JP5114935B2 - Liquid resin composition for electronic components, and electronic component device using the same - Google Patents

Description

  The present invention relates to a liquid resin composition for electronic components that is particularly suitable for sealing electronic component devices that require strict reliability, and an electronic component device that includes an element sealed with the 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 epoxy resin compositions have been widely used. This is because the epoxy resin is balanced in various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness 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.

In addition, to provide an epoxy resin composition for sealing excellent in moisture-resistant adhesive strength and low-stress property, and an electronic component device having high reliability (moisture resistance and thermal shock resistance) provided with an element sealed thereby. , (A) liquid epoxy resin, (B) curing agent containing liquid aromatic amine, (C) rubber particles, (D) epoxy resin composition for sealing containing inorganic filler, and for sealing An electronic component device including an element sealed with an epoxy resin composition is disclosed (for example, 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. In addition, the underfill material fills the gap between the wiring board and the semiconductor element, and then a certain amount of spots are formed on the periphery of the semiconductor element to form a fillet. However, if the shape of the fillet is not uniform, the fillet may be damaged during temperature cycling. May crack or peel off from the substrate or semiconductor element. The generation of such voids and the formation of non-uniform fillets greatly affects the reliability of the flip chip semiconductor device.

  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, a liquid resin composition for electronic parts having excellent fluidity in a narrow gap, no generation of voids, and excellent fillet-forming properties, and sealing by this An object of the present invention is to provide an electronic component device having high reliability (moisture resistance and thermal shock resistance).

  As a result of intensive studies to solve the above problems, the present inventors have achieved the above object by using a curing agent containing a liquid aromatic amine and a surfactant as the curing agent, and completed the present invention. It came to do.

  The present invention relates to the following.

1. A liquid resin composition for electronic parts used for sealing electronic parts, wherein (A) a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) a nonionic surfactant, (D) A liquid resin composition for electronic parts containing an inorganic filler.

2. A silicone-modified epoxy resin obtained by a reaction between an epoxy resin and an organosiloxane having a functional group that reacts with an epoxy group and a nonionic surfactant as the component (C) having a weight average molecular weight of 500 or more and 5000 or less. 2. The liquid resin composition for electronic parts as described in 1 above.

3. The liquid resin composition for electronic parts as described in 1 or 2 above, which is used in an electronic part apparatus for directly bump-connecting electronic parts on a wiring board.

4. The liquid resin composition for electronic parts as described in 3 above, wherein the bump is a metal containing no lead.

5. The electronic component according to 3 or 4 above, wherein the length of the long side of the electronic component is 5 mm or more, and the distance between the wiring board constituting the electronic component device and the bump connection surface of the electronic component is 80 μm or less. Liquid resin composition.

6. The electronic component according to any one of 3. to 5. above, wherein the electronic component is a semiconductor element having a dielectric layer having a dielectric constant of 3.0 or less, wherein the length of the long side of the electronic component is 5 mm or more. Liquid resin composition.

7. An electronic component device comprising an electronic component sealed with the liquid resin composition for electronic components according to any one of 1. to 6. above.

8. The electronic component device as described in 7 above, wherein the bump is a metal containing no lead.

9. The electronic component according to 7 or 8 above, wherein the length of the long side of the electronic component is 5 mm or more and the distance between the wiring board constituting the electronic component device and the bump connection surface of the electronic component is 80 μm or less. apparatus.

10. The electronic component as described in any one of 7 to 9 above, wherein the electronic component is a semiconductor element having a long side length of 5 mm or more and the electronic component having a dielectric layer having a dielectric constant of 3.0 or less. apparatus.

  Since the liquid resin composition for electronic parts of the present invention suppresses voids during molding by reducing the surface tension and has high adhesive strength with various substrates even after moisture absorption, this liquid resin composition for electronic parts Since the electronic component device having excellent reliability can be obtained by sealing the element using, its industrial value is great.

