JP2008111106A - Liquid resin composition for sealing electronic parts and electronic component device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid resin composition for sealing electronic parts excellent in the fluidity in a narrow gap, free from the occurrence of voids and excellent in fillet forming property, and to provide an electronic component device sealed by using the same, with high reliability (moisture resistance and thermal shock resistance). <P>SOLUTION: The liquid resin composition for sealing electronic parts comprising (A) an epoxy resin containing a liquid epoxy resin, (B) a hardener containing a liquid aromatic amine, (C) a hydrazide compound with less than 2 μm of an average particle diameter and (D) an inorganic filler with less than 2 μm of an average particle diameter. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid resin composition for sealing an electronic component and an electronic component device using the same.

  2. Description of the Related Art Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, sealing with a resin 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. In a semiconductor device mounted with bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package), a liquid resin composition for sealing electronic components is widely used as a sealing material. Further, in a semiconductor device (flip chip method) in which a semiconductor element is directly bump-connected on a wiring board using ceramic, glass / epoxy resin, glass / imide resin, polyimide film or the like as a substrate, the bump-connected semiconductor element and wiring A liquid resin composition for sealing electronic parts is used as an underfill material for filling a gap (gap) between substrates. These liquid resin compositions for sealing electronic components play an important role in protecting electronic components from temperature and humidity and mechanical external force.

As the curing agent for the resin composition for encapsulating electronic components, many acid anhydride curing agents have been used so far. The reason for this is that a low-viscosity liquid can be easily obtained and that the curability can be adjusted relatively easily by selecting a curing accelerator. However, when an acid anhydride type curing agent is used, there is a drawback that the moisture resistance of the cured product is inferior, and from the viewpoint of improving moisture resistance, an underfill material using an amine type curing agent as a curing agent is mainstream. (For example, see Patent Document 1).
JP-A-2005-350618

  However, the progress of semiconductors is remarkable, and in the flip-chip method in which bump connection is performed, the bump pitch is narrowed and the bump height is reduced with the increase in the number of bumps, resulting in a narrow gap. In addition, the chip size has been increased with higher integration of semiconductor elements. As an underfill material, a characteristic of flowing a large area in a narrow gap has been demanded. In addition, the number of bumps increases and the pitch of the bumps becomes narrow as the gap becomes narrower, so the flow path of the underfill material becomes complicated and voids are likely to occur. In addition, the underfill material fills the gap between the wiring board and the semiconductor element, and then a certain amount of stains are formed around the periphery of the semiconductor element to form a fillet. May crack, or may be separated from the wiring board or semiconductor element. The generation of such voids and the formation of fillets with non-uniform shapes have a great influence on the reliability of a semiconductor device formed by flip chip mounting. In particular, regarding voids, it has been found that it is effective to reduce the generation of voids after the underfill material is filled, and then it is quickly cured.

  As described above, it was relatively easy to adjust the curability with the conventional acid anhydride-based curing agent, but with the amine-based curing agent, it is generally difficult to adjust the curability and the curability can be increased. The problem that adhesiveness falls will come out.

  The present invention includes a liquid resin composition for sealing an electronic component, which has good fluidity in a narrow gap, does not generate voids, and is excellent in fillet formation, and an electronic component sealed thereby. An object of the present invention is to provide a highly reliable electronic component device excellent in moisture resistance and thermal shock resistance.

  In order to solve such problems, the present inventors have made extensive studies and found that a curing agent containing a liquid aromatic amine and a hydrazide compound having an average particle size of less than 2 μm may be used. Based on this finding Thus, the present invention has been completed.

  The present invention includes (1) (A) an epoxy resin containing a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) a hydrazide compound having an average particle size of less than 2 μm, and (D) an average particle size. The present invention relates to a liquid resin composition for sealing electronic parts, which contains an inorganic filler of less than 2 μm.

  In the present invention, (2) the hydrazide compound is at least one selected from an aliphatic polybasic acid dihydrazide compound having 2 to 10 carbon atoms and an aromatic polybasic acid dihydrazide compound having 8 to 15 carbon atoms. It is related with the liquid resin composition for electronic component sealing of said (1) characterized by these.

  Moreover, this invention relates to the electronic component apparatus provided with the electronic component sealed with the liquid resin composition for electronic component sealing of (3) said (1) or (2) description.

  The present invention also relates to (4) the electronic component device according to (3), wherein the electronic component is a semiconductor element, and the semiconductor element is directly bump-connected on a wiring board.

  The present invention also relates to (5) the electronic component device according to (4), wherein the bump is a metal containing no lead.

  In the present invention, (6) the electronic component has a long side length of 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 60 μm or less. (3) It is related with the electronic component apparatus as described in any one of (5).

