 25 ° C, and a particle having a core-shell structure, and is measured at 25 ° C using an EMD type rotational viscometer. The viscosity is 1.2 Pa. s below.

<2> The liquid resin composition for an electronic component according to <1>, which is obtained by using a preliminary mixture obtained by preliminary mixing and mixing the particles having the core-shell structure in an epoxy resin.

<3> The liquid resin composition for electronic components according to <2>, wherein the amount of free chlorine ions contained in the preliminary mixture is 100 ppm or less.

The liquid resin composition for an electronic component according to any one of the above-mentioned, wherein the core of the core-shell structure contains a polyoxyalkylene compound.

The liquid resin composition for an electronic component according to any one of the above-mentioned, wherein the content of the particle having the core-shell structure is the total of the liquid resin composition for the electronic component. 1% by mass or more and 10% by mass or less.

The liquid resin composition for an electronic component according to any one of the above-mentioned, wherein the cyclic acid anhydride which is liquid at normal temperature has an acid anhydride equivalent of 200 or more.

The liquid resin composition for electronic components of any one of <1> to <6> which further contains an antioxidant.

The liquid resin composition for an electronic component according to any one of <1> to <7> which further contains an ion trapping agent.

The liquid resin composition for electronic components of any one of <1> to <8> further contains a hardening accelerator.

The liquid resin composition for an electronic component according to any one of the above aspects, which further contains an inorganic filler, and the content of the inorganic filler is a liquid resin for the electronic component. The composition is 10% by mass or less or less in total.

The liquid resin composition for an electronic component according to any one of the above-mentioned <1>, which is used in an electronic component device having a structure in which an electronic component is flip-chip bonded to a wiring board.

<12> The liquid resin composition for an electronic component according to <11>, which is used in the electronic component device in which the wiring substrate is a substrate.

<13> An electronic component device comprising: a support member, an electronic component disposed on the support member, and any one of <1> to <12> that seals or follows the support member and the electronic member. A cured product of a liquid resin composition for an electronic component.

<14> A method for producing a liquid resin composition for an electronic component, It comprises: mixing a particle having a core-shell structure with a preliminary mixture of a first epoxy resin, a second epoxy resin, and a cyclic anhydride which is a liquid at 25 ° C.

<15> The method for producing a liquid resin composition for an electronic component according to the above aspect, wherein the amount of free chlorine ions contained in the preliminary mixture is 100 ppm or less.

According to the present invention, it is possible to provide a liquid resin composition for an electronic component which is excellent in both the filling property and the ion mobility resistance after curing, a method for producing the same, and an electronic component device.

In this specification, the term "step" means not only an independent step, but even in the case where it cannot be clearly distinguished from other steps, it is included in the term as long as the intended purpose of the step can be achieved. In addition, the numerical range represented by "~" in this specification shows the range which has the numerical value of the before and after "~" as a minimum and maximum. Further, in the present specification, when a plurality of substances corresponding to the respective components are present in the composition in the amount of each component in the composition, unless otherwise specified, the plurality of substances present in the composition are referred to. Total amount. In the present specification, the term "liquid at normal temperature" means a state in which fluidity is exhibited at 25 °C. Further, in the present specification, the term "liquid" means fluidity and viscosity, and the viscosity as a measure of viscosity is 0.0001 Pa at 25 ° C. s~10 Pa. s substance.

In the present specification, the viscosity is defined as a value obtained by multiplying the measured value when the EMD type rotational viscometer is rotated at 25 ° C for 1 minute at a predetermined sub-fraction (rpm, 1/60 ^-1 ). The value obtained by the conversion factor. The above-mentioned measured value was obtained by using an EMD type rotational viscometer equipped with a conical rotor having a cone angle of 3° and a conical radius of 14 mm for a liquid maintained at 25 ± 1 °C. The sub-division and the conversion factor are different depending on the viscosity of the liquid to be measured. Specifically, the viscosity of the liquid to be measured is estimated in advance, and the sub-perimeter and the conversion factor are determined based on the estimated value.

In the present specification, the estimated value of the viscosity of the liquid to be measured is 0 Pa. s~1.25 Pa. In the case of s, the next minute is set to 100 rpm, the conversion factor is set to 0.0125, and the estimated value of viscosity is 1.25 Pa. s~2.5 Pa. In the case of s, the next minute is set to 50 rpm, the conversion factor is set to 0.025, and the estimated value of viscosity is 2.5 Pa. s~6.25 Pa. In the case of s, the next minute is set to 20 rpm, the conversion factor is set to 0.0625, and the estimated value for viscosity is 6.25 Pa. s~12.5 Pa. In the case of s, the next minute is set to 10 rpm and the conversion factor is set to 0.125.

<Liquid resin composition for electronic components>

The liquid resin composition for an electronic component of the present invention contains an epoxy resin, a cyclic acid anhydride which is liquid at 25 ° C, and a particle having a core-shell structure, and the viscosity at 25 ° C measured by an EMD type rotational viscometer is 1.2. Pa. s below. The liquid resin composition for an electronic component is excellent in both the filling property of the liquid resin composition and the ion mobility resistance after curing.

That is, the present invention provides a softening property obtained by using a cyclic acid anhydride which is a liquid at 25 ° C in combination with particles having a core-shell structure, and a viscosity suitable for filling a narrow gap, thereby achieving filling. Sexual and hardened A liquid resin composition for an electronic component excellent in ion mobility resistance.

Hereinafter, the physical properties and components of the liquid resin composition for an electronic component will be described.

[viscosity]

The viscosity of the liquid resin composition for an electronic component using an EMD type rotational viscometer at 25 ° C is 1.2 Pa. s below. If the above viscosity exceeds 1.2 Pa. In other words, it is not possible to ensure the fluidity and permeability corresponding to the recent miniaturization of the electronic component, the fine pitch of the connection terminals of the semiconductor element, and the fine wiring of the wiring substrate. The above viscosity is preferably 0.8 Pa. s below, and then preferably 0.7 Pa. s below. The lower limit of the above viscosity is not particularly limited, and from the viewpoint of encapsulation, it is preferably 0.01 Pa. s above, and then preferably 0.1 Pa. s above.

The viscosity can be appropriately adjusted by controlling the type or content of each of the above-exemplified components depending on the type of the electronic component and the electronic component device to be sealed or attached.

[Epoxy Resin (A)]

The liquid resin composition for an electronic component contains an epoxy resin (A). The epoxy resin (A) is preferably an epoxy resin having two or more epoxy groups in one molecule, and an epoxy resin generally used in a liquid resin composition for an electronic component can be used without particular limitation.

The epoxy resin may be a glycidyl ether type epoxy resin obtained by a reaction with epichlorohydrin such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalenediol or hydrogenated bisphenol A. a novolac novolac type epoxy resin represented by a phenolic aldehyde which is obtained by condensing or co-condensing a phenol compound with an aldehyde compound; a novolac type epoxy resin obtained by epoxidizing a lacquer resin; a glycidyl ester type epoxy resin obtained by a reaction of a polybasic acid such as phthalic acid or a dimer acid with epichlorohydrin; and a diamine group a glycidylamine type epoxy resin obtained by reacting a polyamine such as diphenylmethane or isocyanuric acid with epichlorohydrin; a linear aliphatic epoxy resin obtained by oxidizing an olefin bond by a peracid such as peracetic acid; an alicyclic ring; Family epoxy resin and the like. These epoxy resins may be used alone or in combination of two or more.

In the epoxy resin, as long as the liquid resin composition for an electronic component is a liquid at normal temperature, the epoxy resin itself may be either a solid or a liquid at normal temperature, or may be used in combination. In view of the low viscosity of the liquid resin composition for an electronic component, it is preferably an epoxy resin which is liquid at normal temperature, and more preferably shrinks from the viewpoint of reactivity with a cyclic acid anhydride. The glyceryl ether type liquid epoxy resin is preferably a bisphenol type liquid epoxy resin obtained by a reaction with epichlorohydrin such as bisphenol A, bisphenol F, bisphenol AD or bisphenol S.

Further, in order to further improve ion migration resistance, it is preferred that the epoxy resins have a low content of ionic impurities which are a cause of ion migration. As the ionic impurities, free Na ions or free Cl ions are known as factors that promote corrosion or ion migration of metals. Therefore, it is preferred that the content of the free Na ions and the free Cl ions contained in the epoxy resin (A) is small. It is particularly preferable that the content of free Cl ions is as small as possible. In practical use, the effect of improving the ion mobility resistance of the liquid resin composition for an electronic component can be sufficiently exhibited by suppressing the content of the free Cl ions to 500 ppm or less, and is preferably 400 ppm or less, more preferably 300 ppm or less.

In the liquid resin composition for an electronic component, the content of the epoxy resin is preferably from 10% by mass to 100% by mass, and more preferably from 20% by mass to 90%, in terms of the fluidity and the properties of the cured material. The mass%, and more preferably 30% by mass to 80% by mass.