  The liquid epoxy resin of component (A) used in the present invention is not limited as long as it has one or more epoxy groups in one molecule and is liquid at room temperature, and is generally used in liquid resin compositions for electronic components. A liquid epoxy resin can be used. 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 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 resin obtained by the above reaction, linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid, alicyclic epoxy resin, etc. May be used in combination of two or more kinds thereof may be used alone. 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.

  The above two types of epoxy resins may be used alone or in combination of two or more, but the blending amount is based on the total amount of the liquid epoxy resin 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 (B) containing a liquid aromatic amine used in the present invention is not particularly limited as long as it contains an amine having a liquid aromatic ring at room temperature, and examples thereof include diethyltoluenediamine and 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'-diaminodiphenylmethane and the like. These liquid aromatic amine compounds are, for example, commercially available products such as jER Cure-W, jER Cure-Z (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Kayahard A-A, Kayahard AB, Kayahard AS ( Nippon Kayaku Co., Ltd. product name), Totoamine HM-205 (Toto Kasei Co., Ltd. product name), Adeka Hardener EH-101 (Asahi Denka Kogyo Co., Ltd. product name), Epomic Q-640, Epomic Q-643 (Trade name manufactured by Mitsui Chemicals, Inc.), DETDA80 (trade name manufactured by Lonza), 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. What contains 60 mass% or more of 3,5-diethyltoluene-2,4-diamine is preferable.

  In addition, the liquid resin composition for electronic parts of the present invention includes, in addition to a curing agent containing a liquid aromatic amine, an electron such as a phenolic curing agent or an acid anhydride as long as the effects of the present invention are achieved. Curing agents generally used in liquid resin compositions for parts can be used in combination, and solid curing agents such as solid amines and imidazole compounds can also be used in combination. Among these, solid amines are preferable from the viewpoint of heat resistance, and allylated phenol novolac resins are preferable from the viewpoint of fluidity.

  When other curing agents are used in combination, the blending amount of the curing agent (B) containing the liquid aromatic amine is preferably 60% by mass or more based on the total amount of the curing agent in order to exhibit its performance. The equivalent ratio of the component (A) and the epoxy resin containing the solid epoxy resin and the total amount of the (B) curing agent is not particularly limited. It is preferably set in the range of not less than 0.7 equivalents and not more than 1.6 equivalents, more preferably not less than 0.8 equivalents and not more than 1.4 equivalents, and still more preferably not less than 0.9 equivalents and not more than 1.2 equivalents.

  The surfactant of component (C) used in the present invention is not particularly limited as long as it is a nonionic surfactant. For example, polyoxyethylene alkyl ether type, polyoxyalkylene alkyl ether type, sorbitan fatty acid ester type, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide, polyether-modified silicone, aralkyl-modified silicone , Polyester-modified silicone and polyacrylic surfactants, among others, polyether-modified silicone surfactants and aralkyl-modified silicone surfactants are liquid resin groups for electronic components. Effect is in the surface tension reduction of thing. As these nonionic surfactants, for example, BYK-307, BYK-333, BYK-377, BYK-323 (trade names manufactured by Big Chemie Japan) and the like are available as commercial products. Further, a surfactant other than nonionic may be used in combination.

  Furthermore, a silicone-modified epoxy resin can be added as a nonionic 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. The silicone-modified epoxy resin is localized on the surface of the liquid and can reduce the surface tension of the liquid. As a result, the wettability is high and the fluid is easy to flow, which is effective in improving the permeability to a narrow gap and reducing entrainment voids.

  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. These organosiloxanes are, for example, commercially available products BY16-799, BY16-871, BY16-004 (trade name made by Toray Dow Corning Silicone), X-22-1821, KF-8010 (trade name made by Shin-Etsu Chemical). Etc. are available. The molecular structure of the organosiloxane may be either linear or branched. The silicone-modified epoxy resin is preferably obtained by reacting 50 to 150 parts by mass of a silicone component having a functional group capable of reacting with an epoxy group with respect to 100 parts by mass of the raw material epoxy resin.

