JP5277537B2 - 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 and an electronic component device using the same.

  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. An important role of the underfill material is to maintain the reliability of bump connection by dispersing the stress generated between the semiconductor elements with different expansion coefficients and the wiring board. Due to the narrowing of the gap, it has become difficult to maintain the reliability of bump connection with conventional materials. In particular, lead-free solder tends to be used for bumps from the viewpoint of environmental protection. Compared to conventional lead solder, lead-free solder has weaker mechanical properties, so that the reliability of bump connection becomes more severe. In order to maintain the reliability of the bump connection, it is necessary to maintain good adhesion to the semiconductor element and the wiring board and to disperse the stress generated between them. Further, the stress generated at the interface between the semiconductor element and the underfill material leads to failure of the semiconductor element. In particular, with the increase in the speed of semiconductor devices, in semiconductor devices using a low dielectric material such as black diamond as an interlayer insulating layer, the insulating layer is fragile, so that a significant stress reduction is required for the underfill material.

  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, and has a good fluidity in a narrow gap, a liquid resin composition for an electronic component having excellent adhesion to an electronic component component, and low stress, and An object of the present invention is to provide an electronic component device that is sealed and has high reliability (moisture resistance and thermal shock resistance).

  In order to solve the above-mentioned problems, the present inventors have made extensive studies, and in order to obtain a liquid epoxy resin composition excellent in adhesiveness and low-stress property with electronic component constituent members, various curing agents, various stress reductions As a result of studying the agent, when a curing agent containing a liquid aromatic amine is used as the curing agent, the moisture-resistant adhesive strength with various electronic component constituent members is improved and the moisture resistance reliability is excellent. Silicone polymer particles are used as the low-stress agent. It was found that the use of this material has high reliability and excellent low-stress effect, and the above object has been achieved and the present invention has been completed.

  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) silicone polymer particles, (D) inorganic A liquid resin composition for electronic parts containing a filler.

2. (C) The liquid resin composition for electronic components as described in 1. above, wherein the silicone polymer particles as the component have a primary particle diameter of 0.05 μm or more and 10 μm or less.

3. 3. The liquid resin composition for electronic components as described in 1 or 2 above, which is used in an electronic component device in which electronic components are directly bump-connected on a wiring board.

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

5. 3. The liquid for electronic components as described in 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. Resin composition.

6). The liquid for electronic components according to any one of 3 to 5 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. 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). 7. The electronic component device as described in 7 above, wherein the bump is a metal containing no lead.

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

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

  The liquid resin composition for electronic parts according to the present invention is excellent in moldability such as impregnation and void generation as well as reliability such as moisture resistance reliability and thermal shock resistance as shown in Examples, and this liquid resin for electronic parts. If an element is sealed using a composition, an electronic component device having excellent reliability can be obtained even for a state-of-the-art semiconductor element, and its industrial value is great.

  The liquid epoxy resin of component (A) used in the present invention has one or more epoxy groups in one molecule and is not limited as long as it is liquid at room temperature, and is generally used in liquid resin compositions for electronic components. The liquid epoxy resin currently used can be used.

  The liquid epoxy resin of component (A) used in the present invention has one or more epoxy groups in one molecule, and is not limited as long as it is liquid at room temperature, and is generally used in an epoxy resin composition for sealing. The liquid epoxy resin currently used can be used.

  Examples of (A) liquid 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, and hydrogenated bisphenol A, and orthocresol novolac type epoxy resins. Such as epoxidized novolak resins of phenols and aldehydes, glycidyl ester type epoxy resins obtained by reaction of polybasic acids such as phthalic acid and dimer acid and epichlorohydrin, p-aminophenol, diaminodiphenylmethane, isocyanuric acid, etc. Examples include glycidylamine-type epoxy resins obtained by reaction of amine compounds with epichlorohydrin, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, and alicyclic epoxy resins. It is, may be used in combination of two or more even with these 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. However, the blending amount is (A) 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.

  Furthermore, the purity of these epoxy resins, especially the amount of hydrolyzable chlorine, is better because it is related to corrosion of aluminum wiring on ICs and other elements. In order to obtain a liquid resin composition for electronic parts with 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.