[cyclic anhydride (B) which is liquid at normal temperature]

The liquid resin composition for an electronic component contains a cyclic acid anhydride (B) which is liquid at normal temperature. The cyclic acid anhydride (B) which is liquid at normal temperature functions, for example, as a curing agent for the epoxy resin (A). Moreover, the fluidity of the liquid resin composition for electronic components is improved by being liquid at normal temperature. Further, by combining a cyclic acid anhydride which is liquid at normal temperature with particles having a core-shell structure, it is possible to suppress the elution of the metal and improve the adhesion, and to improve the ion mobility resistance of the fine-pitched electronic component device. .

The term "cyclic anhydride" means that two carbon atoms C of "-CO-O-CO-" as represented by phthalic anhydride form a chemical bond with two other carbon atoms, and the above two carbon atoms are directly or It is a ring by one or more atomic bonds.

From the viewpoint of fluidity, the above cyclic anhydride which is liquid at normal temperature is preferably a viscosity at 25 ° C using an EMD type rotational viscometer of 10 Pa. Below s, more preferably 5Pa. s below, and then preferably 1Pa. s below. From the viewpoint of chemical stability and safety of the cyclic acid anhydride, the lower limit of the viscosity at 25 ° C using the EMD type rotational viscometer is preferably 0.001 Pa. Above s, more preferably 0.005Pa. s above, and then preferably 0.01Pa. s above.

The above anhydride equivalent of the cyclic acid anhydride (B) which is liquid at normal temperature Preferably, it is 160 or more, and more preferably 200 or more. The "anhydride equivalent" is represented by (molecular weight of an acid anhydride) / (the number of acid anhydride groups in an acid anhydride molecule). By setting the acid anhydride equivalent to 160 or more, the ester bond in the cured product is reduced, so that the influence of hydrolysis under high temperature and high humidity can be minimized, and moisture resistance, particularly ion permeation resistance, can be improved. Further, since the water absorption rate is also reduced by the reduction of the ester bond, the Cl plasma impurity amount eluted in the moisture-absorbing water can be reduced, and the ion migration resistance can be further improved. This phenomenon further functions more effectively by using a cyclic acid anhydride having an acid anhydride equivalent of 200 or more. Further, by using a cyclic acid anhydride having a liquidity at room temperature and having an acid anhydride equivalent of 200 or more in combination with particles having a core-shell structure, a synergistic effect of suppressing elution of metal and improving adhesion can be obtained, and finely pitched electrons can be obtained. The component device also ensures sufficient migration resistance.

As the cyclic acid anhydride having an acid anhydride equivalent of 160 or more and a liquid at a normal temperature, for example, YH306, which is a commercially available product having an acid anhydride equivalent of 234, can be obtained from Mitsubishi Chemical Corporation.

The structure of the cyclic acid anhydride (B) which is liquid at normal temperature is not particularly limited, and from the viewpoint of ion mobility resistance, it is preferred that the molecule does not contain a halogen atom such as chlorine or bromine or an ester bond.

The cyclic acid anhydride (B) which is liquid at normal temperature may, for example, be phthalic anhydride, maleic anhydride, methylhimic anhydride, biscycloheptylene anhydride, succinic anhydride, or the like. Hydrogen phthalic anhydride, hexahydrophthalic anhydride, chloro-bromic anhydride, methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic acid Formaldehyde anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, benzophenone Tetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, hydrogenated methylic acid anhydride, and more obtained by the Diels-Alder reaction of maleic anhydride and diene compound Alkyl alkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, and the like. Among the above cyclic acid anhydrides, trialkyltetrahydrophthalic anhydride and dodecenylsuccinic anhydride are preferred from the viewpoint of improving ion mobility resistance.

The liquid resin composition for an electronic component may contain a curing agent other than the cyclic acid anhydride (B) which is liquid at normal temperature. As the above hardener, those which are generally used as a hardener for an epoxy resin can be used. For example, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylamine Propylamine, isophoronediamine, 1,3-diaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornene diamine, 1,2-diaminocyclohexane , Laromin ("Laromin" is a registered trademark), diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylphosphonium, polyoxypropylenediamine, polyoxygen Amine compounds such as propylene triamine, polycyclohexyl polyamine mixture, N-aminoethylpiperazine, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl) 2-ethyl-4-methylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))ethyl-s-triazine, 2-phenylimidazoline, 2, An imidazole compound such as 3-dihydro-1H-pyrrolo(1,2-a)benzimidazole, a tertiary amine, 1,8-diazabicyclo[5.4.0]undec-7-ene (1, 8-Diazabicyclo [5.4.0]undec-7-ene, DBU), dicyandiamide, organic acid dihydrazine, N,N-dimethylurea derivative, and the like. Among them, from the viewpoint of low viscosity, an amine compound is preferred.

The liquid resin composition for the electronic component described above is contained in a liquid at normal temperature In the case of a curing agent other than the cyclic acid anhydride (B), the content of the cyclic acid anhydride (B) which is liquid at normal temperature is preferably 30% by mass or more based on the total amount of the curing agent. More preferably, it is 40% by mass or more, and further preferably 60% by mass or more.

The equivalent ratio of the epoxy resin (A) to all the hardeners contained in the cyclic acid anhydride (B) which is liquid at normal temperature is not particularly limited, and is preferably relative to the epoxy in order to suppress the respective unreacted components. The resin (A) is set to a range of from 0.6 equivalents to 1.6 equivalents, more preferably from 0.7 equivalents to 1.4 equivalents, still more preferably from 0.8 equivalents to 1.2 equivalents. By setting the range of 0.6 equivalent to 1.6 equivalent, the hardening reaction proceeds sufficiently, and the reliability accompanying the hardening failure can be avoided. Here, the equivalent means the reaction equivalent, for example, the acid anhydride equivalent of the acid anhydride is calculated by the amount of one anhydride group reacted with respect to one epoxy group, and the equivalent weight of the phenol resin is 1 with respect to 1 epoxy group. The amount of the phenolic hydroxyl group is calculated by calculating the amount of the amine equivalent by the amount of one active hydrogen reacted with respect to one epoxy group.

[Particles with core-shell structure (C)]

The liquid resin composition for an electronic component of the present invention contains particles (C) having a core-shell structure. The particles (C) having the core-shell structure described above are not particularly limited, and those known to use can be used. The "particle having a core-shell structure" means a particle having a structure in which a part of the surface or the entire surface of the particle which becomes a core is covered by the film. By containing the particles (C) having a core-shell structure, flexibility is imparted to the liquid resin composition for an electronic component, and the force is increased and the elution of the metal is suppressed, whereby the migration resistance can be improved.

The above-mentioned particle having a core-shell structure from the viewpoint of uniform dispersibility The shape of (C) is preferably approximately spherical. The average particle diameter of the primary particles of the core-shell-structured particles (C) is preferably 5 nm or more and 1000 nm or less, more preferably 10 nm or more and 800 nm or less, and further preferably 100 nm or more and 500 nm or less. By setting the average particle diameter of the primary particles to 5 nm or more, aggregation of the particles can be prevented, and the dispersibility as the primary particles can be further improved. In addition, by setting the primary particle average particle diameter to 1000 nm or less, the liquid resin composition for an electronic component can be filtered by a filter having a small pore diameter, and the impurities which are the cause of lowering the insulation reliability are not hindered from being removed. A liquid resin composition for a high-purity electronic component can be obtained. In addition, in the present specification, the "average particle diameter" means a cumulative distribution expressed by the accumulation of the number of degrees by using a laser diffraction/scattering method and setting the particle diameter to the level and the volume to the degree. The cumulative distribution reaches a particle size of 50%.

The core material which becomes the core of the above-mentioned core-shell structured particle (C) may, for example, be polybutadiene; polyisoprene; polychloroprene; polyoxyalkylene; butyl acrylate, acrylic acid-2- A rubber elastomer or the like of a copolymer of ethylhexyl ester or lauryl methacrylate. Among them, from the viewpoint of high heat resistance, low water absorption, and adhesion retention with an electronic member in a high-temperature and high-humidity environment, a core material containing polyoxyalkylene as a component is preferable.

As the shell layer which is the outer layer of the above-described core-shell structured particles (C), those containing acrylate, aromatic vinyl compound, acrylonitrile compound, acrylamide derivative, maleimide derivative, etc. may be used. The polymer of the component, etc. The uniform dispersibility in the epoxy resin is good, and the selectivity of the micro foreign matter is achieved by filtering using a filter having a small pore size. From the viewpoint of removal, a shell layer composed of an acrylate is preferable.

