JP2019135311A - Liquid resin composition for electronic component, and electronic component apparatus - Google Patents

Abstract

To provide a liquid resin composition for an electronic component excellent in flowability through a narrow gap, and having suppressed void, bleeding and creeping; and to provide an electronic component apparatus sealed thereby.SOLUTION: A liquid resin composition for an electronic component contains (A) a resin, (B) an inorganic filler (C) an inorganic filler having a peak of 100 nm or less, preferably, 50 nm or less in a laser diffraction method, in which a content of the inorganic filler obtained by adding (B) the inorganic filler to (C) the inorganic filler is 67-77 mass% to the whole liquid resin composition for the electronic component.SELECTED DRAWING: None

Description

  The present invention relates to a liquid resin composition for an electronic component particularly suitable for sealing an electronic component device, and an electronic component device including an element sealed with this composition.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and various types of resin compositions have been applied. Among them, epoxy resins are widely used because they have a good balance of workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesive properties with inserts. Liquid resin compositions for electronic components are widely used as sealing materials in semiconductor devices mounted on bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package). Further, in a semiconductor device (flip chip) in which a semiconductor element is directly bump-connected to a wiring board using ceramic, glass / epoxy resin, glass / imide resin or polyimide film as a substrate, the bump-connected semiconductor element and wiring board A liquid resin composition for electronic parts is used as an underfill material for filling the gap. These liquid resin compositions for electronic parts play an important role in protecting electronic parts from temperature and humidity and mechanical external force.

  For example, to provide an electronic component device with high reliability (moisture resistance and thermal shock resistance) including an epoxy resin composition for sealing excellent in moisture-resistant adhesive strength and low stress resistance, and an element sealed thereby. (A) Liquid epoxy resin, (B) Curing agent containing liquid aromatic amine, (C) Rubber particles, (D) An epoxy resin composition for sealing containing an inorganic filler, and for sealing An electronic component device including an element sealed with an epoxy resin composition is disclosed (see Patent Document 1).

JP 2001-270976 A

  However, the progress of semiconductors is remarkable, and in the flip-chip method in which bump connection is performed, the bump pitch and bump height are reduced as the number of bumps is increased, and as a result, the gap is being narrowed. With higher integration, the chip size has also increased, and underfill materials have been required to have a characteristic of flowing over a large area with a narrow gap. Further, since the number of bumps is increased and the bump pitch is narrowed along with the narrowing of the gap, the flow path of the underfill material becomes complicated, and voids are easily generated. The generation of such voids greatly affects the reliability of the flip chip semiconductor device. In addition, the bleeding (bleeding) of the resin component to the substrate in the fillet portion may contaminate a semiconductor element or a terminal for electrical connection disposed on the substrate, and it is preferable not to occur. Further, creeping in which the resin component crawls up on the back surface of the semiconductor element is not only a cause of trouble during mounting because the flatness of the back surface of the semiconductor element of the flip chip semiconductor device cannot be ensured, but also the electronic component device becomes difficult after curing the liquid resin composition When overmolded, peeling may occur from the creeping portion as a starting point, and there is concern about a decrease in reliability.

  As described above, taking the underfill material as an example, the liquid resin composition for electronic parts is required to solve various problems as the semiconductor advances. The present invention has been made in view of such circumstances, the fluidity in a narrow gap is good, and a liquid resin composition for electronic parts that suppresses voids, bleed and creeping, and is sealed by this. An object is to provide an electronic component device.

  As a result of intensive studies in order to solve the above problems, the present inventors have made the inorganic filler contained in the resin composition contain an ultrafine inorganic filler, thereby improving the fluidity and void resistance of the resin composition. Characteristics, bleed resistance and creep resistance could be improved more than before.

The present invention relates to the following.
[1] (A) a resin, (B) an inorganic filler, and (C) an inorganic filler having a peak of 100 nm or less by a laser diffraction method, and the (B) inorganic filler and the (C) inorganic filler The liquid resin composition for electronic components whose content of the inorganic filler which match | combined these is 67-77 mass% of the said whole liquid resin composition for electronic components.
[2] The liquid resin composition for electronic parts according to [1], wherein the (C) inorganic filler is an inorganic filler having a peak of 50 nm or less by a laser diffraction method.
[3] The liquid resin composition for electronic parts as described in [1] or [2] above, wherein the inorganic filler (B) contains an inorganic filler having a peak in a laser diffraction method of 0.3 to 10 μm. object.
[4] The electron according to any one of [1] to [3], wherein the inorganic filler (B) includes an inorganic filler having a peak in a laser diffraction method of 0.3 to 3 μm. Liquid resin composition for parts.
[5] In any one of [1] to [4], the blending amount of the inorganic filler (C) is 0.1 to 10% by mass with respect to the entire liquid resin composition for electronic components. The liquid resin composition for electronic components as described.
[6] The viscosity at 110 ° C. is 0.2 Pa. Liquid resin composition for electronic parts as described in any one of said [1]-[5] which is s or less.
[7] The liquid resin composition for electronic components according to any one of [1] to [6], wherein the (A) resin includes (A1) an epoxy resin and (A2) a curing agent.
[8] The liquid resin composition material for electronic components according to any one of [1] to [7], further including a flexibilizer.
[9] The liquid resin composition for electronic parts according to any one of [1] to [8], further including a surfactant.
[10] The liquid resin composition for electronic components according to any one of [1] to [9], further including an ion trap agent.
[11] The liquid resin composition for electronic parts according to any one of [1] to [10], further including a curing accelerator.
[12] The liquid resin composition for electronic components according to any one of [1] to [11], further including a coupling agent.
[13] The liquid resin composition for electronic parts according to any one of [1] to [12], further containing an antioxidant.
[14] The liquid resin for electronic components according to any one of [1] to [13], wherein the organic solvent content is 5% or less of the entire electronic component liquid composition containing the organic solvent. Composition.
[15] Used to seal the connection part of the electronic component device in which the electronic component and the wiring board are electrically connected via the connection part, and the gap between the electronic component and the wiring board is filled. The liquid resin composition for electronic parts according to any one of [1] to [14].
[16] The liquid resin composition for electronic components according to [15], wherein the connection part does not contain lead.
[17] The liquid resin composition for electronic components according to [15] or [16], wherein the connection part contains copper.
[18] An electronic component device sealed with the liquid resin composition for electronic components according to any one of [1] to [17].

  The liquid resin composition for electronic parts of the present invention can shorten the filling time, suppress the flow disturbance during the flow, further suppress the void during molding, and suppress bleeding and creeping.

  The liquid resin composition for electronic parts of the present invention is an inorganic filler conventionally used to improve the penetration into a narrow gap between an electronic part such as a semiconductor element and a wiring board, for example, 0.5 μm. To reduce the viscosity of the material by using an inorganic filler having a particle size distribution peak at ˜20 μm together with an ultrafine inorganic filler having a particle size distribution peak newly measured by a laser diffraction method of 100 nm or less. It was made by finding out that it can do.