  If the liquid aromatic amine contained in (B) component used for this invention is an amine which has a liquid aromatic ring at normal temperature, there will be no restriction | limiting in particular. For example, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl Examples include -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, from the viewpoint of storage stability, 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine are preferable, and (B) the curing agent is any one of these or these It is preferable to use a mixture as a main component. 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 a liquid resin for electronic parts such as phenolic curing agents and acid anhydrides in addition to the liquid aromatic amine as long as the effects of the present invention are achieved. Curing agents generally used in the composition 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 another curing agent is used in combination, the blending amount of the liquid aromatic amine is preferably 60% by mass or more based on the total amount of the (B) curing agent in order to exhibit its performance. The equivalent ratio of the (A) component-containing epoxy resin and the (B) curing agent is not particularly limited, but in order to suppress each unreacted component to a small amount, the curing agent is added in an amount of 0.7 equivalent or more to the epoxy resin. It is preferably set in the range of 6 equivalents or less, more preferably 0.8 equivalents or more and 1.4 equivalents or less, and even more preferably 0.9 equivalents or more and 1.2 equivalents or less.

  The silicone polymer particles of the component (C) in the present invention are mainly used for improving flexibility. The silicone polymer particles are not particularly limited, but silicone rubber particles obtained by crosslinking polyorganosiloxanes such as linear polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane, and the surface of these silicone rubber particles are used. Examples thereof include those coated with a silicone 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.

  Further, as the silicone polymer particles of the component (C), core-shell polymer particles composed of a solid silicone polymer core and an organic polymer shell such as an acrylic resin or an acrylic resin copolymer can be used. The core-shell polymer particles can be obtained by synthesizing a core silicone polymer by emulsion polymerization and then adding an acrylic monomer and an initiator to form a shell by second-stage polymerization. There are ways to do it. In this case, by appropriately blending the siloxane monomer or oligomer component used for the first stage polymerization with a siloxane compound having a double bond, the acrylic resin is grafted through the double bond, and the interface between the core and the shell is strong. Therefore, the strength of the liquid resin cured product for electronic parts can be increased by using the silicone polymer particles thus obtained.

  The primary particle diameter of the silicone polymer particles of component (C) 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. More preferably, it is in the range of 0.1 μm to 5 μm. 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 primary particle size is a value obtained by directly observing the silicone polymer particles with an electron microscope or the like.

  The blending amount of the silicone polymer particles of component (C) 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% by mass. When the blending amount of the silicone polymer particles is less than 1% by mass, the effect of low stress 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. There is.

  In the present invention, rubber particles other than the silicone polymer particles of the component (C) can be blended. Examples thereof include rubber particles such as styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic 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. In addition, the rubber particles can be used in the form of fine powder and finely dispersed in an epoxy resin or a curing agent in advance from the viewpoint of handleability and dispersibility with resin components. For example, rubber-modified epoxy resin that is liquid at room temperature. Is mentioned.

  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 One of these may be used alone, or two or more may be used in combination.

  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 of the liquid epoxy resin as the component (A) and the curing agent containing the component (B) can be used as necessary. 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 maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3- Quinone compounds such as dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone; A compound having intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane or phenol resin,
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 phosphine compounds such as triphenylphosphine and alkyl group-substituted triphenylphosphine, and maleic anhydride to these compounds 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2 A compound having intramolecular polarization formed by adding a quinone compound such as 1,3-dimethoxy-1,4-benzoquinone or phenyl-1,4-benzoquinone, a compound having a π bond such as diazophenylmethane or phenol resin, and the like. This Including al derivatives, and the like, more 2-ethyl-4-methylimidazole tetraphenyl borate, etc. phenylboronic salts such as N- methylmorpholine tetraphenylborate and the like. One of these may be used alone, or two or more may be used in combination.

  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 (Ajinomoto Co., Inc., trade name), NovaCure (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) in which microencapsulated imidazole derivatives are dispersed in bisphenol A type epoxy resin and 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. For example, 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 preferable, and from the viewpoint of storage stability, NovaCure (trade name, manufactured by Asahi Kasei Chemicals) is preferable, and in particular, phenyl group and hydroxyl group are substituted. 2-Phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole, which are imidazole derivatives as groups, are preferred.

  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.

  Various surfactants can be mix | blended with the liquid resin composition for electronic components of this invention from a viewpoint of the adhesive force improvement by the void reduction at the time of shaping | molding, and the wettability improvement to various to-be-adhered bodies. The surfactant is not particularly limited, but is preferably a nonionic surfactant. For example, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether Oxyethylene 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, polyacrylic These may be used, 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. 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. 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 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. 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.

  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. When the amount is less than 0.01% by mass, a sufficient addition effect cannot be obtained. When the amount is more than 1.5% by mass, bleeding from the surface of the cured product occurs at the time of curing and the adhesive strength tends to decrease.