As a particle having a core-shell structure containing a core material containing a polyoxyalkylene as a component and a shell layer containing an acrylate as a component, for example, a brand name of Wacker Chemie Co., Ltd., which is a commercially available product, can be used. GENIOPERL ("GENIOPERL" is a registered trademark), and Rohm & Haas Company's trade name Pallalodid ("PARALOID") Registered trademark), trade name F351 manufactured by GANZ Chemical Co., Ltd., etc.

From the viewpoint of exhibiting an appropriate elastic modulus and adhesion as the underfill material, the mass ratio (core/shell) of the core material to the shell layer of the core-shell-structured particle (C) is preferably 1/. 150~1/0.01, more preferably 1/10~1/0.1.

The radius ratio (core radius/shell thickness) of the core material and the shell layer of the particle (C) having the core-shell structure is preferably from the viewpoint of exhibiting an appropriate elastic modulus and adhesion as the underfill material. 1.9/8.1~9.97/0.03, more preferably 4.5/5.5~9.7/0.3.

The particle (C) itself having a core-shell structure may be mixed in the liquid resin composition for an electronic component, and the preliminary mixture (C1) may be mixed, and the preliminary mixture (C1) is a particle having a core-shell structure (C). It is obtained by dispersing in an organic solvent such as an alcohol or a ketone, an epoxy resin, or another liquid organic compound by preliminary mixing.

(preparation mixture C1)

In order to improve ion migration resistance, the above-mentioned particles having a core-shell structure (C) is preferably uniformly dispersed in the liquid resin composition for an electronic component, and the particles (C) having a core-shell structure are stably and uniformly dispersed in the state of primary particles. In order to obtain such a dispersed state, it is effective to mix the preliminary mixture (C1) into the liquid resin composition for an electronic component, and the preliminary mixture (C1) is such that the particles (C) having a core-shell structure are previously prepared in an organic solvent. It is obtained by mixing and dispersing an epoxy resin or another liquid organic compound.

The preliminary mixture (C1) can be produced, for example, by a dispersion treatment at a temperature of 25 ° C to 80 ° C for 30 minutes using a high pressure wet micronization apparatus. For the high-pressure wet micronization apparatus, for example, Nanomizer NM-2000AR ("Nanomizer") manufactured by Yoshida Machinery Co., Ltd. can be used as a registered trademark. The content of the core-shell-containing particles (C) in the preliminary mixture (C1) is preferably from 1% by mass to 70% by mass, from the viewpoint of the adhesion durability and ion migration resistance of the adherend. Preferably, it is 5 mass% to 60 mass%.

In particular, the preliminary mixture (C1) is a mixture of particles (C) having a core-shell structure and an epoxy resin (A1), thereby improving compatibility with the epoxy resin (A), or epoxy resin at room temperature. The reactivity of the liquid cyclic acid anhydride (B) is such that the particles (C) having a core-shell structure are uniformly dispersed in the cured product of the liquid resin composition for an electronic component, and the liquid resin composition for an electronic component can be further improved. Resistance to ion mobility. Further, the efficiency or mass productivity of the preparation step can be improved.

The epoxy resin (A1) contained in the preliminary mixture (C1) and the epoxy resin (A) contained in the liquid resin composition for electronic components may be the same. The compounds may also be different compounds. By formulating a cyclic acid anhydride (B) which is liquid at normal temperature in accordance with the epoxy equivalent of the liquid resin composition in the preliminary mixture and the epoxy resin (A), a liquid resin composition for an electronic component can be obtained. Things.

The epoxy resin (A1) in which the particles (C) having a core-shell structure are dispersed is exemplified by the epoxy resin exemplified in the above epoxy resin (A). These epoxy resins may be used alone or in combination of two or more, and are preferably those having a low viscosity at normal temperature.

Preparation of a liquid having a core-shell structure (C) stably dispersed in the epoxy resin (A1) in a state of primary particles, and a liquid resin composition for an electronic component capable of maintaining a sufficiently low viscosity Kane Ace MX (MX-136: particles having a core-shell structure of 25% by mass) manufactured by Kaneka Co., Ltd., which is a commercial product, is available as a mixture (C1). , MX-960: Particles having a core-shell structure of 25% by mass or the like ("Kane Ace" is a registered trademark)).

From the viewpoint of further improving the ion mobility resistance of the liquid resin composition for an electronic component, the free Na contained in the mixture (C1) of the core-shell structured particle (C) and the epoxy resin (A1) The content of ions and free Cl ions, particularly the content of free Cl ions, is preferably as low as possible. In the practical aspect, the effect of improving the ion mobility resistance of the liquid resin composition for an electronic component can be further improved by reducing the content of the free Cl ions to 100 ppm or less, more preferably 80 ppm or less, and still more preferably 50 ppm or less. .

The content of the particles (C) having a core-shell structure is preferably 1.0% by mass or more and 10.0% by mass or less, more preferably 3.0% by mass or more and 9.0% by mass or less, based on the liquid resin composition for an electronic component. By setting the content ratio to 1.0% by mass or more, the effect of improving ion mobility can be further exhibited. By setting the content ratio to 10.0% by mass or less, the fluidity of the liquid resin composition and the impregnation property in the narrow gap of the electronic component can be ensured to be practically sufficient.

The mass ratio of the above-described core-shell structured particles (C) to the above-mentioned cyclic acid anhydride (B) which is liquid at normal temperature from the viewpoint of improving the durability and migration resistance ((C)/(B)) It is preferably 1/0.5 to 1/50, more preferably 1/1 to 1/10, and further preferably 1/2 to 1/5.

[Antioxidant (D)]

The liquid resin composition for an electronic component preferably further contains an antioxidant (D). By containing the above-mentioned antioxidant (D), the ion migration resistance can be further improved, and deterioration of the cured product can be more reliably suppressed. The antioxidant is not particularly limited, and those previously known can be used. Examples of the antioxidant include a phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenolic hydroxyl group, a dicyclohexylamine, an organic sulfur compound-based antioxidant, an amine compound-based antioxidant, and a phosphorus compound-based antioxidant.

The phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenolic hydroxyl group may, for example, be 2,6-di-tert-butyl-4-methylphenol or n-octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis-(4-methyl-6-tert-butylphenol), 3,9-double [ 2-[3-(3-Tertibutyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl]-2,4,8,10-tetra Oxygen Spiro[5.5]undecane, 4,4'-butylenebis-(6-t-butyl-3-methylphenol), 4,4'-thiobis(6-t-butyl-3- Methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,2-thio-di-extension ethyl bis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis[3-(3,5-di-t-butyl- 4-hydroxyphenyl)propanamine], isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2 , 4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 4,6-bis(dodecylthiomethyl)-o-cresol, double (3,5 -di-t-butyl-4-hydroxybenzylphosphonic acid ethyl)calcium, 2,4-1-bis[(octylthio)methyl]-o-cresol, 1,6-hexanediol-double [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) Propyl]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphopene heptane (6-[3-(3-t) -butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepin), 2-tert-butyl-6 -(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate 2-[1-(2-hydroxy-3,5-di-p-pentylphenyl)ethyl]-4,6-di-third-pentyl phenyl acrylate, 2,2'-methylene Bis-(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-tris(2-methyl-4-hydroxyl) -5-t-butylphenyl)butane, triethylene glycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], three (3, 5-di-t-butyl-4-hydroxybenzyl)isocyanurate, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]- Phosphate, 2,5,7,8-tetramethyl-2-(4',8',12'-trimethyltridecyl)benzodihydrofuran-6-ol, 2,4 - bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and the like.

Dicyclohexylamine is commercially available as a commercial product, D-CHA-T, etc., manufactured by Shin-Nippon Chemical Co., Ltd., and derivatives thereof include dicyclohexyl ammonium nitrite and N, N-bis (3-A). Alkyl-cyclohexylamine, N,N-bis(2-methoxy-cyclohexyl)amine, N,N-bis(4-bromo-cyclohexyl)amine, and the like.

Examples of the organic sulfur compound-based antioxidant include dilaurin 3,3'-thiodipropionate, 3,3'-thiodipropionate dimyristyl ester, and 3,3'-thiodipropionic acid di-hard. Lipid ester, pentaerythritol tetrakis(3-lauryl thiopropionate), di-tridecyl 3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thio Bis(6-tert-butyl-3-methylphenol), 2,2-thio-di-extension ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propane Acid ester], 4,6-bis(dodecylthiomethyl)-o-cresol, 2,4-1-bis[(octylthio)methyl]-o-cresol, 2,4-dual- (n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and the like.

Examples of the amine compound-based antioxidant include N,N'-diallyl-p-phenylenediamine, N,N'-di-t-butyl-p-phenylenediamine, octylated diphenylamine, 2,4- Bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and the like.