  Liquid resin compositions for electronic parts containing ultrafine inorganic fillers having a particle size distribution peak of 100 nm or less have been studied as underfill materials. However, this ultrafine inorganic filler is generally used for the purpose of imparting thixotropy from the viewpoint of suppressing bleeding, and the viscosity of the resin composition tends to increase. Therefore, the amount of the inorganic filler that can be contained in the low-viscosity underfill material is practically restricted to 65% by mass or less. The ultrafine inorganic filler of 100 nm or less may be applied as an underfill material for ensuring visibility by utilizing the effect of increasing the transparency of the material, for example. In addition, application as a non-flow underfill material that can be used even when the viscosity is slightly increased has been attempted. Other than the use of an underfill material, as a liquid sealing material used for packaging for protecting a semiconductor element from the external environment, an ultrafine inorganic filler of 100 nm or less is an inorganic filler having a larger particle diameter than that. Sometimes used in combination.

  On the other hand, the liquid resin composition for electronic parts of the present invention can suppress an increase in the viscosity of the material even when the filling amount of the inorganic filler is high, and can increase the fluidity as compared with the conventional one, and also has a low thermal expansion. And a relatively high elasticity, the stress reducing effect is high and the bump connection retention is excellent. Therefore, it can be applied to a highly reliable semiconductor device as an underfill material that fills a narrow gap between an electronic component such as a semiconductor element and a wiring board on which the electronic component is mounted. In addition, the combined use with an inorganic filler having a particle size distribution peak of 100 nm or less only has an effect of reducing the viscosity of the material, and has the effect of uniformizing the flow disturbance during flow and suppressing voids during molding. can get. This is because an extremely fine inorganic filler having a particle size distribution peak of 100 nm or less is interposed between the larger non-filler and the resin, and the resin separates from the large inorganic filler during the flow and flows. This is considered to suppress the functioning and to develop a function of causing the resin and the inorganic filler to flow together.

  The above-described function has a great effect not only in suppressing the bleeding of the resin to the wiring board but also in suppressing the creeping in which the resin crawls up on the back surface of the semiconductor element. Bleed and creeping are major factors that reduce the reliability of semiconductor devices. To achieve high reliability, it is necessary to solve both problems at the same time. Inorganic packing with a particle size distribution peak of 100 nm or less It has been found that the combined use with the material is particularly effective.

  In order to achieve the effect of the present invention, it is essential to use an inorganic filler having a peak flow distribution of 100 nm or less as an inorganic filler, but the ultrafine particle size is further reduced and the peak is reduced. If an inorganic filler having a thickness of 50 nm or less is used, the fluidity as an underfill material can be further improved.

  As described above, the liquid resin composition for an electronic component of the present invention includes (A) a resin, (B) an inorganic filler, and (C) an inorganic filler having a peak of 100 nm or less by a laser diffraction method as a basic configuration. From the viewpoint of improvement of moldability such as high fluidity, suppression of voids, bleed and creep and high reliability of flip chip semiconductor device, (B) inorganic filler and (C) inorganic filler combined with inorganic filler It is characterized in that the content is 67 to 77% by mass of the entire liquid resin composition for electronic parts. Furthermore, the (B) inorganic filler has a peak in the laser diffraction method of 0.3 to 10 μm, preferably 0.3 to 3 μm, in order to meet the technical problem of narrowing the bump pitch described above. is there.

  The liquid resin composition for electronic parts according to the present invention preferably has a viscosity at 110 ° C. of 0.3 Pa · s or less. Thereby, since the permeability and fluidity into the fine gap are improved and the filling speed can be increased, the impregnation time can be shortened and the generation of voids can be suppressed. Furthermore, from the viewpoint of shortening the impregnation time, it is particularly preferably 0.2 Pa · s or less. The viscosity is measured at a temperature of 30 to 140 ° C. using a rheometer AR2000 (TA instrument) under the conditions of a 40 mm parallel plate and a shear rate of 32.5 (1 / s). The viscosity at 110 ° C. is used as a measure of the permeability and fluidity of the liquid resin composition for electronic parts in the present invention. The viscosity of 110 ° C. is the highest temperature that can be practically used when injecting the liquid resin composition into the fine gap in the manufacture of the flip-chip semiconductor device. In particular, the gap between the semiconductor element and the substrate is 100 μm or less, It is a physical property value that most reflects the fluidity as an underfill material in an electronic component having a narrow width of 50 μm or less.

  The resin (A) used in the liquid resin composition for electronic parts of the present invention is not particularly limited, but a low-viscosity acrylic resin, a low-stress polyurethane resin, a silicone resin, an epoxy resin that easily obtains a balance of various properties, and the like You can choose from. Among them, epoxy resin is not only easy to obtain a balance of various properties, but also has electrical properties, moisture resistance, heat resistance, mechanical properties, and insert properties that are necessary for manufacturing highly reliable semiconductor devices. Therefore, it is preferable to include (A1) an epoxy resin and (A2) a curing agent.

  The (A1) epoxy resin used in the present invention has one or more epoxy groups in one molecule and is preferably liquid at room temperature, and is a liquid epoxy generally used in liquid resin compositions for electronic components. Resin can be used suitably. Examples of epoxy resins that can be used in the present invention include diglycidyl ether type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, hydrogenated bisphenol A, and phenols typified by orthocresol novolac type epoxy resins. Epoxidized aldehyde novolak resin, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, amine compound such as p-aminophenol, diaminodiphenylmethane, isocyanuric acid and epichlorohydrin Glycidylamine type epoxy resins obtained by the above reaction, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, and alicyclic epoxy resins. Be used et alone may be used in combination of two or more. Among these, a liquid bisphenol type epoxy resin is preferable from the viewpoint of fluidity, and a liquid glycidylamine type epoxy resin is preferable from the viewpoint of heat resistance, adhesiveness, and fluidity. It is particularly preferable to use a liquid bisphenol type epoxy resin and a liquid glycidylamine type epoxy resin in combination.

Two epoxy resin mentioned above may be also used in the two or more combining viewed used alone either one, but the amount thereof, to liquid epoxy resin total amount in order to exhibit its performance In total, it is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more.