The weight average molecular weight of the organosiloxane is preferably in the range of 500 to 5000, and more preferably in the range of 100 to 3000. 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 mm ² / s, the compatibility with the resin system becomes too bad and the silicone-modified epoxy resin becomes poor. This is because, during molding, separation and oozing occur and the adhesiveness and appearance are impaired. In the present invention, the weight average molecular weight is measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. Specifically, as GPC, a pump (L-6200 model manufactured by Hitachi, Ltd.), a column (TSKgel-G5000HXL and TSKgel-G2000HXL, both of which are trade names manufactured by Tosoh Corporation), a detector (L-manufactured by Hitachi, Ltd.) 3300RI type), and the result of measurement using tetrahydrofuran as an eluent at a temperature of 30 ° C. and a flow rate of 1.0 ml / min is referred to.

  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. Particularly preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin.

  In the present invention, various flexible agents can be blended from the viewpoint of improving thermal shock resistance and reducing stress on the semiconductor element. The flexible agent is not particularly limited, but rubber particles are preferable. Examples thereof include styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic. Examples thereof include rubber particles such as rubber (AR). Among these, rubber particles made of 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 the rubber particles other than those described above. For example, a silicone obtained by crosslinking a polyorganosiloxane such as a linear polydimethylsiloxane, polymethylphenylsiloxane, or polydiphenylsiloxane. Examples thereof include rubber particles, those obtained by coating the surface of silicone rubber particles with a silicone resin, and core-shell polymer particles comprising a core of solid silicone particles obtained by emulsion polymerization and a shell of an organic polymer such as an acrylic resin. 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 rubber particles is preferably finer in order to uniformly modify the composition, and the primary particle diameter is preferably in the range of 0.05 μm to 10 μm, preferably 0.1 μm or more. More preferably, it is in the range of 5 μm or less. If the primary particle size is less than 0.05 μm, the dispersibility in the liquid epoxy resin composition tends to be inferior, and if it exceeds 10 μm, the effect of reducing stress reduction tends to be low, and the fineness as a liquid resin composition for electronic components There is a tendency for the permeability and fluidity to the gap to be lowered, and voids and unfilling to occur easily.

  The blending amount of these rubber particles is preferably set in a range of 1% by mass or more and 30% by mass or less, and more preferably 2% by mass or more and 20% by mass of the entire liquid resin composition for electronic parts excluding the filler. It is as follows. When the blending amount of the rubber particles is less than 1% by mass, the low stress effect tends to be low, and when it exceeds 30% by mass, the viscosity of the liquid resin composition for electronic parts tends to increase and the moldability (flow characteristics) tends to be inferior. .

  Examples of the inorganic filler of the component (D) used together with the components (A) to (C) include silica such as fused silica and crystalline silica, alumina such as calcium carbonate, clay and alumina oxide, silicon nitride and silicon carbide. , Boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc., or spherical beads of these, glass fibers, etc. .

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 is 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 components.

  The average particle size of the inorganic filler is preferably in the range of 0.3 μm to 10 μm, and more preferably in the range of 0.5 μm to 5 μm, particularly in the case of spherical silica. If the average particle size is less than 0.5 μm, the dispersibility in the liquid resin tends to be inferior, or the liquid resin composition for electronic parts tends to have thixotropic properties and the flow properties tend to be inferior. If it exceeds 10 μm, filler sedimentation occurs. There is a tendency that it becomes easy, and the permeability / fluidity to the fine gap as the liquid resin composition for electronic parts tends to be lowered, and voids / unfilled tend to be caused. The blending amount of the inorganic filler is preferably set in the range of 20% by mass or more and 90% by mass or less of the entire liquid resin composition for electronic parts, more preferably 25% by mass or more and 80% by mass or less, and still more preferably. 30% by mass or more and 60% by mass or less. When the blending amount is less than 20% by mass, the effect of reducing the thermal expansion coefficient tends to be low. When the blending amount exceeds 90% by mass, the viscosity of the liquid resin composition for electronic parts increases, and the fluidity / penetration and dispensing properties decrease. Tend to invite.