Examples of the phosphorus compound-based antioxidant include tridecyl phenyl phosphite, triphenyl phosphite, calcium bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate), and phosphorous acid tri (2,4-di-t-butylphenyl) ester, 2-[[2,4,8,10-tetrakis(1,1-dimethylether)dibenzo[d,f][1, 3,2]dioxaphosphocycloheptan-6-yl]oxy]-N,N-bis[2-{[2,4,8,10-tetra(1,1-dimethylethyl)di Benzo[d,f][1,3,2]dioxaphosphocycloheptan-6-yl]oxy}-ethyl]ethylamine, 6-[3-(3-tert-butyl-4- Hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphane heptane, Diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate and the like.

These antioxidants may be used alone or in combination of two or more. Further, among the above-mentioned antioxidants, a compound containing one or more of a phenolic hydroxyl group and a phosphorus atom, a sulfur atom or an amine in the same molecule is also included in the group of the phenol compound-based antioxidant and other antioxidant groups. Repeated records in the group.

Among the above antioxidants, in particular, from the viewpoint of improving ion migration resistance, it is more preferably a group selected from a phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenolic hydroxyl group and dicyclohexylamine. At least one of the groups. For a phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenolic hydroxyl group, it is generally considered that since the ortho-group alkyl group is an electron-donating group, the electron concentration is unpaired in the oxygen atom of the phenolic hydroxyl group. The electron site is increased, and the antioxidant is disposed on the surface of the anode metal to suppress oxidative degradation of the metal, and the ion mobility resistance is further improved. Further, in the case of dicyclohexylamine, it is considered that the electron concentration is increased in the unpaired electron sites of the nitrogen atom of the amine, and the antioxidant is disposed on the surface of the anode metal to suppress oxidative degradation of the metal, and the ion mobility resistance is further improved.

Further, as the phenol compound-based antioxidant having at least one alkyl group in the ortho position to the phenolic hydroxyl group, a compound having a solid or powder property is generally known. In order to prevent the viscosity, permeability, and fluidity of the liquid resin composition for an electronic component from being lowered, it is preferable that the epoxy resin (A) which is a component of the liquid resin composition for an electronic component is liquid for the electronic component. When the resin composition is cured, it has a sufficient degree of resistance to ion mobility and is dissolved. Specifically, a conventional epoxy resin, for example, a known bisphenol F-type epoxy resin which is also used as an epoxy resin which is liquid at normal temperature in the present invention The amount of saturated dissolution is preferably 5% by mass or more, and more preferably 10% by mass or more. When the amount of the saturated solution is 5% by mass or more, the phenol compound-based antioxidant is dissolved in the epoxy resin, and the phenol compound-based antioxidant can be uniformly dispersed in the liquid resin composition for an electronic component, and is resistant to ions. The tendency to further improve mobility. Here, since the application of the liquid resin composition for an electronic component is usually performed at room temperature, the above-mentioned saturated dissolution amount is room temperature (25 ° C) in consideration of the stability of the liquid composition for an electronic component. value.

In the phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenolic hydroxyl group, the phenol compound-based antioxidant having a saturated solubility of 5% by mass or more may, for example, be 4,4'-butylene -(6-tert-butyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 3, 9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl]-2,4,8 , 10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate] and the like.

Further, among the phenol compound-based antioxidants which are dissolved in the epoxy resin which is liquid at normal temperature, the phenol compound-based antioxidant having one methyl group in the ortho position of the phenol core has a greater effect of improving ion mobility resistance. Propensity. It is generally believed that the reason is that the methyl group has a small steric hindrance and is an electron donating group, so that the unpaired electrons of the phenolic hydroxyl group of the antioxidant are more easily disposed on the surface of the anode metal. Such a phenol compound-based antioxidant may, for example, be 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1- Dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methyl Phenyl) propionate] and the like.

Further, the property of dicyclohexylamine at normal temperature is a liquid. Therefore, compared with the solid or powder antioxidant, there is an advantage of uniform dispersion without impairing the viscosity, permeability, and fluidity of the liquid resin composition for an electronic component.

When the liquid resin composition for an electronic component contains an antioxidant, the content of the ion-resistant resin is preferably from 0.005 mass% to 0.5 mass%, more preferably from 0.01 mass% to 0.1%. quality%.

When the liquid resin composition for an electronic component contains a phenol compound-based antioxidant having at least one alkyl group in the ortho position of the phenolic hydroxyl group, the content of the epoxy resin (A) is preferably 0.1. The mass % to 10% by mass, more preferably 0.5% by mass to 5.0% by mass. By setting the content ratio to 0.1% by mass or more, the effect of suppressing the ion transport can be further exerted, and by setting it to 10% by mass or less, it is possible to more reliably suppress the decrease in fluidity of the liquid resin composition for an electronic component. Further, the saturated dissolved amount X of the phenol compound-based antioxidant having at least one alkyl group in the ortho position to the phenolic hydroxyl group is 5% by mass < X mass% < 10% by mass based on the epoxy resin (A). In the case, the content ratio is preferably from 0.1% by mass to X% by mass, more preferably from 0.5% by mass to 5.0% by mass.

When the liquid resin composition for an electronic component contains dicyclohexylamine, the content of the epoxy resin (A) is preferably from 0.1% by mass to 30% by mass, more preferably from 0.5% by mass to 10% by mass. %. By setting the content ratio to 0.1% by mass or more, the effect of suppressing the ion transport can be further exhibited, and by setting the content to 30% by mass or less, the storage stability of the liquid resin composition for an electronic component can be more reliably prevented from being lowered. The glass transition temperature of the hardened material is lowered.

[ion trapping agent (E)]

The liquid resin composition for an electronic component preferably further contains an ion scavenger (E). The ion trapping agent (E) is contained, and the ion migration resistance, the moisture resistance, and the high-temperature standing characteristics tend to be further improved.

When the liquid resin composition for an electronic component contains the ion scavenger (E), the content thereof is applied to the wiring board and the semiconductor device without impairing the filling property or fluidity of the liquid resin composition for an electronic component. The range is not particularly limited as long as an anion such as a halogen ion is sufficiently trapped. For example, the content of the ion scavenger (E) is preferably from 0.1% by mass to 3.0% by mass, and more preferably from 0.3% by mass to 1.5%, based on the liquid resin composition for electronic components. quality%. The average particle diameter of the ion scavenger is preferably from 0.1 μm to 3.0 μm from the viewpoint of ensuring fluidity, and the maximum particle diameter is preferably 10 μm or less from the viewpoint of foreign matter removal property. The ion scavenger is not particularly limited, and those known in the art can be used. Particularly preferred is the hydrotalcite represented by the following composition formula (I) or the hydrous oxide of hydrazine represented by the following composition formula (II).

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _X/2 . mH ₂ O (I)

(In the formula (I), 0<X≦0.5, m is a positive number)

BiO _x (OH) _y (NO ₃ ) _z (II)

(in formula (II), 0.9≦x≦1.1, 0.6≦y≦0.8, 0.2≦z≦0.4)

Further, the compound of the above formula (I) is commercially available under the trade name DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd. as a commercial product. Further, the compound of the above formula (II) is commercially available under the trade name IXE500 manufactured by Toagosei Co., Ltd. as a commercial product. In addition, other ion trapping agents can be used as needed. For example, an aqueous oxide or the like of an element selected from the group consisting of magnesium, aluminum, titanium, zirconium, hafnium, and the like can be mentioned. These ion trapping agents may be used alone or in combination of two or more.

[hardening accelerator (F)]

The liquid resin composition for an electronic component preferably further contains a curing accelerator (F) which promotes a reaction between the epoxy resin and the curing agent. In order to have both the curability and the pot life of the liquid resin composition for an electronic component, the hardening accelerator is effective as a latent curing accelerator. The latent hardening accelerator refers to a person who exhibits a hardening promoting function under conditions of a specific temperature or the like. For example, a structure in which a usual curing accelerator is protected by a microcapsule or the like, or a salt which is added to various compounds can be mentioned. When the latent curing accelerator exceeds a specific temperature, the curing agent is released from the microcapsule or the adduct, and exhibits a hardening promoting function.

Examples of the latent curing accelerator include a latent hardening accelerator comprising a core of an epoxy group-containing compound which is solid at normal temperature and which is coated with a core of an epoxy compound which is solid at normal temperature. For the commercial product of such a latent hardening accelerator, Amicure ("Amicure"), which is manufactured by Ajinomoto Fine-Techno Co., Ltd., is a registered trademark. ) or disperse the microencapsulated amine in a bisphenol A epoxy resin or a bisphenol F ring Asahi Kasei E-Materials Co., Ltd., which is made of oxy-resin, is manufactured under the trade name Novacure ("Novacure" is a registered trademark).

Further, the following compounds can also be used as a latent curing accelerator: a liquid resin composition which is insoluble in an electronic component, a solid which is solid at normal temperature, and an amine compound or phosphorus which exhibits a hardening promoting action upon heat molding. A salt of a compound and a compound having intramolecular polarization obtained by adding a compound having a π bond thereto.