  Further, the present invention is (7) the semiconductor element (3), wherein the electronic component has a long side length of 5 mm or more and the electronic component has a dielectric layer having a dielectric constant of 3.0 or less. It is related with the electronic component apparatus as described in any one of-(6).

  According to the present invention, there is provided a liquid resin composition for sealing an electronic component that has good fluidity in a narrow gap, does not generate voids, and has excellent fillet formability, and an electronic component sealed thereby. It is possible to provide a highly reliable electronic component device having excellent moisture resistance and thermal shock resistance.

  The liquid resin composition for sealing electronic parts of the present invention shortens the gel time as shown in the examples, thereby suppressing the generation of voids during molding and lowering the curing temperature. Since the adhesive strength with various base materials is high, if the electronic component is sealed using this liquid resin composition for sealing an electronic component, a highly reliable electronic component device with small chip warpage can be obtained. , Its industrial value is great.

  The liquid resin composition for sealing electronic parts of the present invention comprises (A) an epoxy resin containing a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) a hydrazide compound having an average particle size of less than 2 μm, and (D) An inorganic filler having an average particle diameter of less than 2 μm is contained.

(A) Epoxy Resin The (A) epoxy resin used in the present invention contains a liquid epoxy resin. The liquid epoxy resin is not particularly limited as long as it is liquid at normal temperature, and a liquid epoxy resin generally used in a liquid resin composition for sealing electronic parts can be used. Specific examples of the liquid epoxy resin include diglycidyl ether type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A;
Epoxidized phenol and aldehyde novolak resins, typified by orthocresol novolac type epoxy resins;
Glycidyl ether type epoxy resin obtained by reaction of low molecular weight polyphenols such as resorcinol and pyrogallol with epichlorohydrin;
Glycidyl ester type epoxy resin obtained by reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin;
a glycidylamine type epoxy resin obtained by reaction of an amine compound such as p-aminophenol, diaminodiphenylmethane, and isocyanuric acid with epichlorohydrin;
A linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid;
Alicyclic epoxy resin; and the like. These liquid epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

The epoxy equivalent of the liquid epoxy resin is preferably in the range of 50 to 500.
Among the liquid epoxy resins, bisphenol-type epoxy resins are preferable from the viewpoint of fluidity, and glycidylamine-type epoxy resins are preferable from the viewpoint of heat resistance, adhesiveness, and fluidity. Any one of these suitable liquid epoxy resins may be used alone, or two or more thereof may be used in combination. The blending amount of these suitable liquid epoxy resins is preferably 20% by weight or more, more preferably 30% by weight or more, particularly preferably 50% by weight or more based on the total amount of the liquid epoxy resin in order to exhibit the above performance. is there.

  Moreover, as long as the effects of the present invention are achieved, the (A) epoxy resin may contain a solid epoxy resin, and the blending amount of the solid epoxy resin is an epoxy from the viewpoint of fluidity during molding. Preferably it is 20 weight% or less with respect to resin whole quantity.

  In the present invention, (A) the amount of hydrolyzable chlorine contained in the epoxy resin is preferably less because it involves corrosion of the aluminum wiring on the IC and other elements, and the liquid resin composition for sealing electronic components with excellent moisture resistance In order to obtain a product, the hydrolyzable chlorine content is preferably 500 ppm or less. Here, the amount of hydrolyzable chlorine is a value obtained by dissolving 1 g of epoxy resin in 30 ml of dioxane, adding 5 ml of 1N-KOH methanol solution and refluxing for 30 minutes, and then determining by potentiometric titration.

(Curing agent)
The (B) curing agent used in the present invention contains a liquid aromatic amine. The liquid aromatic amine is not particularly limited as long as it is an amine having a liquid aromatic ring at room temperature. Specific examples of the liquid aromatic amine include diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1, 3,5-triethyl-2,6-diaminobenzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,5,3 ′, 5′-tetramethyl-4,4′-diaminodiphenylmethane, etc. Can be mentioned. Commercial products of these liquid aromatic amine compounds are Epicure-W, Epicure-Z (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Kayahard A-A, Kayahard AB, Kayahard AS (Nippon Kayaku Co., Ltd.) Company name, product name), Totoamine HM-205 (product name, manufactured by Toto Kasei Co., Ltd.), Adeka Hardener EH-101 (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), Epomic Q-640, Epomic Q-643 ( Mitsui Chemicals, Inc., trade name), DETDA80 (Lonza, trade name) and the like.

  The said liquid aromatic amine may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the liquid aromatic amines, 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine are preferable from the viewpoint of storage stability. Examples of diethyltoluenediamine include 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine. These may be used alone or both of them. Although it may be used as a mixture, it is preferably used as a mixture containing 60% by weight or more of 3,5-diethyltoluene-2,4-diamine.