  In the liquid resin composition for electronic parts of the present invention, a coupling agent can be used for the purpose of strengthening the interfacial adhesion between the resin and the inorganic filler or between the resin and the component of the electronic part, if necessary. 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 (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) 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. The blending amount of the coupling agent is preferably 0.1 to 3.0% by mass, more preferably 0.2 to 2.5% by mass, and more preferably 0.2 to 2.5% by mass with respect to the liquid resin composition. More preferably, it is 2.5 mass%. If the amount is less than 0.1% by mass, the adhesion between the substrate and the cured product of the liquid resin composition tends to decrease, and if it exceeds 3.0% by mass, voids tend to be generated.

In the liquid resin composition for electronic parts of the present invention, a curing accelerator that accelerates the reaction between the epoxy resin containing the liquid epoxy resin (A) and the curing agent (B) containing the liquid aromatic amine is used as necessary. Can do. There is no restriction | limiting in particular in a hardening accelerator, A conventionally well-known thing can be used. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8- Cycloamidine compounds such as diaza-bicyclo (5,4,0) undecene-7 and derivatives thereof,
Tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof;
2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 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, 2-hepta Imidazole compounds such as decylimidazole and derivatives thereof,
Trialkylphosphine such as tributylphosphine, dialkylarylphosphine such as dimethylphenylphosphine, alkyldiarylphosphine such as methyldiphenylphosphine, organic phosphines such as triphenylphosphine and alkyl group-substituted triphenylphosphine, and derivatives thereof,
And maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl Molecule formed by adding a quinone compound such as -1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, a compound having a π bond such as diazophenylmethane, phenol resin Examples thereof include compounds having internal polarization, and derivatives thereof, and further include phenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. The seeds may be used alone or in combination of two or more.

  Further, as a curing accelerator having a potential, a core-shell particle formed by coating a shell of a normal temperature solid epoxy compound with a core having a normal temperature solid amino group, particularly an imidazole derivative as a core, is a commercially available product. Amicure (trade name, manufactured by Ajinomoto Co., Inc.), Novacure (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) in which a microencapsulated imidazole derivative is dispersed in a bisphenol A type epoxy resin or a bisphenol F type epoxy resin can be used. A latent curing accelerator is a substance that exhibits a curing acceleration function under conditions such as a specific temperature. For example, a normal curing accelerator is protected by a microcapsule or the like or added with various compounds. There are things that are structured. In this case, when a specific temperature is exceeded, the curing accelerator is released from the microcapsules and adducts.

  The curing accelerator is preferably an imidazole derivative. From the viewpoint of achieving both curability and moldability, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 4-Diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine and 2-heptadecylimidazole are preferred, and from the viewpoint of storage stability, the above Novacure (trade name, manufactured by Asahi Kasei Chemicals) is Particularly preferred are 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole, which are imidazole derivatives having a phenyl group and a hydroxyl group as a substituent.

  Although the compounding quantity of a hardening accelerator will not be restrict | limited especially if the hardening acceleration effect is achieved, it is 0.2 mass% with respect to the epoxy resin containing (A) liquid epoxy resin and solid epoxy resin. The content is preferably 5% by mass or less and more preferably 0.5% by mass or more and 3% by mass or less. If it is less than 0.2% by mass, the curability at low temperature tends to be inferior, and if it exceeds 5% by mass, the curing rate is too fast and it becomes difficult to control, and the storage stability such as pot life and shell life is inferior. Tend. On the other hand, when the amount is less than 0.2% by mass, the effect of adding the curing accelerator is not sufficiently exhibited, and as a result, generation of voids during molding cannot be suppressed and the effect of reducing warpage tends to be insufficient.

  It should be noted that the curing accelerator is not a curing accelerating component alone but is dispersed when blending a curing accelerator component, an epoxy compound, and a curing accelerator having an epoxy resin component like a latent curing accelerator. Considering everything as a curing accelerator, including epoxy resins, the blending amount with respect to other epoxy resins is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, 0.8 mass% or more and 10 mass% or less are more preferable. If it is less than 0.1% by mass, the curability at low temperature tends to be inferior, and if it exceeds 40% by mass, the curing rate is too high and control becomes difficult, and the storage stability such as pot life and shell life is inferior. Tend.