Examples of such compounds include 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-di Butylamino-1,8-diaza-bicyclo[5.4.0]undecene-7, etc., an intramolecularly polarized compound obtained by adding a cyclic ruthenium compound and a compound having a π bond; Derivatives of tertiary amine compounds such as diamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-ethyl- Derivatives of imidazole compounds such as 4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenyl An organic phosphine compound such as phosphine, triphenylphosphine, diphenylphosphine or phenylphosphine is added to maleic anhydride, 1,4-benzoquinone, 2,5-toluene, 1,4-naphthoquinone, 2, 3-dimethylphenylhydrazine, 2,6-dimethylphenylhydrazine, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1, a phosphorus compound having intramolecular polarization, such as a quinone compound such as 4-phenylhydrazine or phenyl-1,4-benzoquinone, a compound having a π bond such as diazophenylmethane or a phenol resin, and such a derivative Thereof; triphenylphosphine triphenylborane, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N- methylmorpholine tetraphenyl borate Phenyl boron salts, such derivatives, and the like. These compounds may be used alone or in combination of two or more.

Among the above-mentioned hardening accelerators, from the viewpoint of storage stability and rapid hardenability, it is preferred that the microencapsulated amine is dispersed in a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. .

In the case where the liquid resin composition for an electronic component contains a curing accelerator, it may contain only a latent curing accelerator, or may contain only a non-latent curing accelerator, or both may be used in combination. In the case where the liquid resin composition for an electronic component contains a curing accelerator, the content thereof is not particularly limited as long as it is an amount that achieves a curing-promoting effect. For example, it is preferably from 0.1% by mass to 40% by mass, and more preferably from 0.5% by mass to 30% by mass based on the total amount of the epoxy resin. By setting the above content ratio to 0.1% by mass or more, the curability in a short period of time can be improved. By setting the content ratio to 40% by mass or less, the following tendency can be avoided: the curing rate is too fast and it is difficult to control, or the storage stability such as the pot life and the shelf life is poor.

[Inorganic Filler (G)]

The liquid resin composition for an electronic component preferably further contains an inorganic filler (G). By containing the inorganic filler (G), the thermal expansion coefficient at the time of curing the liquid resin composition for an electronic component can be more effectively controlled, and the occurrence of cracks and peeling can be more reliably suppressed.

The inorganic filler may be a usual user of the liquid resin composition for an electronic component, and is not particularly limited. Examples of the inorganic filler include: cerium oxide such as molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, calcium carbonate, talc, clay, alumina, cerium nitride, cerium carbide, boron nitride, calcium citrate, Titanic acid Powders of potassium, aluminum nitride, cerium oxide, zirconium oxide, zircon, forsterite, stataite, spinel, mullite, titanium dioxide, or the like, or These spheroidized beads, glass fibers, and the like. Further, inorganic nanoparticles such as nano cerium oxide obtained by hydrolysis or condensation reaction of an alkoxide compound may be used as a filler. These inorganic fillers may be used singly or in combination of two or more.

The shape of the inorganic filler is preferably approximately spherical in view of moldability such as fluidity. The average particle diameter of the inorganic filler is preferably in the range of 5 nm to 10 μm, more preferably in the range of 10 nm to 1 μm. By setting the average particle diameter to 10 μm or less, sedimentation of the inorganic filler can be prevented, and the permeability of the liquid resin composition for electronic components to the fine gap and the decrease in fluidity or unfilling can be more reliably prevented. An inorganic filler which has been treated with a coupling agent may also be used as needed.

In the case where the liquid resin composition for an electronic component contains the inorganic filler (G), the content thereof is preferably set so as not to impair the filling property or fluidity between the gaps. For example, it is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the liquid resin composition for an electronic component. By setting the content ratio to 10% by mass or less, it is possible to more reliably prevent an increase in the linear expansion coefficient difference between the cured product of the liquid resin composition for an electronic component and the flexible wiring board using the film substrate. Peeling at the interface. Further, since the viscosity of the liquid resin composition for an electronic component is increased or the surface tension is increased, fluidity can be ensured, the coefficient of thermal expansion can be controlled, and cracking and peeling can be more reliably suppressed. The content of the inorganic filler (G) is preferably 0.1% by mass or more, and more preferably 1.0%, from the viewpoint of controlling the coefficient of thermal expansion. %the above.

[coupler]

The liquid resin composition for an electronic component may further contain a coupling agent. When the coupling agent is contained, there is a tendency that the wet resin property or the adhesion property of the liquid resin composition for an electronic component and the electronic component can be improved. The coupling agent is not particularly limited, and those previously known can be used. For example, a decane compound having at least one selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amine group, an epoxy decane, a decyl decane, an alkyl decane, a ureido decane, and a vinyl group may be mentioned. a decane compound such as decane, a titanium compound, an aluminum chelate compound, an aluminum/zirconium compound or the like. The coupling agent may be used alone or in combination of two or more.

Among the coupling agents, a decane coupling agent and a titanate coupling agent are preferred. Examples of the decane coupling agent include vinyl trichlorodecane, vinyl triethoxy decane, vinyl tris(β-methoxyethoxy) decane, and γ-methyl propylene methoxy propyl trimethoxy decane. --(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, vinyl Triethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyltriethyl Oxydecane, γ-aminopropylmethyldiethoxydecane, γ-anilinopropyltrimethoxydecane, γ-anilinopropyltriethoxydecane, γ-(N,N-dimethyl Aminopropyltrimethoxydecane, γ-(N,N-diethyl)aminopropyltrimethoxydecane, γ-(N,N-dibutyl)aminopropyltrimethoxydecane , γ-(N-methyl)anilinopropyltrimethoxydecane, γ-(N-ethyl)anilinopropyltrimethoxydecane, γ-(N,N-dimethyl)aminopropyl Triethoxy decane, γ-(N,N-diethyl)aminopropyltriethoxy Decane, γ-(N,N-dibutyl)aminopropyltriethoxydecane, γ-(N-methyl)anilinopropyltriethoxydecane, γ-(N-ethyl)aniline Propyltriethoxydecane, γ-(N,N-dimethyl)aminopropylmethyldimethoxydecane, γ-(N,N-diethyl)aminopropylmethyldi Methoxydecane, γ-(N,N-dibutyl)aminopropylmethyldimethoxydecane, γ-(N-methyl)anilinopropylmethyldimethoxydecane, γ- (N-ethyl)anilinopropylmethyldimethoxydecane, N-(trimethoxydecylpropyl)ethylenediamine, N-(dimethoxymethyldecylisopropyl)ethylene Amine, methyltrimethoxydecane, dimethyldimethoxydecane, methyltriethoxydecane, γ-chloropropyltrimethoxydecane, hexamethyldioxane, vinyltrimethoxydecane, γ - Mercaptopropylmethyldimethoxydecane, and the like.

Examples of the titanate coupling agent include isopropyl triisostearate titanate, Isopropyl tri(dioctylpyrophosphate) titanate, and isopropyl group. Tris(N-Aminoethyl-aminoethyl) titanate, Tetraoctyl bis(ditridecylphosphite) titanate, four (2) , 2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite decyl titanate, bis(dioctylpyrophosphate decyloxy)oxyacetamidine Titanium titanate, bis(dioctylpyrophosphate decyloxy)-extended ethyl titanate, isopropyl trioctadecyl titanate, isopropyldimethylmethenylisostearyl decyl titanate, Isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearyl decyl bisacryl decyl titanate, isopropyl tris(dioctylphosphonium oxy) titanate, Isopropyl cumyl phenyl titanate, tetraisopropyl bis(dioctylphosphite decyloxy) titanate, and the like.

In the case where the liquid resin composition for an electronic component contains a coupling agent, the content of the liquid resin composition for an electronic component is preferably from 0.037% by mass to 5.0% by mass, more preferably from 0.05% by mass to 4.75%. The mass% is further preferably 0.1% by mass to 2.5% by mass. By setting the content ratio to 0.037% by mass or more, the adhesion between the substrate and the liquid resin composition for an electronic component can be improved. By setting the content ratio to 5.0% by mass or less, it is possible to more reliably avoid a decrease in physical properties such as a glass transition temperature or a bending strength.

[leveling agent]

The liquid resin composition for an electronic component may further contain a leveling agent. By containing a leveling agent, it is possible to control the wettability or permeability of the liquid resin composition for an electronic component to an electronic component. The leveling agent is not particularly limited, and examples thereof include a usual anthrone-modified epoxy resin. The addition of the fluorenone-modified epoxy resin is effective for improving the leveling property of the liquid resin composition for an electronic component, improving the fillet formation property, and reducing voids. From the viewpoint of ensuring fluidity, an fluorenone-modified epoxy resin which is liquid at normal temperature is preferred. The fluorenone modified epoxy resin is locally present on the surface of the liquid to lower the surface tension of the liquid. As a result, the wettability of the liquid becomes high and it is easy to flow, so that it is effective in improving the permeability to the narrow gap or reducing the entrapment gap.