  Moreover, if it is in the range by which the effect of this invention is achieved, (B) hardening | curing agent will be what was conventionally used as a hardening | curing agent for epoxy resins, such as a phenolic hardening | curing agent and an acid anhydride type hardening | curing agent. It may contain, and a solid hardening | curing agent can also be used together.

  The content of the liquid aromatic amine is preferably 60% by weight or more, more preferably 80% by weight or more based on the total amount of the curing agent (B) in order to exhibit its performance.

  Further, the equivalent ratio of (A) epoxy resin to (B) curing agent, that is, the ratio of the number of reactive groups in (B) curing agent to the number of epoxy groups in (A) epoxy resin (number of active hydrogens in curing agent + The number of hydroxyl groups + the number of hydroxyl groups / the number of epoxy groups in the epoxy resin is not particularly limited, but is preferably in the range of 0.7 to 1.6 in order to suppress each unreacted component to a small value. More preferably, it is in the range of 0.8 to 1.4, and particularly preferably in the range of 0.9 to 1.2.

(C) Hydrazide Compound In the present invention, it is essential to use a hydrazide compound having an average particle size of less than 2 μm, whereby (A) an epoxy resin containing a liquid epoxy resin and (B) a curing containing a liquid aromatic amine. Liquid resin composition for encapsulating electronic components with a good adhesion to the solder resist on the substrate surface, copper wiring or polyimide film on the semiconductor chip surface, passivation film such as silicon nitride or silicon oxide, etc. Is obtained.

  The (C) hydrazide compound used in the present invention is a compound in which the hydroxy group of a monobasic acid or polybasic acid is substituted with a hydrazino group. Specific examples of such hydrazide compounds include aliphatic monobasic hydrazide compounds such as acetic hydrazide, propionic hydrazide, butyric hydrazide, pentanoic hydrazide, caproic hydrazide, enanthic hydrazide, caprylic hydrazide; succinic dihydrazide, Maleic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid dihydrazide, aliphatic dibasic acid dihydrazide compounds such as cyclohexanedicarboxylic acid hydrazide; aromatic monobasic acid hydrazide compounds such as benzoic acid hydrazide; phthalic acid dihydrazide And aromatic polybasic acid dihydrazide compounds such as isophthalic acid dihydrazide and terephthalic acid dihydrazide.

  The said hydrazide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the hydrazide compounds, an aliphatic polybasic acid dihydrazide compound having 2 to 10 carbon atoms or an aromatic polybasic acid dihydrazide compound having 8 to 15 carbon atoms is preferred from the viewpoint of curing acceleration.

  In the present invention, it is important that the average particle diameter of the (C) hydrazide compound is less than 2 μm. By setting the average particle size to less than 2 μm, a sufficient curing accelerating action can be exhibited with a small blending amount, the curability of the liquid resin composition for sealing electronic components is improved, and a highly reliable electronic component device is obtained. Can be obtained. The average particle diameter is preferably 0.1 to 2 μm, more preferably 0.5 to 1.8 μm.

  In addition, the maximum particle size of the (C) hydrazide compound is preferably 20 μm or less, more preferably 5 to 15 μm from the viewpoint of reactivity.

  Moreover, when using the liquid resin composition for electronic component sealing of this invention as an underfill material, since the distance (gap) between a wiring board and the bump connection surface of an electronic component is narrow, the average particle diameter of (C) hydrazide compound Is preferably 1/20 or less of the gap, and the maximum particle size of the (C) hydrazide compound is preferably 1/2 or less of the gap.

  In the present invention, the average particle size and the maximum particle size can be obtained by, for example, particle size distribution measurement by a laser light diffraction method or the like, and the average particle size can be obtained as a weight average value.

  (C) Although the compounding quantity of a hydrazide compound will not be restrict | limited especially if the hardening acceleration | stimulation effect is achieved, (A) The active hydrogen equivalent of (B) hardening | curing agent with respect to 1 equivalent of epoxy resins. And (C) the active hydrogen equivalent of the hydrazide compound is 1 equivalent, the active hydrogen equivalent of the (C) hydrazide compound is preferably in the range of 0.02 to 0.3 equivalent, A range of 0.20 equivalent is more preferable.