  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. Moreover, the compound of the said formula (II) is available as a brand name IXE500 by Toa Gosei Co., Ltd. as a commercial item. Further, other ion trapping agents can be added as necessary. 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.

  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 red lead, flame retardants, diluents, leveling agents, other stress relaxation agents, A foaming 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 of 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 impregnation time, void observation, and reliability evaluation.

(Non low-k specification flip chip BGA)
Chip size 20 × 20 × 0.55 tmm (circuit is daisy chain connection of aluminum, 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)
Chip size 20 x 20 x 0.55 tmm (3 dielectric layers with a dielectric constant of 2.7 are formed, circuit is daisy chain connection of aluminum, passivation: polyimide film product name HD4000 manufactured by Hitachi Chemical DuPont Microsystems), bump: solder Ball (Sn—Ag—Cu, Φ80 μm, 7,744 pins), bump pitch: 190 μm, substrate: FR-5 (trade name SR7000, 60 × 60 × 0.8 tmm, manufactured by Hitachi Chemical Co., Ltd.), chip / substrate Gap between: 50 μm.

  The semiconductor device was manufactured by underfilling the liquid resin composition for electronic components to each of the above BGAs by a dispensing method and curing under a heating condition of 165 ° C. for 2 hours. The test piece was cured at 150 ° C. for 3 hours.

(1) Viscosity and Fluctuation Index 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). The change index was the ratio of the viscosity measured at 2.5 rpm and the viscosity measured at 10 rpm.

(2) 165 ° C. Gel Time Using a gelation tester, a suitable amount of the blended liquid resin composition for electronic parts was placed on a hot plate at 165 ° C., and then the time until gelation started was measured.

(3) Elastic modulus A test piece (width 4 mm length 40 mm thickness 1 mm) cured under predetermined conditions was measured using a dynamic viscoelasticity measuring apparatus DMA-Q800 (trade name, manufactured by TA Instruments) with a span of 22 mm. The storage elastic modulus at 25 ° C. was measured under the conditions of a temperature of −60 to 300 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz.

(4) 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 produced. The strength at which the test piece 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 the test piece and after 150 h treatment at 130 ° C. and 85% RH HAST (Highly Accelerated Temperature and Humidity Stress Test) conditions.

(5) 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, and bond tester DS100 type ( The strength at which the test piece 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 150 h treatment at 130 ° C. and 85% RH HAST conditions.

(6) 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) Reliability evaluation (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 85 ° C. and 60% RH for 168 hours, and a far-infrared heating type reflow furnace (preheating 150 ° C. For 3 seconds, and the inside is observed with an ultrasonic flaw detector to separate the cured resin from the chip and the substrate, and the cured resin. The number of defective packages / evaluation packages was evaluated.

(Heat shock resistance)
A semiconductor device in which a liquid resin composition for an electronic component is underfilled and cured is subjected to 1000 cycles with a heat cycle of −50 ° C. to 150 ° C. for 30 minutes each, and a continuity test is performed to check for disconnection defects in aluminum wiring and pads. Evaluation was performed by the number of packages / number of evaluation packages.

(Moisture resistance reliability)
Semiconductor device with underfill and hardened liquid resin composition for electronic components is treated for 150h under HAST conditions of 130 ° C and 85% RH, then the presence or absence of disconnection of aluminum wiring and pads is confirmed by continuity test, and the number of defective packages / evaluation packages Evaluated by number.

(Examples 1-7, Comparative Examples 1-4)
(A) Epoxy equivalent 160 liquid diepoxy resin obtained by epoxidizing bisphenol F as a liquid epoxy resin (Liquid epoxy 1, Japan Epoxy Resin Co., Ltd., trade name jER806), epoxy equivalent 95 obtained by epoxidizing aminophenol Trifunctional liquid epoxy resin (Liquid epoxy 2, Japan Epoxy Resin Co., Ltd. trade name jER630),
(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) Product name Kayahard AA), solid amine with active hydrogen equivalent 63 (Nippon Kayaku Co., Ltd. product name Kayabond C-200S), liquid anhydride with acid anhydride equivalent 168 (product name, manufactured by Hitachi Chemical Co., Ltd.) HN5500),
(C) Spherical silicone fine particles 1 having an average particle diameter of 2 μm, the surface of dimethyl type solid silicone rubber particles being modified with an epoxy group as silicone polymer particles (trade name Trefil E-601 manufactured by Toray Dow Corning Silicone) The core layer is made of dimethyl solid silicone and the shell layer is made of acrylic resin, the core / shell mass ratio is 2/1, and the silicone fine particles 2 have an average particle size of 0.12 μm. For comparison, butadiene, acrylonitrile, methacrylic acid, NBR particles (trade name: XER-91, manufactured by JSR Corporation), which is a copolymer of divinylbenzene and has an average particle size of 0.19 μm, were prepared.