An anthrone-modified epoxy resin can be obtained as a reactant which is a reactant of an organic siloxane having a functional group reactive with an epoxy group and an epoxy resin. Specifically, the following method is employed: an organic siloxane having a functional group reactive with an epoxy group is mixed with an epoxy resin at 130 ° C to 150 ° C for 6 hours to 8 hours.

An officer having an epoxy group reaction to obtain an anthrone-modified epoxy resin Examples of the organic siloxane of the energy group include dimethyl methoxy oxane, diphenyl siloxane, methyl benzene having one or more amine groups, carboxyl groups, hydroxyl groups, phenolic hydroxyl groups, sulfhydryl groups and the like in one molecule. Base oxane and the like. The weight average molecular weight of the organic siloxane is preferably in the range of 500 to 5,000. By setting the weight average molecular weight to 500 or more, it is possible to prevent excessive compatibility with the resin and to sufficiently exhibit the effect as an additive. By setting the weight average molecular weight to 5,000 or less, separation and bleeding of the leveling agent at the time of molding can be prevented, and fluidity or wettability can be improved without impairing adhesion or appearance.

The epoxy resin which is used to obtain the fluorenone-modified epoxy resin is not particularly limited as long as it is compatible with the resin system of the liquid resin composition for electronic components, and can be usually used for the liquid resin composition for electronic components. Epoxy resin. For example, a glycidyl ether type epoxy resin obtained by a reaction with epichlorohydrin such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalenediol or hydrogenated bisphenol A; a novolac type epoxy resin represented by a cresol novolac type epoxy resin which is obtained by epoxidizing a novolac resin obtained by condensing or co-condensing a phenol compound with an aldehyde compound; by phthalic acid or dimer acid a glycidyl ester type epoxy resin obtained by reacting a polybasic acid with epichlorohydrin; a glycidylamine type ring obtained by reacting a polyamine such as diaminodiphenylmethane or isocyanuric acid with epichlorohydrin Oxygen resin; a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; an alicyclic epoxy resin or the like. These epoxy resins may be used singly or in combination of two or more. From the viewpoint of low viscosity, an epoxy resin which is liquid at normal temperature is preferred.

In the case where the liquid resin composition for an electronic component contains a leveling agent In the liquid resin composition for electronic components, the content of the liquid resin composition is preferably from 0.005 mass% to 1.0 mass%, more preferably from 0.01 mass% to 0.1 mass%, in terms of fluidity and wettability control. Further preferably, it is 0.015 mass% to 0.08 mass%.

[Flame retardant]

The liquid resin composition for an electronic component may further contain a flame retardant. By including a flame retardant, it is possible to suppress an increase in combustion when an electrical short circuit occurs. A brominated epoxy resin or antimony trioxide can be used as the flame retardant. From the viewpoint of safety and environmental compatibility, it is preferred to use a halogen-free, flawless flame retardant. Examples of the halogen-free and antimony-free flame retardant include red phosphorus, a phosphorus compound such as a red phosphorus, a phosphate ester or a triphenylphosphine oxide coated with a thermosetting resin such as a phenol resin, and a melamine, a melamine derivative, and a melamine modification. a phenol resin, a compound having a triazine ring, a nitrogen-containing compound such as a cyanuric acid derivative or an isocyanuric acid derivative, a compound containing phosphorus and nitrogen such as cyclophosphazene, and a metal complex compound such as ferrocene, which is oxidized. a zinc compound such as zinc, zinc stannate, zinc borate or zinc molybdate; a metal oxide such as iron oxide or molybdenum oxide; a metal hydroxide such as aluminum hydroxide or magnesium hydroxide; and a composite represented by the following composition formula (III) Metal hydroxides, etc.

p(M ¹ _a O _b ). q(M ² _c O _d ). r(M ³ _c O _d ). mH ₂ O (III)

(In the composition formula (III), M ¹ , M ² and M ³ represent mutually different metal elements, and a, b, c, d, p, q and m represent a positive number, and r represents a 0 or a positive number)

M ¹ , M ² and M ³ in the above composition formula (III) are not particularly limited as long as they are mutually different metal elements. From the viewpoint of flame retardancy, it is preferred that M ¹ is selected from the group consisting of metal elements of the third cycle, alkaline earth metal elements of group IIA, and belonging to groups IVB, IIB, VIII, IB, IIIA, and IVA. a group consisting of metal elements, and M ² is selected from the group consisting of transition metal elements of group IIIB to IIB, more preferably M ¹ is selected from the group consisting of magnesium, calcium, aluminum, tin, titanium, iron, In the group consisting of cobalt, nickel, copper and zinc, and M ² is selected from the group consisting of iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferred that M ¹ is magnesium, M ² is zinc or nickel, and r=0. The molar ratio of p, q and r is not particularly limited, and is preferably r = 0 and p/q is 1/99 to 1/1. Furthermore, the above classification of the metal element is based on a periodic table of the periodic period in which the typical element is the A subfamily and the transition element is the B subfamily. These flame retardants may be used alone or in combination of two or more.

[diluent]

The liquid resin composition for an electronic component may further contain a diluent. The viscosity of the liquid resin composition for an electronic component can be easily adjusted by containing a diluent. The diluent is not particularly limited, and from the viewpoint of compatibility, a reactive diluent having an epoxy group is preferred. Examples of the reactive diluent having an epoxy group include n-butyl glycidyl ether, glycidyl kelic acid, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, and butylphenyl glycidyl ether. 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like. These diluents may be used alone or in combination. Two or more.

[Other additives]

The liquid resin composition for an electronic component may contain other additives other than the above components as needed. Examples of such additives include coloring agents such as dyes, carbon black, titanium oxide, and red lead, stress relieving agents, antifoaming agents, and subsequent accelerators. When the liquid resin composition for an electronic component contains the additives, it is preferably added in a range that does not impair the filling property or fluidity of the liquid resin composition for an electronic component when applied to a wiring board or a semiconductor device. .

[Preparation method of liquid resin composition for electronic components]

The method for producing the liquid resin composition for an electronic component is not particularly limited as long as the above components can be uniformly dispersed and mixed. Examples of the usual method include a method of mixing and kneading a predetermined amount of components using a kneader, a mixing roll, a planetary mixer, a high-pressure wet micronization apparatus, and the like, and if necessary Defoaming is carried out.

The above method may further comprise the steps of mixing particles having a core-shell structure with a preliminary mixture of the first epoxy resin, a second epoxy resin, and a cyclic anhydride which is liquid at 25 ° C.

<Electronic component device>

An electronic component device according to the present invention includes a support member, an electronic component disposed on the support member, and a cured product of the liquid resin composition for sealing the electronic component or the electronic component. Since the liquid resin composition for an electronic component described above is used for sealing or the subsequent sealing of the electronic component, the insulation of the electronic component mainly caused by ion migration can be reduced. good. Therefore, even in the case of finely pitched electronic components, long-term insulation reliability can be ensured.

Examples of the electronic component device include a semiconductor wafer packaged on a support frame such as a lead frame, a tape carrier, a rigid or flexible wiring board, a glass or a germanium wafer. An active component such as a transistor, a diode, or a thyristor, and an electronic component such as a capacitor, a resistor, a resistor array, a coil, a switch, and the like, and the liquid resin composition for the electronic component is used to seal or necessary to seal the necessary portion Electronic component device.

The liquid resin composition for an electronic component is particularly useful for sealing the electronic component device in which the electronic component is directly bump-bonded on the wiring substrate having the film as a base material, and the insulation property between the narrow gaps can be more significantly exhibited. . An example of such an electronic component device is a semiconductor device in which a semiconductor element is flip-chip bonded to a wiring formed on a support member such as a rigid or flexible wiring board or glass by bump connection. Specific examples of the semiconductor device include a Hall Grid Array (BGA), a Chip On Film (COF), and a Chip On Glass (COG). The liquid resin composition for an electronic component is particularly suitable as an underfill for COF which is excellent in ion mobility resistance. Further, the liquid resin composition for an electronic component described above can also be effectively used for a printed circuit board.

The method of sealing the electronic component disposed on the substrate using the liquid resin composition for electronic components described above or obtaining the electronic component device is not particularly limited. For example, a distribution method, an injection molding method, a printing method, and the like can be cited. law. The sealing can be performed by using an appropriate method according to the packaging method of the electronic component.