  Further, the liquid resin composition for electronic parts of the present invention can contain an ion trap agent as necessary from the viewpoint of improving the migration resistance, moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. 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 not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but from the viewpoint of migration resistance, it is 0.1% by mass or more based on the liquid resin composition. 0 mass% or less is preferable, More preferably, it is 0.3 mass% or more and 1.5 mass% or less. 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. In addition, the compound of the said formula (I) is available as Kyowa Chemical Industry Co., Ltd. brand name DHT-4A as a commercial item. The compound of the above formula (II) is commercially available as IXE500 (trade name, manufactured by Toagosei Co., Ltd.). In addition, other anion exchangers can be added as necessary, for example, hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, etc., and these can be used alone or in combination of two or more. They can be used in combination.

  In the liquid resin composition for electronic parts of the present invention, as other additives, coloring agents such as dyes, carbon black, titanium oxide, and lead tan, flame retardants, diluents, leveling agents, other flexing agents, An antifoaming agent etc. can be mix | blended as needed.

  A brominated epoxy resin or antimony trioxide can be used as the flame retardant, but it is preferable to use a halogen-free or non-antimony flame retardant. For example, red phosphorus coated with a thermosetting resin such as red phosphorus, phenol resin, phosphorous ester, phosphorus compound such as triphenylphosphine oxide, melamine, melamine derivative, melamine modified phenolic resin, compound having triazine ring, Nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, metal complex compounds such as dicyclopentadienyl iron, zinc oxide, zinc stannate, zinc borate, and zinc molybdate Examples thereof include zinc compounds, metal oxides such as iron oxide and molybdenum oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and composite metal hydroxides represented by the following composition formula (III).

(Chemical formula 3)
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 different metal elements, a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number. Show.)
M ¹ , M ² and M ^{3 in the} composition formula (III) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ is a metal element of the third period, group IIA alkaline earth metal elements, IVB group, IIB group, VIII, IB, selected from metal elements belonging to group IIIA and group IVA, it is preferable that M ² is selected from transition metal elements of group IIIB～IIB, More preferably, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferable 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, but preferably r = 0 and p / q is 1/99 to 1/1. The classification of the metal elements was performed based on a long-period type periodic table in which the typical element is the A subgroup and the transition element is the B subgroup. The above flame retardants may be used alone or in combination of two or more.

  As a diluent, you may mix the reactive diluent which has an epoxy group for viscosity adjustment. Examples of the reactive diluent having an epoxy group include n-butyl glycidyl ether, versatic acid glycidyl ether, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, butyl phenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neodymium Examples include pentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether. One of these may be used alone, or two or more may be used in combination.

  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.

  Electronic component devices obtained by sealing electronic components with the liquid resin composition for electronic components obtained in the present invention include support for lead frames, wired tape carriers, rigid and flexible wiring boards, glass, silicon wafers, etc. An element such as an active element such as a semiconductor chip, a transistor, a diode, or a thyristor, or a passive element such as a capacitor, a resistor, a resistor array, a coil, or a switch is mounted on the member, and the necessary part is a liquid resin for electronic components according to the present invention. Examples thereof include an electronic component device obtained by sealing with a composition. In particular, it is preferably used for sealing an electronic component device in which an electronic component is directly bump-connected on a wiring board. For example, a semiconductor device in which a semiconductor element is flip-chip bonded by bump connection to a rigid and flexible wiring board or a wiring formed on glass 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. The liquid resin composition of the present invention can also be used effectively for printed circuit boards.

  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, the flip chip is suitable for a large element having a semiconductor element size of 5 mm or more on the longer side, and the distance between the wiring board constituting the electronic component and the bump connection surface of the semiconductor element is 80 μm or less. It is possible to provide a semiconductor device that exhibits good fluidity and filling properties for connection and is excellent in 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 stress reduction from the underfill material is required. The dielectric layer having a semiconductor element size of 5 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 electronic component using the liquid resin composition for an electronic component of the present invention include a dispensing method, a casting method, and a printing method.