  Further, in the liquid resin composition for electronic parts of the present invention, a solid epoxy resin can be used in combination as long as the effect of the present invention is achieved, but the solid resin used in combination from the viewpoint of fluidity during molding. The epoxy resin is preferably 20% by mass or less based on the total amount of the epoxy resin. Further, the purity of these epoxy resins, particularly the amount of hydrolyzable chlorine, is preferably less because it relates to the corrosion of aluminum wiring on ICs and other elements. In order to obtain a liquid resin composition for electronic parts having excellent moisture resistance, 500 ppm. The following is preferable. Here, the amount of hydrolyzable chlorine is a value obtained by dissolving 1 g of an epoxy resin of a sample in 30 ml of dioxane, adding 5 ml of a 1N-KOH methanol solution and refluxing for 30 minutes, and then obtaining by potentiometric titration. is there.

  The curing agent of component (A2) used in the present invention is preferably liquid at normal temperature. As the curing agent, an amine having a liquid aromatic ring, an acid anhydride, or the like may be included. Examples of those containing an amine having an aromatic ring include diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene. 1,3,5-triethyl-2,6-diaminobenzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,5,3 ′, 5′-tetramethyl-4,4′-diamino And diphenylmethane. These liquid aromatic amine compounds are, for example, commercially available products such as EpiCure-W, EpiCure-Z (Japan Epoxy Resin Co., Ltd., trade name), Kayahard AA, Kayahard AB, Kayahard AS (Nipponization) Yakuhin Co., Ltd., trade name), Totoamine HM-205 (Toto Kasei Co., Ltd., trade name), Adeka Hardener EH-101 (ADEKA, trade name), Epomic Q-640, Epomic Q-643 (Mitsui Chemicals) Company, product name), DETDA80 (Lonza, product name), etc. are available, and these may be used alone or in combination of two or more.

  As the liquid aromatic amine contained in the curing agent, 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine are preferable from the viewpoint of storage stability, and the curing agent is any one of these or these It is preferable to use a mixture of Examples of diethyltoluenediamine include 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine, and these may be used alone or as a mixture. Those containing 60% by weight or more of 3,5-diethyltoluene-2,4-diamine are preferred.

  Examples of the acid anhydride as the curing agent include phthalic anhydride, maleic anhydride, methyl hymic anhydride, hymic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, methyl Tetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, methylhexahydrophthalic acid, benzophenonetetracarboxylic anhydride, trimellitic anhydride Trialkyltetrahydrophthalic anhydride, dodecenyl obtained from Diels-Alder reaction from acid, pyromellitic anhydride, methyltetrahydrophthalic anhydride, hydrogenated methylnadic anhydride, maleic anhydride and diene compound Anhydrous Various cyclic acid anhydride such as click acid.

  Further, the liquid resin composition for electronic parts of the present invention may be other than aromatic amines and acid anhydrides as long as the effects of the present invention are achieved, and in addition, phenolic curing agents. The hardening | curing agent generally used with the liquid resin composition for electronic components, such as these, can be used together, and a solid hardening | curing agent can also be used together.

  The equivalent ratio of (A1) epoxy resin and (A2) curing agent is not particularly limited, but in order to suppress each unreacted component to a small amount, 0.7 equivalent or more and 1.6 equivalent of curing agent with respect to the epoxy resin. It is preferable to set the following range, 0.8 equivalents or more and 1.4 equivalents or less are more preferable, and 0.9 equivalents or more and 1.2 equivalents or less are more preferable.

  (B) Examples of inorganic fillers include fused silica, deflagration silica obtained by deflagration method, silica such as crystalline silica, alumina such as calcium carbonate, clay, and alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate , Powders of potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, or the like, or spherical beads or glass fibers. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. These inorganic fillers may be used alone or in combination of two or more. Of these, fused silica and deflagration silica are preferred, and spherical silica is more preferred from the viewpoint of fluidity and permeability into the fine gaps of the liquid resin composition for electronic parts.

  The particle diameter of the inorganic filler (B) is preferably in the range of 0.2 μm to 20 μm, particularly in the case of spherical silica, and in the range of 0.3 μm to 10 μm. More preferably, those in the range of 0.3 μm to 3 μm are particularly preferable. If the average particle size is less than 0.2 μm, the dispersibility in the liquid resin tends to be inferior and the viscosity tends to be inferior in the flow characteristics. If the average particle size exceeds 20 μm, the liquid resin composition for electronic parts tends to be settled. As a result, the permeability / fluidity to the fine gaps tends to decrease, and voids and unfilling tend to occur. (B) If the inorganic filler has a peak of 0.3 μm or more in the laser diffraction method, the smaller the value is 3 μm or less, the lower the viscosity of the liquid resin composition, while the The effect of suppressing the occurrence of leaping is enhanced. Therefore, when priority is given to improving the reliability of the semiconductor device, it is practical to use an inorganic filler whose peak in the laser diffraction method is in the range of 0.3 μm to 3 μm.

  (C) Examples of the inorganic filler having a peak of 100 nm or less in the laser diffraction method include silica such as fused silica, deflagration silica and crystalline silica, alumina such as calcium carbonate, clay and alumina, silicon nitride, silicon carbide, Examples thereof include powders such as boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, beads formed by spheroidizing them, and glass fibers. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. These inorganic fillers may be used alone or in combination of two or more. Of these, fused silica and deflagration silica are preferred, and spherical silica is more preferred from the viewpoint of fluidity and permeability into the fine gaps of the liquid resin composition for electronic parts.

  (C) The particle size of the inorganic filler having a peak of 100 nm or less in the laser diffraction method is preferably in the range of 50 μm or less in the laser diffraction method, particularly in the case of spherical silica. By being 100 nm or less, separation of the resin and the inorganic filler can be suppressed, and viscosity reduction, suppression of voids, bleed and creep, and good fillet formation can be exhibited.

  The content of the inorganic filler in which the (B) inorganic filler and the (C) inorganic filler are combined is in the range of 67% by mass to 77% by mass of the entire liquid resin composition for electronic components, preferably It is 68 mass% or more and 75 mass% or less. When the blending amount is 67% by mass or more, not only the thermal expansion coefficient tends to be small and the temperature cycle resistance tends to be excellent, but also the generation of voids can be suppressed, and further bleeding and creeping can be sufficiently suppressed. can do. By setting it as 77 mass% or less, the fall of the fluidity | liquidity by the increase in the viscosity of the liquid resin composition for electronic components, permeability, and dispense property can fully be suppressed. Moreover, it is preferable that content of the said (C) inorganic filler is 0.1-10 mass% with respect to the whole liquid resin composition for electronic components. (C) When content of an inorganic filler shall be 0.1 mass% or more, the viscosity reduction effect of the liquid resin composition for electronic components and the suppression effect of a bleed and creep can be expressed. Moreover, the content of (C) inorganic filler shall be 10 mass% or less, and the fall of the osmosis | permeability and dispensing property by the increase in the viscosity of the liquid resin composition for electronic components can be suppressed.