Fig. 1 (a) is a schematic cross-sectional view showing an example of a film on film (COF) from the long side of the semiconductor element, and Fig. 1 (b) is a schematic cross section of the COF viewed from the short side of the semiconductor element. Figure. As shown in Fig. 1 (a) and Fig. 1 (b), a semiconductor element 1 is flip-chip mounted on a flexible printed circuit (FPC) 2 made of polyimide. Specifically, the Sn-plated Cu wiring 3 on the substrate 2 side and the connection terminals (bumps) 4 on the semiconductor element 1 side are connected by a Eu/Sn eutectic (not shown). As the connection terminal 4, a connection terminal formed of Au, a connection terminal formed of Au-plated Cu, a solder terminal, or the like can be used. The insulation between the connection terminals 4 is realized and physically protected by the gaps between the adjacent connection terminals 4 and the cured product 5 of the liquid resin composition for electronic components in the gap between the semiconductor element 1 and the substrate 2. The solder resist 6 also functions as a banknote so that the liquid resin composition for electronic components before hardening does not expand on the substrate 2.

[Examples]

Hereinafter, the present invention will be described with reference to the examples, but the scope of the invention is not limited to the examples.

<Preparation of Liquid Resin Composition for Electronic Components>

The following materials were kneaded and dispersed for 30 minutes at 25 ° C in the mass parts shown in Table 1 and Table 2 at 25 ° C using a masher (manufactured by Ishikawa Kogyo Co., Ltd., product name: 6RA). Thereafter, it was degassed under vacuum at 25 ° C for 10 minutes using a defoaming device (manufactured by EME Co., Ltd., product name UFO-20). borrow The liquid resin compositions for electronic components of Examples 1 to 34 and Comparative Examples 1 to 4 were prepared.

In Example 3, Example 5, Example 9, Example 11, Example 20, Example 22, Example 26 and Example 28, core-shell particles 1 or core-shell particles 2 were mixed to epoxy resin 4. A preliminary mixture is prepared in the epoxy resin 5. Specifically, a high-pressure wet micronization apparatus (manufactured by Yoshida Machinery Co., Ltd., trade name: Nanomizer NM-2000AR ("Nanomizer" is a registered trademark)) is used. The mixing treatment was carried out for 30 minutes at °C.

In Example 2, Example 6, Example 8, Example 12 to Example 17, Example 19, Example 23, Example 25, Example 29 to Example 34, and Comparative Example 2 to Comparative Example 4, A commercially available core-shell epoxy dispersion 1 or core-shell epoxy dispersion 2 was used as a preliminary mixture.

Epoxy Resin 1: Bisphenol F-type liquid epoxy resin with an epoxy equivalent of 160 (manufactured by Nippon Steel Chemical Co., Ltd., trade name: YDF-8170C)

Epoxy Resin 2: bisphenol A type epoxy resin having an epoxy equivalent of 185 (manufactured by Nippon Steel Chemical Co., Ltd., trade name: YDF-127)

Anhydride 1: a cyclic anhydride having a anhydride equivalent of 234 which is liquid at normal temperature, manufactured by Mitsubishi Chemical Corporation, trade name: YH306, viscosity 0.13 Pa. s)

Anhydride 2: a cyclic anhydride which is liquid at room temperature with an anhydride equivalent of 166, manufactured by Hitachi Chemical Co., Ltd., trade name: HN-2200, viscosity 0.07 Pa. s)

Anhydride 3: a cyclic acid which is solid at room temperature with an anhydride equivalent of 155 Anhydride, manufactured by New Japan Physical and Chemical Co., Ltd., trade name: Rikacid HH, "Rikacid" is a registered trademark)

Amine compound: manufactured by Mitsubishi Chemical Corporation, trade name: jER cure W (addition amount: 25 phr (25 parts by mass relative to 100 parts by mass of epoxy resin), "jER cure" is a registered trademark)

Core-shell particle 1: manufactured by Ganz Chemical Co., Ltd., trade name: F351 (anthracene nucleus, acrylic shell, average particle size of primary particles is 200 nm to 300 nm)

Core-shell particle 2: Manufactured by Wacker Chemie, trade name: GENIOPERL-P52 (anthracene nucleus, acrylic shell, primary particle average particle size from 100 nm to 150 nm)

Epoxy resin 4 for premixing core-shell particles: bisphenol F-type liquid epoxy resin having an epoxy equivalent of 165 (manufactured by Mitsubishi Chemical Corporation, trade name: jER806, "jER" is a registered trademark)

Epoxy resin 5 for premixing core-shell particles: bisphenol F-type epoxy resin having an epoxy equivalent of 163 (manufactured by Nippon Steel Chemical Co., Ltd., trade name: YDF-870GS)

Core-shell epoxy dispersion 1: manufactured by Kaneka Co., Ltd., trade name: MX-136 (butadiene core, acrylic shell, primary particle average particle size 100 nm~500 nm, bisphenol F Epoxy resin with a particle content of 25% by mass)

Core-shell epoxy dispersion 2: manufactured by Kaneka Co., Ltd., trade name: MX-960 (anthracene nucleus, acrylic shell, primary particle average particle size 100 nm~500 nm, bisphenol A type Epoxy resin, particle containing The amount is 25% by mass)

Rubber particle component: acrylonitrile-butadiene-methacrylic acid-divinylbenzene copolymer (manufactured by JSR Co., Ltd., trade name: XER-91P, "XER" is a registered trademark) in bisphenol F-type liquid epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name: YDF-8170C) in mass ratio (copolymer/epoxy resin) = 1/4 at 85 ° C for 5 hours, at 115 ° C 3 Rubber modified epoxy resin obtained by heating and mixing and microdispersion under an hour condition

Coupling agent: γ-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403)

Leveling agent: phenol modified ketone with a hydroxyl equivalent of 750 (manufactured by Toray Dow Coring Co., Ltd., trade name: BY16-799) and bisphenol F liquid epoxy resin (Nippon Steel Chemical Co., Ltd. Manufactured by the company, trade name: YDF-8170C) Anthrone modified epoxy resin obtained by heating and mixing for 6 hours at a mass ratio of 1/1 at 130 °C

Hardening accelerator 1: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., trade name: 2E4MZ)

Hardening accelerator 2: manufactured by Asahi Kasei Electronic Materials Co., Ltd., trade name: Novacure HX-3921HP)

Antioxidant 1: 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl] -2,4,8,10-Tetraoxaspiro[5.5]undecane (Manufactured by ADEKA Co., Ltd., trade name: AO-80)

Antioxidant 2: Dicyclohexylamine (manufactured by New Japan Physical and Chemical Co., Ltd., trade name: D-CHA-T)

Ion trapping agent: lanthanide ion scavenger (manufactured by Toagosei Co., Ltd., trade name: IXE-500, "IXE" is a registered trademark)

Inorganic filler: spherical synthetic cerium oxide (MRC-Unitec Co., Ltd., trade name: QS-4F2) with a specific surface area of 1 m ² /g and an average particle diameter of 4 μm

<evaluation>

The liquid resin compositions for electronic components produced in Examples 1 to 34 and Comparative Examples 1 to 4 were evaluated by the following tests. The results are shown in Tables 1 and 2.

(1) Viscosity

EMD type rotational viscometer (manufactured by Tokimec Co., Ltd.) equipped with a conical rotor having a cone angle of 3° and a conical radius of 14 mm, and a liquid resin for electronic components maintained at 25 ° C ± 1 ° C The composition was multiplied by a conversion factor of 0.0125 in a measurement value when rotated at 100 rpm for 1 minute, and this was used as the viscosity of the liquid resin composition for electronic components.

(2) Gelation time

0.1 g of a liquid resin composition for an electronic component was dropped on a hot plate at 150 ° C, and stirred by a spatula so as not to excessively diffuse. After the dropwise addition, the viscosity of the liquid resin composition for the electronic component is increased until the time when the shovel is lifted up without drawing and the liquid resin composition for the electronic component is cut is taken as the gelation time.

(3) Water absorption rate

The liquid resin composition for an electronic component was cured at 150 ° C for 2 hours to prepare a test piece of 50 mm × 50 mm × 1 mm. Determination of the above test After the initial mass W1 of the sheet, it was placed in a high-temperature and high-humidity bath at 85 ° C / 85%, and the mass W2 after 100 hours was measured. The water absorption rate was determined by the following formula.

(water absorption rate) = {(W2-W1) / W1} × 100 (%)

(4) Next force

Coated with a polyimide film (made by Toray DuPont Co., Ltd., trade name: Kapton ("Kapton" is a registered trademark)) The liquid resin composition for a cloth electronic component was cured at 150 ° C for 2 hours, and was cut into a short strip having a length of 50 mm and a width of 10 mm to obtain a test piece. The tear strength at the time when the polyimide film was peeled off 90 degrees from the test piece was measured using a tensile tester (manufactured by Shimadzu Corporation), and the tear strength was used as an adhesion force.

(5) Infiltration

A separator made of stainless steel (Stainless Steel, SUS) having a thickness of 20 μm was sandwiched between two sheets of glass to prepare a flow path having a width of 5 mm and a height of 20 μm. After the horizontally placed on a hot plate at 70° C., the liquid resin composition for an electronic component was dropped into the opening of the flow path, and the time until the depth of 20 mm was infiltrated into the flow path was measured. The case of less than 3 minutes was evaluated as good, and the case of 3 minutes or more was evaluated as defective.