  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. In addition, various characteristics and impregnation time of the used liquid resin composition for electronic components, observation of a void, and evaluation of various reliability were performed with the following method and conditions. The following two types of flip chip BGAs were used as semiconductor devices used for the impregnation time, void observation, and reliability evaluation of (5) to (9).

(Non low-k specification flip chip BGA)
Specifications are: chip size 20 × 20 × 0.55 tmm (circuit is aluminum daisy chain connection, passivation: polyimide film product name HD4000 manufactured by Hitachi Chemical DuPont Microsystems), bump: solder ball (Sn—Ag—Cu, Φ80 μm, 7, 744 pin,), bump pitch: 190 μm, substrate: FR-5 (trade name SR7000 manufactured by Hitachi Chemical Co., Ltd., 60 × 60 × 0.8 tmm), and chip / substrate gap: 50 μm.

(Low-k specification flip chip BGA)
Specifications are: chip size 20 × 20 × 0.55 tmm (dielectric layer with a dielectric constant of 2.7, three layers are formed, aluminum daisy chain connection, passivation: polyimide film HD4000, product name manufactured by Hitachi Chemical DuPont Microsystems) ), Bumps: solder balls (Sn—Ag—Cu, Φ80 μm, 7,744 pin), bump pitch: 190 μm, substrate: FR-5 (trade name SR7000, Hitachi Chemical Co., Ltd., solder resist product name, 60 × 60 × 0.8 tmm) Chip / substrate gap: 50 μm.

  The semiconductor device was produced by underfilling the above BGA with a liquid resin composition for electronic components by a dispensing method and curing it at 165 ° C. for 2 hours. Also, the curing conditions for various test pieces were 165 ° C. and 2 hours.

(1) Viscosity The viscosity at 25 ° C. of the liquid resin composition for electronic parts was measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm).

(2) Surface tension The surface tension at 25 ° C. of the liquid resin composition for electronic parts was measured using a plate tension method (19.9 mm × 10 mm × 0.2 mm, platinum − Iridium Wilhelmi plate).

(3) Adhesive strength / SR adhesive strength A test piece obtained by molding a liquid resin composition for electronic parts to a surface of a solder resist SR7000 (trade name, manufactured by Hitachi Chemical Co., Ltd.) with a diameter of 3 mm and a height of 3 mm was prepared. The strength at which the molded product peels from the solder resist was measured by applying a shear stress under the conditions of a head speed of 50 μm / sec and 25 ° C. This measurement was performed immediately after molding of the test piece and after the treatment for 150 hours under HAST (Highly Accelerated Temperature and Humidity Stress Test) conditions at 130 ° C. and 85% RH.

(4) PI adhesive strength A test piece was prepared by molding a liquid resin composition for electronic parts to a surface of photosensitive polyimide HD4000 (trade name, manufactured by Hitachi Chemical DuPont Microsystems) to a diameter of 3 mm and a height of 3 mm. The strength at which the molded product peels from the photosensitive polyimide was measured by applying a shear stress under the conditions of a head speed of 50 μm / sec and 25 ° C. This measurement was performed immediately after molding of the test piece and after 150 h treatment under HAST conditions of 130 ° C. and 85% RH.

(5) 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.

(6) Void Observation The inside of the semiconductor device obtained by underfilling and curing the liquid resin composition for electronic components was observed with an ultrasonic flaw detector AT-5500 (manufactured by Hitachi Construction Machinery Co., Ltd.) to examine the presence or absence of voids.

(7) Reflow resistance A semiconductor device obtained by underfilling and curing a liquid resin composition for electronic parts is heated and dried at 120 ° C. for 12 hours, and then absorbed at 168 hours under 85 ° C. and 60% RH, and the far infrared heating system is used. After passing through the reflow furnace (preheating 150 ° C-180 ° C for 50 seconds, peak temperature 260 ° C, heating time 40 ° C or more 40 seconds) three times, the inside was observed with an ultrasonic flaw detector, and the cured resin and chip In addition, the presence or absence of peeling from the substrate and cracks in the cured resin was examined and evaluated by the number of defective packages / number of evaluation packages.