  In the liquid resin composition for electronic parts of the present invention, when an epoxy resin containing (A1) an epoxy resin and (A2) a curing agent is used as the (A) resin, the flexibilizer and surface activity described below are used. By containing at least one selected from the group consisting of an agent, an ion trapping agent, an effect accelerator, a coupling agent and an antioxidant, it is possible to further improve the characteristics and functions.

  The flexibilizing agent can be blended from the viewpoint of improving the thermal shock resistance and reducing the stress on the semiconductor element. There are no particular restrictions on the type of the flexibilizing agent, but rubber particles are preferable. For example, styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber ( Rubber particles such as UR) and acrylic rubber (AR). Among these, rubber particles containing acrylic rubber are preferable from the viewpoint of heat resistance and moisture resistance, and core-shell type acrylic polymers, that is, core-shell type acrylic rubber particles are more preferable.

  Silicone rubber particles can also be suitably used as a flexibilizer other than those described above. For example, a polyorganosiloxane such as linear polydimethylsiloxane, polymethylphenylsiloxane, or polydiphenylsiloxane is crosslinked. Silicone rubber particles, those obtained by coating the surface of silicone rubber particles with a silicone resin, core-shell polymer particles comprising a core of solid silicone particles obtained by emulsion polymerization and the like, and a shell of an organic polymer such as an acrylic resin, etc. It is done. These silicone polymer particles can be used in an amorphous or spherical shape, but in order to keep the viscosity related to the moldability of the liquid resin composition for electronic parts low, a spherical one is used. It is preferable to use it. These silicone polymer particles are commercially available from Toray Dow Corning Silicone Co., Ltd. and Shin-Etsu Chemical Co., Ltd.

  The primary particle diameter of these flexibilizers is preferably finer in order to uniformly modify the composition, and the average primary particle diameter is preferably in the range of 0.05 μm to 10 μm. More preferably, it is in the range of 1 μm or more and 5 μm or less. When the average particle size is 0.05 μm or more, there is a tendency to suppress a decrease in dispersibility in the liquid epoxy resin composition. By setting the average particle size to 10 μm or less, an effect of reducing stress can be expected. The liquid resin composition for parts tends to be able to suppress a decrease in permeability and fluidity into fine gaps and sufficiently suppress generation of voids and unfilled.

  The blending amount of these flexibilizers is preferably set in the range of 1% by mass to 30% by mass of the entire liquid resin composition for electronic parts excluding the filler, more preferably 2% by mass to 20%. It is below mass%. When the blending amount of the rubber particles is 1% by mass or more, a low stress effect can be expected, and when it is 30% by mass or less, the moldability (flow characteristics) due to the increase in viscosity of the liquid resin composition for electronic parts. It is possible to suppress the decrease.

  The surfactant can be blended from the viewpoint of reducing voids during molding and improving adhesive strength by improving wettability to various adherends. The type of the surfactant is not particularly limited, but a nonionic surfactant is preferable. For example, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester , Polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkyl alkanolamide, polyether modified silicone, aralkyl modified silicone, polyester modified silicone, poly Examples of the surfactant include acrylic, and these may be used alone or in combination of two or more. These surfactants are commercially available from Big Chemie Japan, Kao Corporation and the like.

  Further, a silicone-modified epoxy resin can be added as a surfactant. The silicone-modified epoxy resin can be obtained as a reaction product of an organosiloxane having a functional group that reacts with an epoxy group and an epoxy resin, but is preferably liquid at room temperature. Examples of organosiloxanes having functional groups that react with epoxy groups are dimethylsiloxane, diphenylsiloxane, methylphenyl having at least one amino group, carboxyl group, hydroxyl group, phenolic hydroxyl group, mercapto group, etc. in one molecule. Examples thereof include siloxane. The weight average molecular weight of the organosiloxane is preferably in the range of 500 or more and 5000 or less. The reason for this is that if it is less than 500, the compatibility with the resin system becomes too good and the effect as an additive is not exhibited, and if it exceeds 5000, it becomes incompatible with the resin system. This is because exudation occurs and the adhesiveness and appearance are impaired. The epoxy resin for obtaining the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin system of the liquid resin composition for electronic parts, and is generally used for the liquid resin composition for electronic parts. For example, glycidyl ether type epoxy resins, orthocresol novolac type epoxy resins obtained by the reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like with epichlorohydrin Glycidyl ester type obtained by reaction of a polybasic acid such as phthalic acid and dimer acid with epichlorohydrin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of phenols and aldehydes Glycidylamine type epoxy resin obtained by reaction of polyamine such as poxy resin, diaminodiphenylmethane, isocyanuric acid and epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, alicyclic epoxy Resins and the like can be mentioned, and these may be used alone or in combination of two or more, but those at room temperature are preferred.

  The addition amount of the surfactant is preferably 0.01% by mass or more and 1.5% by mass or less, and more preferably 0.05% by mass or more and 1% by mass or less with respect to the entire liquid resin composition for electronic parts. If it is 0.01% by mass or more, a sufficient addition effect can be obtained, and if it is 1.5% by mass or less, exudation that occurs from the surface of the cured product at the time of curing is difficult to occur, and the adhesive strength is reduced due to exudation. There is a tendency to be able to suppress.

  When the liquid resin composition for electronic parts of the present invention has an epoxy resin suitable as the resin (A), ions can be added as necessary within the range not impairing the filling property and fluidity when applied to a wiring board and a semiconductor device. A trapping agent can be contained from the viewpoint of improving migration resistance, moisture resistance and high temperature storage characteristics. There is no restriction | limiting in particular as an ion trap agent, A conventionally well-known thing can be used, Especially the hydrotalcite represented by the following compositional formula (I) or the hydrous oxide of bismuth represented by (II) is preferable.

(Chemical formula 1)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (I)
(In formula (I), 0 <X ≦ 0.5, m is a positive number.)
(Chemical formula 2)
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)

  The addition amount of these ion trapping agents is preferably 0.1% by mass or more and 3.0% by mass or less, more preferably 0.3% by mass or more and 1.5% by mass or less of the entire liquid resin composition for electronic parts. . The average particle size of the ion trapping agent is preferably 0.1 μm or more and 3.0 μm or less, and the maximum particle size is preferably 10 μm or less. The compound of the above formula (I) is commercially available as DHT-4A (Kyowa Chemical Industry Co., Ltd., trade name). Moreover, the compound of the said formula (II) is available as IXE500 (Toagosei Co., Ltd., brand name) as a commercial item. Further, other anion exchangers can be added as necessary. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Examples thereof include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like, and these can be used alone or in combination of two or more.