  Spherical fused silica with an average particle size of 1 μm as an inorganic filler, 2-phenyl-4-methyl-5-hydroxymethylimidazole as a curing accelerator, and bismuth ion trapping agent IXE500 (trade name, manufactured by Toagosei Co., Ltd.) as an ion trapping agent Further, γ-glycidoxypropyltrimethoxysilane (trade name: Silaace S510, manufactured by Chisso Corporation) was used as a coupling agent, and carbon black (trade name: MA-100, manufactured by Mitsubishi Chemical Corporation) was prepared as a coloring agent.

These were blended in the compositions shown in Table 1 and kneaded and dispersed with a three roll and vacuum crusher, and then liquid resin compositions for electronic components of Examples 1 to 7 and Comparative Examples 1 to 4 were produced. .

Various evaluation results are shown in Table 2.

  In Comparative Example 1 that does not include the silicone polymer of the component (C) in the present invention, the moisture resistance adhesive strength, moisture resistance reliability, and thermal shock resistance were remarkably inferior. In Comparative Example 2 in which NBR particles were blended as a flexibilizer instead of the component (C), although an improvement effect was seen in the moisture-resistant adhesive force and thermal shock resistance, it was still insufficient. Although the comparative example 3 which contains the silicone polymer of component (C) and the curing agent is a solid amine has a high viscosity, the impregnation time is long and the production is inferior, and the moisture resistance reliability and the thermal shock resistance are lowered due to voids. In addition, although the silicone polymer of component (C) is contained but the curing agent is a liquid acid anhydride instead of a liquid aromatic amine, the liquid acid anhydride is superior in moldability but has poor moisture resistance adhesion, so reflow resistance and moisture resistance reliability. Was significantly inferior. On the other hand, Examples 1-7 mix | blend liquid aromatic amine and (C) silicone polymer particle | grains, These are excellent in the impregnation property at the time of shaping | molding, there is no void generation, and the initial stage and the time of humidification Because of its excellent adhesive properties, the reliability of moisture resistance, thermal shock resistance, etc. was also significantly improved.

Claims (9)

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) silicone polymer particles, (D) inorganic Contains a filler,
The primary particle diameter of the silicone polymer particles of the component (C) is 0.05 μm or more and 10 μm or less,
The electronic component is a semiconductor element having a dielectric layer having a dielectric constant of 3.0 or less,
The blending amount of (C) is 1% by mass or more and 30% by mass or less of the entire liquid resin composition for electronic parts excluding the filler,
The blending amount of (D) is 20% by mass or more and 90% by mass or less of the entire liquid resin composition for electronic parts ,
The (A) liquid epoxy resin includes a liquid bisphenol type epoxy resin and a liquid glycidylamine type epoxy resin,
The equivalent ratio of the curing agent containing (B) liquid aromatic amine to (A) liquid epoxy resin is 0.7 to 1.6 equivalents,
(D) The liquid resin composition for electronic components whose average particle diameter of an inorganic filler is 0.3-10 micrometers .   The liquid resin composition for electronic components according to claim 1, which is used in an electronic component device in which electronic components are directly bump-connected on a wiring board.   The liquid resin composition for electronic parts according to claim 2, wherein the bump is a metal containing no lead.   4. The liquid resin for electronic components according to claim 2, 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. Composition. The liquid resin composition for an electronic component according to claim 2 or 3 , wherein the length of the long side of the electronic component is 5 mm or more.   It is an electronic component apparatus provided with the electronic component sealed with the liquid resin composition for electronic components in any one of Claims 1-5, Comprising: The said electronic component has a dielectric material layer whose dielectric constant is 3.0 or less. Electronic component devices that are semiconductor elements.   The electronic component device according to claim 6, wherein the bump is a metal containing no lead.   The electronic component device according to claim 6 or 7, wherein a length of a long side of the electronic component is 5 mm or more and a distance between a wiring board constituting the electronic component device and a bump connection surface of the electronic component is 80 µm or less.   The electronic component device according to any one of claims 6 to 8, wherein a length of a long side of the electronic component is 5 mm or more.