(8) Temperature cycle resistance The semiconductor device obtained by underfilling and curing the liquid resin composition for electronic parts is processed at -50 ° C. to 150 ° C. with a heat cycle of 30 minutes for 1000 cycles, conducting a continuity test, and aluminum wiring and pads. The disconnection failure was checked and evaluated by the number of defective packages / number of evaluation packages.

(9) Moisture resistance reliability After underfilling and curing the semiconductor resin liquid resin composition for electronic parts under HAST conditions of 130 ° C and 85% RH for 150 hours, the presence or absence of disconnection of aluminum wiring and pads was confirmed by continuity test. The number of defective packages / the number of evaluation packages was evaluated.

(Examples 1-13, Comparative Examples 1-6)
(A) Epoxy equivalent 160 liquid diepoxy resin obtained by epoxidizing bisphenol F as a liquid epoxy resin (Epoxy resin 1, trade name jER806 manufactured by Japan Epoxy Resin Co., Ltd.), epoxy equivalent 95 obtained by epoxidizing aminophenol A trifunctional liquid epoxy resin (epoxy resin 2, trade name jER630 manufactured by Japan Epoxy Resin Co., Ltd.) was prepared.

  (B) Diethyltoluenediamine having 45 active hydrogen equivalents (Liquid amine 1, trade name jER Cure W manufactured by Japan Epoxy Resin Co., Ltd.), diethyl-diamino-diphenylmethane having 63 active hydrogen equivalents (Liquid amine 2, Nippon Kayaku) Trade name Kayahard AA), for comparison, tetramethyl-diamino-diphenylmethane (solid amine, Nippon Kayaku Co., Ltd. trade name Kayabond C-200S), acid anhydride equivalent 168 for comparison. Liquid acid anhydride (trade name HN5500, manufactured by Hitachi Chemical Co., Ltd.) was prepared.

  (C) Polyether-modified silicone surfactant (BIC Chemie trade name BYK-377, surfactant 1), aralkyl-modified silicone surfactant (BIC Chemie trade name BYK-323, interface) as nonionic surfactant Activator 2), phenol-modified silicone having a hydroxyl equivalent weight of 750 and a weight average molecular weight of 1600 (trade name BY16-799 manufactured by Toray Dow Corning Silicone Co., Ltd.) and bisphenol F type liquid epoxy resin (jER806) at a weight ratio of 1/1. Silicone-modified epoxy resin (surfactant 3) obtained by heat-mixing, phenol-modified silicone (trade name BY16-871 manufactured by Toray Dow Corning Silicone Co., Ltd.) and bisphenol having an active hydrogen equivalent weight of 130 and a weight average molecular weight of 470 F-type liquid epoxy resin (Japan Epoxy Resin Co., Ltd., trade name jER806), a silicone-modified epoxy resin (surfactant 4) obtained by heating and fusing at a 1/1 weight ratio, a carbinol-modified silicone having a hydroxyl group equivalent of 3500 and a weight average molecular weight of 8500 (Toray Silicone modified epoxy resin (interface) obtained by heating and fusing Dow Corning Silicone product name BY16-004) and bisphenol F type liquid epoxy resin (Japan Epoxy Resin Co., Ltd. product name jER806) at a weight ratio of 1/1. Activators 5) and polyoxyethylene alkyl ether surfactants (trade name Pegnol L-4, surfactant 6 manufactured by Toho Chemical Industry Co., Ltd.) were prepared.

  Spherical silicone fine particles with a mean particle size of 2 μm (trade name Treffil E-601 manufactured by Toray Dow Corning Silicone Co., Ltd.) whose surface of dimethyl type solid silicone rubber particles is modified with an epoxy group as a flexibilizing agent, acceleration of curing 2-phenyl-4,5-dihydroxymethylimidazole as the agent, γ-glycidoxypropyltrimethoxysilane (trade name: Silaace S510, manufactured by Chisso Corporation) as the silane coupling agent, and carbon black (manufactured by Mitsubishi Chemical Corporation) as the colorant (Trade name MA-100), a bismuth ion trapping agent (trade name IXE-500, manufactured by Toagosei Co., Ltd.) as an ion trapping agent, and (D) spherical fused silica having an average particle diameter of 1 μm as an inorganic filler.