  The curing accelerator used in the epoxy resin suitable as the (A) resin of the present invention is to accelerate the reaction of the curing agent containing the liquid epoxy resin (A1) and the liquid aromatic amine (A2). For example, 1,8-diaza-bicyclo (5,4,0) undecene-7,1,5-diaza-bicyclo (4,4) can be used without limitation. 3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and other cycloamidine compounds, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol , Tertiary amine compounds such as tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Nilimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, imidazole compounds such as 2-heptadecylimidazole, trialkylphosphine such as tributylphosphine, dimethyl Organic phosphines such as dialkylarylphosphine such as phenylphosphine, alkyldiarylphosphine such as methyldiphenylphosphine, triphenylphosphine, alkyl-substituted triphenylphosphine, and these compounds; Inic acid, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone A compound having intramolecular polarization formed by adding a quinone compound such as 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, a compound having a π bond such as diazophenylmethane and phenol resin, And derivatives thereof, and further, phenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate and the like. You may use it combining. Moreover, as a curing accelerator having a potential, core-shell particles formed by coating a shell having a normal temperature solid amino group as a core and a shell of a normal temperature solid epoxy compound can be cited. Amicure (Ajinomoto Co., Inc.) is commercially available. Company, trade name), NovaCure (Asahi Kasei Chemicals Corporation, trade name) in which a microencapsulated amine is dispersed in a bisphenol A type epoxy resin and a bisphenol F type epoxy resin can be used.

  Of these, imidazole derivatives are preferable from the viewpoint of a balance between curing acceleration and reliability, and 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4- which are imidazole derivatives having a phenyl group and a hydroxyl group as substituents. More preferred is Novacure (Asahi Kasei Chemicals Corporation, trade name) in which methyl-5-hydroxymethylimidazole or microencapsulated amine is dispersed in bisphenol A type epoxy resin and bisphenol F type epoxy resin to provide the potential. More preferred are -phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

  The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but a range of 0.2% by mass to 5% by mass with respect to the weight of the total epoxy resin is preferable. A range of 0.5 mass% to 3 mass% is more preferable. Since a sufficient addition effect of the curing accelerator can be obtained by setting it to 0.2% by mass or more, generation of voids during molding can be more sufficiently suppressed, and the warp reduction effect tends to be sufficient, By setting it as 5 mass% or less, it becomes unnecessary to worry about the fall of storage stability.

  When a suitable epoxy resin is used as the resin (A) in the liquid resin composition for electronic parts of the present invention, the interface between the resin and the inorganic filler or the resin and the component of the electronic part is strengthened as necessary. For this purpose, a coupling agent can be used. These coupling agents are not particularly limited and conventionally known ones can be used. For example, silane compounds having primary and / or secondary and / or tertiary amino groups, epoxy silane, mercaptosilane, Examples thereof include various silane compounds such as alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as A seed may be used independently or may be used in combination of 2 or more types.

  When a suitable epoxy resin is used as the resin (A) in the liquid resin composition for electronic parts of the present invention, an antioxidant can be used. As the antioxidant, a conventionally known one can be used. For example, as a compound having a phenol compound antioxidant and having at least one alkyl group at the ortho position of the phenol nucleus, 2,6-di-t-butyl- 4-methylphenol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-tert-butylphenol), 3, 9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 .5] undecane, 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate], N, N′-hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], isooctyl-3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 4,6-bis (dodecylthio) Methyl) -o-cresol, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, 2,4-1bis [(octylthio) methyl] -o-cresol 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, 2-t-butyl-6- (3-t-butyl- 2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl Acrylate, 2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 2,6-di-t-butyl-4-ethylphenol, 1,1,3-tris (2-methyl-4- Hydroxy-5-t-butylphenyl ) Butane, triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 2,5,7,8-tetramethyl-2 (4 ′, 8 ′, 12′-trimethyltridecyl ) Chroman-6-ol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like. As dicyclohexylamine, D-CHA-T (Shin Nihon Rika Co., Ltd., trade name) and the like are commercially available, and derivatives thereof include dicyclohexylamine ammonium nitrite, N, N-di (3-methyl-cyclohexyl). Amine), N, N-di (2-methoxy-cyclohexyl) amine, N, N-di (4-bromo-cyclohexyl) amine and the like. Organic sulfur compound-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityltetrakis (3-lauryl thiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,2 -Thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,6-bis (dodecylthiomethyl) -o-cresol, 2,4-1bis [( Octylthio) methyl] -o-cresol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- Examples of amine compound-based antioxidants such as 1,3,5-triazine include N, N′-diallyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, 2 , 4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, etc. Phyto, triphenyl phosphite, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris (2,4-di-t-butylphenyl) phosphite, 2-[[2 , 4,8,10-Tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -N, N-bi [2-{[2,4,8,10-tetrakis (1,1dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy} -ethyl] Ethanamine, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2 ] Dioxaphosphepine, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, and the like. One of these may be used alone, or two or more may be used in combination. In addition, in the said phenol compound type antioxidant, in addition to the phenol hydroxyl group, the compound which contains at least 1 or more of a phosphorus atom, a sulfur atom, and an amine in the same molecule was mentioned repeatedly.

  In the liquid resin composition such as an epoxy resin composition for liquid sealing or an acrylic resin used as the liquid resin composition for electronic parts of the present invention, a solvent (D) is blended as necessary for reducing the viscosity. Can do. In particular, when a solid epoxy resin and a curing agent are used as one component of the epoxy resin composition, it is necessary to add a solvent in order to obtain a liquid composition.

  (D) The solvent is not particularly limited, but alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, ketone solvents such as acetone and methyl ethyl ketone, ethylene glycol ethyl ether, ethylene glycol methyl ether, and ethylene. Glycol ether solvents such as glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate, lactone solvents such as butyrolactone, valerolactone, caprolactone, dimethylacetamide, dimethylformamide, etc. Examples include amide solvents, toluene, xylene and other organic solvents. Even if one of these is used alone, two or more The may be used in combination. Among these, a solvent having a boiling point of 170 ° C. or higher is preferable from the viewpoint of avoiding bubble formation due to rapid volatilization during heat curing.

  The amount of the organic solvent is not particularly limited as long as it does not form bubbles, but is preferably 10% by mass or less with respect to other resin compositions such as an epoxy resin composition for liquid sealing or an acrylic resin. 5 mass% or less is more preferable.

  The liquid resin composition for liquid sealing such as an epoxy resin composition for liquid sealing or an acrylic resin used as the liquid resin composition for electronic components of the present invention, as other additives, a coloring agent such as a dye, carbon black, a diluent, A leveling agent, an antifoaming agent, etc. can be mix | blended as needed.

  The liquid resin composition for electronic parts of the present invention can be prepared by any method as long as the above various components can be uniformly dispersed and mixed. However, as a general method, a component having a predetermined blending amount is weighed. It can be obtained by mixing, kneading using a raking machine, mixing roll, planetary mixer or the like, and defoaming as necessary.