(6) Resistance to ion mobility

The liquid resin composition for electronic components produced in Examples 1 to 34 and Comparative Examples 1 to 4 was applied to FIG. 1(a) by a distribution method. In the gap between the substrate 2 of the COF shown in Fig. 1(b) and the semiconductor element 1, it was cured at 150 °C for 2 hours to prepare a test sample. In the test sample, the connection terminal 4 was formed using Au. The outer shape of the flexible substrate (FPC) 2 is a short side of 25 mm × a long side of 40 mm, and the size of the semiconductor element 1 packaged on the substrate 2 is a short side of 2 mm × a long side of 20 mm. The gap between the adjacent connection terminals 4 is about 10 μm, and the gap between the semiconductor element 1 and the substrate 2 is about 20 μm.

Then, a voltage was applied between the adjacent wiring and the connection portion of the bump to evaluate the ion mobility resistance. The gap between the connections was set to 10 μm, the applied voltage was set to 60 V DC, the test environment was set to 110 ° C, 85% RH, and the test time was set to 500 hours. In the test, the resistance value of the test sample was continuously measured, and the test sample having a resistance value of 10 ⁶ Ω or less was judged to be short-circuited. Each of the 50 samples was evaluated for each of the examples and the comparative examples shown in Table 1, and the number of samples determined to be short-circuited was compared. The relationship between the determination criterion and the number of short circuits is as follows, and the case where it is determined to be B or more is regarded as pass.

(judgment basis)

AA: 0~2

A: 3 ~ 5

B: 6~10

C: 11~20

D: 21 ~ 50

The outline of the connection pattern of the test sample is shown in Fig. 2 (a) and Fig. 2 (b). Fig. 2(a) is a view of the test sample viewed from the side of the semiconductor element 1, 2(b) is a diagram showing the cured product 5 of the liquid resin composition for the semiconductor element 1 and the electronic component, and shows the connected wiring pattern. The same members as those shown in Figs. 1(a) and 1(b) are denoted by the same reference numerals as those in Figs. 1(a) and 1(b).

In the evaluation of the ion permeation resistance described above, the lead wires were soldered to the connection pads 7 and the connection pads 7' (two places) provided in the opening portion of the solder resist, and a DC voltage was applied thereto. In the above evaluation, the positive and negative (+-) voltages are the positions shown in FIGS. 2(a) and 2(b), and may be reversed. As will be described with reference to FIG. 2( b ), the + side is applied to the connection terminal 4 from one connection pad 7 via the metal wiring 3 . The side is connected to the connection terminal 4 via the metal wiring 3 from the other connection pad 7', and is further applied to the connection terminal 4 via the wiring 8 formed on the semiconductor element 1. Thereby, a voltage of +- can be alternately applied to the connection terminal 4, and the ion mobility resistance between the connection terminals can be evaluated. In addition, in FIG. 2(a) and FIG. 2(b), only 12 connection terminals are shown, and about 500 similar connection terminals are actually arrange|positioned.

As a result of evaluation of migration resistance, Comparative Example 2 in which no core-shell structure was contained, Comparative Example 2 in which an amine was used in a curing agent, and Comparative Example 3 in which an acid anhydride was solid at normal temperature were all unacceptable. Further, even in Comparative Example 4 in which the viscosity at room temperature is not included in the range of the present invention, even if the particle having a core-shell structure is contained, it is difficult to form a sample having low permeability to the electronic member and causing voids to cause insulation failure. Ion mobility was evaluated.

On the other hand, the liquid resin composition for an electronic component of the present invention shown in Examples 1 to 34 does not impair the viscosity, the gelation time, the water absorption, the adhesion, the penetration, and the like as the liquid for the electronic component. Resin composition All the necessary characteristics, good ion migration resistance. Furthermore, when the vicinity of the connection terminal of the test sample which was determined to be short-circuited was observed, as shown in FIG. 3, the filament-shaped insulating deterioration portion 10 and the dielectric breakdown portion 11 formed between the connection terminals 4 were confirmed. , the corroded portion 12 of the wiring metal, and the like. In the case where the insulation failure caused by the ion migration is less than that of the embodiment of the comparative example, it is considered that the effect of the particles having a core-shell structure and the cyclic acid anhydride which is liquid at normal temperature, and the low viscosity can be obtained. The gap between the narrow gaps is filled, and the deterioration of the cured product of the liquid resin composition for an electronic component in a high-temperature and high-humidity environment is suppressed, and generation of impurity ions or reduction in insulation properties are suppressed.

1‧‧‧Semiconductor components

2‧‧‧Substrate (flexible substrate)

3‧‧‧Metal (Cu) wiring

4‧‧‧Connecting terminal (bump)

5‧‧‧Attenuation of liquid resin composition for electronic components

6‧‧‧ solder resist

7, 7'‧‧‧ Connection pads in the solder resist opening

8‧‧‧Wiring formed on the semiconductor component 1

9‧‧‧ solder resist opening (component hole)

10‧‧‧ Filament-like insulation degradation

11‧‧‧Insulation breaking part of connecting terminal (bump) 4

12‧‧‧Corrosion of wiring metal

Fig. 1 (a) and Fig. 1 (b) are schematic cross-sectional views (a) and a schematic view from the short side as viewed from the long side of the semiconductor element, an example of a chip on film (COF). Section 1 (b).

2(a) and 2(b) are diagrams for explaining a wiring pattern of a test sample.

3 is a schematic view showing an insulation deterioration state of a test sample which is determined to be short-circuited as a result of evaluation of ion mobility resistance.

1‧‧‧Semiconductor components

2‧‧‧Substrate (flexible substrate)

3‧‧‧Metal (Cu) wiring

4‧‧‧Connecting terminal (bump)

5‧‧‧Attenuation of liquid resin composition for electronic components

6‧‧‧ solder resist

Claims (15)

A liquid resin composition for an electronic component comprising an epoxy resin, a cyclic acid anhydride which is liquid at 25 ° C, and a particle having a core-shell structure, and the viscosity at 25 ° C measured by an EMD type rotational viscometer is 1.2. Pa. s Hereinafter, the core of the above-described particle having a core-shell structure contains a polyoxyalkylene compound. The liquid resin composition for an electronic component according to the above aspect of the invention, wherein the shell of the core-shell-containing particles comprises a polymer comprising an acrylate selected from a polymerization component and an aromatic At least one of the group consisting of a vinyl compound, an acrylonitrile compound, a acrylamide derivative, and a maleimide derivative. The liquid resin composition for an electronic component according to the first aspect of the invention is obtained by using a preliminary mixture obtained by preliminarily mixing the particles having the core-shell structure in an epoxy resin. The liquid resin composition for an electronic component according to claim 3, wherein the amount of free chlorine ions contained in the preliminary mixture is 100 ppm or less. The liquid resin composition for an electronic component according to any one of the first aspect, wherein the content of the core-shell-containing particles is the total of the liquid resin composition for the electronic component. 1% by mass or more and 10% by mass or less. The liquid resin composition for an electronic component according to any one of the first to fourth aspect, wherein the cyclic acid anhydride which is liquid at normal temperature has an acid anhydride equivalent of 200 or more. The liquid resin composition for an electronic component according to any one of claims 1 to 4, further comprising an antioxidant. The liquid resin composition for an electronic component according to any one of claims 1 to 4, further comprising an ion scavenger. The liquid resin composition for an electronic component according to any one of claims 1 to 4, further comprising a curing accelerator. The liquid resin composition for an electronic component according to any one of the first aspect of the present invention, further comprising an inorganic filler, wherein the content of the inorganic filler is a liquid resin for the electronic component. The composition is 10% by mass or less or less in total. The liquid resin composition for an electronic component according to any one of claims 1 to 4, which is used in an electronic component device having a structure in which an electronic component is flip-chip bonded to a wiring substrate. The liquid resin composition for an electronic component according to claim 11, which is used in the electronic component device in which the wiring substrate is a substrate. An electronic component device including a support member, an electronic component disposed on the support member, and a sealing or subsequent sealing of the support member and the electronic component, as described in any one of claims 1 to 12 A cured product of a liquid resin composition for an electronic component. A method for producing a liquid resin composition for an electronic component, comprising: mixing a particle having a core-shell structure with a preliminary mixture of a first epoxy resin, a second epoxy resin, and a cyclic acid anhydride which is liquid at 25 ° C And the viscosity at 25 ° C measured by the EMD type rotational viscometer after mixing is 1.2 Pa. s Hereinafter, the core of the above-described particle having a core-shell structure contains a polyoxyalkylene compound. The method for producing a liquid resin composition for an electronic component according to claim 14, wherein the amount of free chlorine ions contained in the preliminary mixture is 100 ppm or less.