These were blended in the compositions shown in Tables 1 to 3 below, kneaded and dispersed with a three roll and vacuum crusher, and then liquid resin compositions for electronic components of Examples 1 to 13 and Comparative Examples 1 to 6 Was made. In addition, the compounding unit in Tables 1-3 is a mass part, and a blank represents no compounding.

Various evaluation results are shown in Tables 4 to 6.

  In Comparative Examples 1 and 2 that do not contain the nonionic surfactant of component (C) in the present invention, the surface tension is large, and the adhesive strength, void, moisture resistance reliability, and temperature cycle resistance after HAST treatment are extremely inferior. It was. In addition, the comparative example 3 in which the curing agent is a solid amine containing a surfactant (C) and the curing agent is a solid amine that does not contain the surfactant (C), and the curing agent is a solid amine. It was inferior in production for a long time, and the moisture resistance reliability and thermal shock resistance decreased due to voids. Furthermore, the comparative example 4 in which the surfactant (C) contains a curing agent and is a liquid acid anhydride, and the comparative example 6 in which the curing agent does not contain a surfactant (C) and a liquid acid anhydride is a moldability. However, the reflow resistance, the temperature cycle resistance, and the moisture resistance reliability were remarkably inferior due to the low moisture adhesion strength. On the other hand, in Examples 1 to 13, the surface tension is low, the void property at the time of molding and the adhesion after HAST treatment are improved, and various reliability of reflow resistance, temperature cycle resistance and moisture resistance is achieved. Excellent.

Claims (12)

A liquid resin composition for electronic parts used for sealing electronic parts, wherein (A) a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) a nonionic surfactant, (D The non-ionic surfactant (C) containing an inorganic filler is obtained by reacting an organosiloxane having a functional group that reacts with an epoxy group with an epoxy resin that is liquid at room temperature, and is a liquid silicone at room temperature. modified epoxy resins der is, the organosiloxane, the electronic component liquid resin composition is not more than the weight average molecular weight of 500 to 5,000. Claim 1 Symbol mounting electronic component liquid resin composition is used on the wiring board in the electronic component device directly bump-connected electronic components. The liquid resin composition for electronic parts according to claim 2 , wherein the bump is a metal containing no lead. Is not less 5mm or more the length of the long side of the electronic components, and electronic components for liquid resin of an electronic component between the equipment and wiring substrate constituting the bump connecting surface of the electronic component is 80μm or less claim 2 or 3, wherein Composition. The liquid resin for electronic components according to any one of claims 2 to 4 , wherein the electronic component is a semiconductor element having a long side length of 5 mm or more and the electronic component having a dielectric layer having a dielectric constant of 3.0 or less. Composition. Furthermore, a hardening accelerator is contained, The said hardening accelerator is an imidazole derivative, The liquid resin composition for electronic components in any one of Claims 1-5 . The liquid resin composition for electronic components according to claim 6 , wherein the curing accelerator is an imidazole derivative having a phenyl group and a hydroxyl group as substituents. The liquid resin composition for electronic parts according to claim 6 or 7 , wherein the imidazole derivative is a microencapsulated imidazole derivative. The electronic component apparatus provided with the electronic component sealed with the liquid resin composition for electronic components in any one of Claims 1-8 . The electronic component device according to claim 9 , wherein the bump is a metal containing no lead. Electronic components is not less 5mm or more the length of the long side, and an electronic component device of the electronic component between the equipment and wiring substrate constituting the bump connecting surface of the electronic component is 80μm or less claim 9 or 10, wherein. The electronic component device according to any one of claims 2 to 11 , wherein the electronic component is a semiconductor element having a long side length of 5 mm or more and the electronic component having a dielectric layer having a dielectric constant of 3.0 or less.