  The electronic component device obtained by sealing the element with the liquid resin composition for electronic components obtained in the present invention includes a lead frame, a wired tape carrier, a rigid and flexible wiring board, a supporting member such as glass and a silicon wafer. In addition, an active element such as a semiconductor chip, transistor, diode, thyristor, etc., an element such as a passive element such as a capacitor, a resistor, a resistor array, a coil, or a switch is mounted on the liquid resin composition for electronic components of the present invention. Examples thereof include an electronic component device obtained by sealing with an object. In particular, a flip-chip bonded semiconductor device in which a semiconductor element is connected to a wiring formed on a rigid and flexible wiring board or glass by a bump is an object. Specific examples include semiconductor devices such as flip chip BGA / LGA and COF (Chip On Film), and the liquid resin composition for electronic components obtained by the present invention is an underfill for flip chip with excellent reliability. Suitable as a material. In the field of flip chip in which the liquid resin composition for electronic parts of the present invention is particularly suitable, the bump material for connecting the wiring substrate and the semiconductor element is not a conventional lead-containing solder, but a lead-free material such as Sn-Ag-Cu. It is a flip chip semiconductor component using solder, and good reliability can be maintained even for a flip chip having a lead-free solder bump connection that is physically brittle compared to conventional lead solder. Furthermore, it is suitable for an element whose semiconductor element size is 2 mm or more on the longer side, and for flip chip connection in which the distance between the wiring board constituting the electronic component and the bump connection surface of the semiconductor element is 200 μm or less. In contrast, it is possible to provide a semiconductor device that exhibits good fluidity and filling properties and excellent reliability such as moisture resistance and thermal shock resistance. In recent years, an interlayer insulating film having a low dielectric constant is formed on a semiconductor element as the speed of the semiconductor element increases. However, these low dielectric insulators have low mechanical strength and are liable to break down due to external stress. . This tendency becomes more prominent as the element becomes larger, and the stress reduction from the underfill material is required. The dielectric layer having a semiconductor element size of 2 mm or more on the longer side and a dielectric constant of 3.0 or less. Excellent reliability can also be provided for a flip-chip semiconductor device on which a semiconductor element having the above is mounted.

  Examples of a method for sealing an element using the liquid resin composition for electronic parts of the present invention include a dispensing method, a casting method, and a printing method. In the present invention, when a semiconductor device in which a semiconductor element is flip-chip bonded by a bump connection to a rigid and flexible wiring board or a wiring formed on glass is used as a target, the semiconductor element is mainly sealed by filling with a dispense method. To do.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.

  The test methods of the characteristic tests performed in the examples and comparative examples are summarized below. The measurement of the viscosity and impregnation time of the liquid resin composition for electronic parts used, the observation of voids, the observation of bleed and the observation of creeping were performed by the following methods and conditions.

  The semiconductor device used for the evaluation has an element size of 20 × 20 × 0.725 tmm, bumps of lead-free solder, bump pitch of 150 μm, number of bumps of 14884, substrate size of 35 × 35 × 1 tmm, and core of E- 679FG (G) (Hitachi Chemical Co., Ltd., trade name) and solder resist are AUS703 (Taiyo Ink Manufacturing Co., Ltd., trade name).

  The semiconductor device was produced by underfilling a liquid resin composition for electronic components by a dispense method and curing at 165 ° C. for 2 hours. The curing conditions for various test pieces were also the same.

The produced liquid resin compositions for electronic parts of Examples and Comparative Examples were evaluated by the following tests. The evaluation results are shown in Table 2 below.
(1) Viscosity The viscosity at 110 ° C. of the liquid resin composition for electronic parts was measured using a rheometer (TA Instruments, AR2000).
(2) Impregnation time The semiconductor device is placed on a hot plate heated to 110 ° C., and a predetermined amount of the liquid resin composition for electronic components is dropped on the side surface (one side) of the chip using a dispenser. The time until penetration into the opposite side was measured.
(3) Void observation The inside of the semiconductor device produced by underfilling the liquid resin composition for electronic components was observed with an ultrasonic flaw detector AT-5500 (Hitachi Construction Machinery Co., Ltd.) to examine the presence or absence of voids.
(4) Bleed observation A substrate in contact with a fillet of a semiconductor device produced by underfilling a liquid resin composition for electronic components was observed with a microscope, and the length of resin oozing was measured.
(5) Creeping observation The back surface of the semiconductor element of the semiconductor device produced by underfilling the liquid resin composition for electronic components was observed with a microscope, and the length of resin oozing was measured.

(Examples 1-8, Comparative Examples 1-2)
Liquid epoxy resin with epoxy equivalent 160 obtained by epoxidizing bisphenol F as a liquid epoxy resin (epoxy resin 1), trifunctional liquid epoxy resin with epoxy equivalent 95 obtained by epoxidizing aminophenol (epoxy resin 2), curing agent Diethyltoluenediamine (curing agent) having an active hydrogen equivalent of 45 as a curing accelerator, 2-phenyl-4-methyl-5-hydroxymethylimidazole (curing accelerator) as a curing accelerator, and the surface of dimethyl type solid silicone rubber particles as a flexibilizing agent Spherical silicone particles having an average particle size of 2 μm , modified with an epoxy group, γ-glycidoxypropyltrimethoxysilane as a coupling agent, and carbon black as a colorant (Mitsubishi Chemical Corporation, trade name MA-100) Bismuth-based ion traps as ion trapping agents (Toagosei Co., Ltd., trade name IXE-500), 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy]-as an antioxidant 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, spherical silica having a peak of 3 μm in the laser diffraction method as the inorganic filler 1, and laser diffraction method as the inorganic filler 2 Spherical silica having a peak of 0.3 μm at 10 nm, spherical silica having a peak of 10 μm by laser diffraction as inorganic filler 3, spherical silica having a peak of 10 nm by laser diffraction as inorganic filler 4, and laser diffraction as inorganic filler 5 Spherical silica with a peak of 20 nm at 50 nm, spherical silica with a peak of 50 nm by laser diffraction as the inorganic filler 6, and peak by laser diffraction as the inorganic filler 7 100 nm spherical silica and spherical silica having a peak of 250 nm in the laser diffraction method as the inorganic filler 8 were blended in the composition shown in Table 1 below, and kneaded and dispersed with a three-roller and a crusher capable of reducing pressure. Liquid resin compositions for electronic parts of Examples 1 to 8 and Comparative Examples 1 and 2 were prepared. In the liquid resin composition for electronic parts shown in Table 1, the content of the inorganic filler is 70% by mass with respect to the whole liquid resin composition for electronic parts.

Unit: parts by mass

  Various evaluation results are shown in Table 2 below.

  In Comparative Example 1 which does not include the inorganic filler (inorganic fillers 4 to 7) having a peak of 100 nm or less by (C) laser diffraction method in the present invention, the impregnation time was long because of high viscosity. In addition, voids thought to be caused by the disturbance of the flow front were observed. On the other hand, when Examples 1, 7, and 8 to which the inorganic filler 1 was applied were compared with Comparative Example 2, (C) the resin composition containing the inorganic filler having a peak of 100 nm or less by the laser diffraction method has a low viscosity. The impregnation time was shortened. Moreover, although no void was generated in all of the examples, it is considered that the effect of uniforming the tip flow was expressed by the inorganic filler having a peak of 100 nm or less by the laser diffraction method. Furthermore, as shown in the Examples, it is considered that it is effective in suppressing bleeding and creeping, and the effect of suppressing the separation between the resin and the inorganic filler was also exhibited.

  Further, when Examples 1 to 3 were compared with Comparative Example 1, they were excellent in terms of viscosity, impregnation time, void, bleed, and creep, and this effect was (C) inorganic having a peak of 100 nm or less by laser diffraction method. It was found to be obtained with a filler. Further, when comparing the evaluation results between Examples 1 to 3, Examples 1 and 2 have a shorter bleed length and creeping length than Example 3, and thus the reliability of the semiconductor device. From the viewpoint of improvement, it is preferable to use an inorganic filler having a peak in the laser diffraction method in the range of 0.3 to 3 μm as the inorganic filler (B). Here, Examples 1 and 2 have a slightly higher viscosity than Example 3, but are in a practically acceptable range of viscosity.

  In Table 2, Examples 1 and 4 having (B) the inorganic filler 1 as the inorganic filler and (C) the inorganic filler having a peak of 100 nm or less by laser diffractometry, the particle size of each being changed. In contrast to Comparative Example 2, when compared to Comparative Example 2, all of (D) inorganic filling having a peak of 10 to 100 nm by laser diffractometry (D) for reducing viscosity, shortening impregnation time, making voidless, and suppressing bleeding and creeping There is an effect of adding a material, and the effect is particularly remarkable by using an inorganic filler of 50 nm or less by laser diffraction method. On the other hand, in Comparative Example 2 in which an inorganic filler having a peak of 250 nm was added by the laser diffraction method, no void improvement effect was observed, and other items could only exhibit a fine improvement effect. This is considered because separation of the resin and the inorganic filler cannot be suppressed if the particle size is too large.

  As described above, in order to achieve the effect of the present invention, an inorganic filler having a peak of 100 nm or less is essential as an inorganic filler. However, by using an inorganic filler having a peak of 50 nm or less, further characteristics can be obtained. Improvements can be made.

(Examples 9-12, Comparative Examples 3-5)
Example 9 wherein the same epoxy resin and inorganic filler as shown in Table 1 were used, and the same amount as in Examples 1 to 8 was used to adjust the blending amounts shown in Table 3 below, and the contents of the inorganic filler were different. To 13 and Comparative Examples 3 to 5 were prepared.

Unit: parts by mass

  Various evaluation results are shown in Table 4 below.

  In Table 4, it can be seen from the comparison between Example 9 and Comparative Example 3 that voids are observed when the content of the inorganic filler is less than 67% by mass. Furthermore, when the content of the inorganic filler is small, the reliability of the semiconductor device tends to decrease due to the generation of stress and the decrease in bump connection retention. Further, as can be seen from the comparison between Example 13 and Comparative Example 5, the generation of voids can be seen even when the content of the inorganic filler exceeds 77% by mass. When the content of the inorganic filler increases, the reliability of the semiconductor tends to improve, but conversely, the increase in viscosity becomes remarkable and the impregnation time becomes long, so that the workability is inevitably lowered. Therefore, in the present invention, the content of the inorganic filler needs to be in the range of 67% by mass to 77% by mass with respect to the entire liquid resin composition for electronic parts. Furthermore, as shown in Examples 1 to 8 in Table 2 and Examples 9 to 13 in Table 4, if the content of the inorganic filler is in the range of 67 to 77% by mass, shortening of the impregnation time and bleeding and Creeping can be suppressed at the same time in a well-balanced manner.

  Further, as can be seen from the comparison between Examples 10-12 and Comparative Example 4, all of (D) laser diffraction method is used for reducing impregnation time, voidless formation, and suppression of bleed and creep. There is an effect of adding an inorganic filler having a peak. Furthermore, in Examples 10 and 11, impregnation time, bleed length, and creeping length were all shorter than in Example 12, and this was achieved by using an inorganic filler of 50 nm or less by laser diffraction. The remarkable effect of the invention can be obtained.

  Next, examples in which an acrylic resin is applied as the resin (A) used in the present invention will be described with reference to Examples 14 to 16 and Comparative Examples 6 to 7.

(Example 14)
75 parts by mass of dicyclopentanyl methacrylate (Fancryl FM-513: Hitachi Chemical Co., Ltd.), 25 parts by mass of polyethylene glycol # 400 dimethacrylate (Shin Nakamura Chemical Co., Ltd.), 1,1-di-t as a radical generator -0.4 part by mass of butylperoxycyclohexane and 227 parts by mass of the inorganic filler 2 (spherical silica having a peak of 3 μm by laser diffraction method) as the inorganic filler and the inorganic filler 4 (peak of 10 nm by the laser diffraction method) 7 parts by mass of spherical silica) were uniformly mixed to prepare a liquid resin composition for electronic parts. In the obtained liquid resin composition for electronic parts, the content of the inorganic filler is 70% by mass with respect to the whole liquid resin composition for electronic parts.

(Example 15)
75 parts by mass of dicyclopentanyl methacrylate (Fancryl FM-513: Hitachi Chemical Co., Ltd.), 25 parts by mass of polyethylene glycol # 400 dimethacrylate (Shin Nakamura Chemical Co., Ltd.), 1,1-di-t as a radical generator -Butyl peroxycyclohexane 0.4 part by mass and 261 parts by mass of the inorganic filler 3 (spherical silica having a peak of 10 μm by laser diffraction method) as the inorganic filler and the inorganic filler 6 (peak of 50 nm by laser diffraction method) A liquid resin composition for electronic parts was prepared by uniformly mixing 10 parts by weight of spherical silica). In the obtained liquid resin composition for electronic parts, the content of the inorganic filler is 73% by mass with respect to the whole liquid resin composition for electronic parts.

(Example 16)
75 parts by mass of dicyclopentanyl methacrylate (Fancryl FM-513: Hitachi Chemical Co., Ltd.), 25 parts by mass of polyethylene glycol # 400 dimethacrylate (Shin Nakamura Chemical Co., Ltd.), 1,1-di-t as a radical generator -0.4 part by mass of butylperoxycyclohexane and 227 parts by mass of the inorganic filler 2 (spherical silica with a peak of 3 μm by laser diffraction method) as the inorganic filler and the inorganic filler 7 (peak of 100 nm by the laser diffraction method) 7 parts by mass of spherical silica) were uniformly mixed to prepare a liquid resin composition for electronic parts. In the obtained liquid resin composition for electronic parts, the content of the inorganic filler is 70% by mass with respect to the whole liquid resin composition for electronic parts.

(Comparative Example 6)
75 parts by mass of dicyclopentanyl methacrylate (Fancryl FM-513: Hitachi Chemical Co., Ltd.), 25 parts by mass of polyethylene glycol # 400 dimethacrylate (Shin Nakamura Chemical Co., Ltd.), 1,1-di-t as a radical generator -Liquid resin composition for electronic parts is prepared by uniformly mixing 0.4 part by mass of butylperoxycyclohexane and 234 parts by mass of inorganic filler 2 (spherical silica having a peak of 3 μm by laser diffraction method) as an inorganic filler. did. In the obtained liquid resin composition for electronic parts, the content of the inorganic filler is 70% by mass with respect to the whole liquid resin composition for electronic parts.

(Comparative Example 7)
75 parts by mass of dicyclopentanyl methacrylate (Fancryl FM-513: Hitachi Chemical Co., Ltd.), 25 parts by mass of polyethylene glycol # 400 dimethacrylate (Shin Nakamura Chemical Co., Ltd.), 1,1-di-t as a radical generator -0.4 part by mass of butylperoxycyclohexane and 345 parts by mass of the inorganic filler 3 (spherical silica having a peak of 10 μm by laser diffraction method) as the inorganic filler and the inorganic filler 6 (peak of 50 nm by the laser diffraction method) 11 parts by mass of spherical silica) was uniformly mixed to prepare a liquid resin composition for electronic parts. In the obtained liquid resin composition for electronic parts, the content of the inorganic filler is 78% by mass with respect to the whole liquid resin composition for electronic parts.

  Using the liquid resin compositions for electronic components obtained in Examples 14 to 16 and Comparative Examples 6 to 7, the viscosity, impregnation time, void observation, bleed observation and creeping observation were performed in the same manner as in Examples 1 to 8. Various evaluations were performed. Various evaluation results are shown in Table 5 below. Here, the semiconductor device is underfilled by a dispense method using the liquid resin compositions for electronic components obtained in Examples 14 to 16 and Comparative Examples 6 to 7, and cured at 110 ° C. for 3 hours and further at 160 ° C. for 1 hour. It was produced by. The curing conditions for various test pieces were also the same.

  As shown in Table 5, when (A) an acrylic resin is used as the resin, as in the case of the epoxy resin, (D) by adding an inorganic filler having a peak of 10 to 100 nm by laser diffraction In addition, the impregnation time can be shortened, voidless, and bleeding and creeping can be suppressed (contrast between Example 14 and Comparative Example 6). Furthermore, in Example 14, the viscosity is lower than that in Example 16, the impregnation time, the bleed length, and the creeping length are all shortened, and an inorganic filler of 50 nm or less is used in the laser diffraction method. Thus, the remarkable effect of the present invention can be obtained. Further, as shown in Comparative Example 7, when the content of the inorganic filler exceeds 77% by mass, the increase in the viscosity becomes remarkable, the impregnation time becomes longer, and the generation of voids is slightly observed.

  When the epoxy resin compositions shown in Tables 2 and 4 and the acrylic resin composition shown in Table 5 are compared from the viewpoint of moldability and workability, it can be seen that the former is slightly better than the latter. Therefore, in this invention, it is suitable from the point of a moldability and workability | operativity to use an epoxy resin composition as a liquid resin composition for electronic components.

  As described above, the liquid resin composition for electronic parts of the present invention can reduce the viscosity of the liquid resin composition, so that the filling time can be shortened and the flow disturbance during the flow can be made uniform. Since voids can be suppressed and bleeding and creeping can be suppressed, an electronic component device having excellent moldability and reliability can be obtained by sealing an element using this liquid resin composition for electronic components. Therefore, it can be applied not only as an underfill material but also as a sealing material for a semiconductor device mounted with bare chips such as COB, COG, and TCP, and its industrial value is extremely high.

Claims (18)

  (A) a resin, (B) an inorganic filler, and (C) an inorganic filler having a peak of 100 nm or less by laser diffraction, and the (B) inorganic filler and the (C) inorganic filler were combined. The liquid resin composition for electronic parts whose content of an inorganic filler is 67-77 mass% of the said whole liquid resin composition for electronic parts.   The liquid resin composition for electronic components according to claim 1, wherein the inorganic filler (C) is an inorganic filler having a peak of 50 nm or less by a laser diffraction method.   The liquid resin composition for electronic components according to claim 1 or 2, wherein the inorganic filler (B) contains an inorganic filler having a peak in a laser diffraction method of 0.3 to 10 µm.   The liquid resin composition for electronic components according to any one of claims 1 to 3, comprising an inorganic filler having a peak in a laser diffraction method of 0.3 to 3 µm as the (B) inorganic filler. .   The liquid amount for electronic components as described in any one of Claims 1-4 whose compounding quantity of the said (C) inorganic filler is 0.1-10 mass% with respect to the said whole liquid resin composition for electronic components. Resin composition.   The viscosity at 110 ° C. is 0.2 Pa. The liquid resin composition for electronic parts as described in any one of Claims 1-5 which is s or less.   The liquid resin composition for electronic components according to any one of claims 1 to 6, wherein the (A) resin includes (A1) an epoxy resin and (A2) a curing agent.   Furthermore, the liquid resin composition for electronic components as described in any one of Claims 1-7 containing a softening agent.   Furthermore, the liquid resin composition for electronic components as described in any one of Claims 1-8 containing surfactant.   Furthermore, the liquid resin composition for electronic components as described in any one of Claims 1-9 containing an ion trap agent.   Furthermore, the liquid resin composition for electronic components as described in any one of Claims 1-10 containing a hardening accelerator.   Furthermore, the liquid resin composition for electronic components as described in any one of Claims 1-11 containing a coupling agent.   Furthermore, the liquid resin composition for electronic components as described in any one of Claims 1-12 containing antioxidant.   Furthermore, the liquid content composition for electronic components as described in any one of Claims 1-13 whose organic solvent content rate is 5% or less of the said whole electronic component liquid composition containing this organic solvent.   The electronic component and the wiring board are used for sealing a connection part of an electronic component device electrically connected via a connection part, and the gap between the electronic component and the wiring board is filled. The liquid resin composition for electronic components as described in any one of 1-14.   The liquid resin composition for electronic components according to claim 15, wherein the connection part does not contain lead.   The liquid resin composition for electronic components according to claim 15 or 16, wherein the connection part contains copper.   The electronic component apparatus sealed with the liquid resin composition for electronic components as described in any one of Claims 1-17.