(Curing accelerator)
The liquid resin composition for encapsulating electronic components of the present invention may contain a curing accelerator other than the (C) hydrazide compound. The curing accelerator is not particularly limited as long as it accelerates the reaction between (A) an epoxy resin containing a liquid epoxy resin and (B) a curing agent containing a liquid aromatic amine, and a conventionally known curing accelerator can be used. Can be used. Specific examples of the curing accelerator include 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino- Cycloamidine compounds such as 1,8-diaza-bicyclo (5,4,0) undecene-7; tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol Compound; 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 Imidazole compounds such as 5-hydroxymethylimidazole, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, 2-heptadecylimidazole; trialkylphosphine such as tributylphosphine Dialkylarylphosphine such as dimethylphenylphosphine; alkyldiarylphosphine such as methyldiphenylphosphine; organic phosphines such as triphenylphosphine and alkyl-substituted triphenylphosphine; and these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1, 4-be Compounds having intramolecular polarization formed by adding a quinone compound such as nzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane, a compound having a π bond such as a phenol resin; and derivatives thereof; and 2-ethyl- And phenylboron salts such as 4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate;

  The said hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Further, as a latent curing accelerator, for example, a core-shell particle (trade name, manufactured by Ajinomoto Co., Inc., having a core layer composed of a compound having an amino group that is solid at room temperature and a shell layer composed of an epoxy compound that is solid at room temperature. “Amicure”), a microencapsulated amine dispersed in bisphenol A type epoxy resin and bisphenol F type epoxy resin (manufactured by Asahi Kasei Chemicals Corporation, trade name “Novacure”), and the like can be used.

  Among the above-mentioned curing accelerators, those obtained by dispersing an imidazole compound or a microencapsulated amine in a bisphenol A type epoxy resin and a bisphenol F type epoxy resin from the viewpoint of a balance between the curing acceleration effect and reliability are preferable. As the compound, an imidazole compound having a phenyl group and a hydroxyl group as a substituent, such as 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole, is more preferable.

(D) Inorganic filler The (D) inorganic filler used in the present invention is not particularly limited as long as it is generally used in a liquid resin composition for sealing electronic components. (D) Specific examples of the inorganic filler include silica such as fused silica and crystalline silica, alumina such as calcium carbonate, clay and alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate and aluminum nitride. , Powders of beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, or the like, or spherical beads or glass fibers. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate.

  The said inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the inorganic fillers, fused silica is preferable, and spherical silica is more preferable from the viewpoint of fluidity and permeability in a narrow gap of the liquid resin composition for sealing an electronic component.

  In the present invention, it is important that the average particle diameter of the inorganic filler (D) is less than 2 μm. When the average particle size is 2 μm or more, the dispersibility of the inorganic filler is inferior, and the fluidity / penetration in a narrow gap of the liquid resin composition for sealing electronic parts is reduced, so that voids are not generated or not filled. I will invite you. The average particle diameter is preferably 0.1 μm or more and less than 2 μm, more preferably 0.5 μm or more and 1.5 μm or less. In the case of spherical silica, the average particle diameter is preferably 0.3 μm or more, and if it is less than 0.3 μm, the dispersibility in the liquid resin composition for sealing electronic parts tends to be inferior. The liquid resin composition for sealing tends to have thixotropic properties and poor flow characteristics.

  (D) The blending amount of the inorganic filler is preferably in the range of 20 to 90% by weight, more preferably in the range of 25 to 80% by weight of the entire liquid resin composition for sealing electronic components, and 30 A range of ˜60% by weight is particularly preferred. If the blending amount is less than 20% by weight, the effect of reducing the thermal expansion coefficient tends to be low. If the blending amount exceeds 90% by weight, the viscosity of the liquid resin composition for encapsulating electronic components increases, and the fluidity and permeability deteriorate. In addition, workability tends to be reduced.

(Flexible agent)
Various flexible agents can be blended in the liquid resin composition for encapsulating electronic components of the present invention from the viewpoints of improving thermal shock resistance and reducing stress on semiconductor elements. There are no particular restrictions on the flexible agent, but rubber particles are preferred. Specific examples include styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic rubber. Examples thereof include rubber particles made of rubber such as (AR). Among these rubber particles, 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 rubber particles other than those described above. Specific examples include silicone rubbers obtained by crosslinking polyorganosiloxanes such as linear polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Particles: The surface of silicone rubber particles coated with a silicone resin; Core-shell polymer particles having a core layer made of solid silicone particles obtained by emulsion polymerization and the like, and a shell layer made of an organic polymer such as an acrylic resin; etc. Is mentioned. These silicone rubber particles may be amorphous or spherical, but are preferably spherical from the viewpoint of moldability of the liquid resin composition for sealing electronic parts. These silicone rubber particles are commercially available from Toray Dow Corning Silicone Co., Ltd. and Shin-Etsu Chemical Co., Ltd.

  The average primary particle size of the rubber particles is preferably 0.05 μm or more and less than 5.0 μm, more preferably 0.1 μm or more and 2.0 μm or less. If the average primary particle size is less than 0.05 μm, the dispersibility in the liquid resin composition for sealing electronic parts tends to be inferior, and if it is 5.0 μm or more, the stress reduction effect tends to be low. The fluidity / penetration in a narrow gap of the liquid resin composition for stopping is lowered, and voids are easily generated or not filled.

  The blending amount of the rubber particles is preferably in the range of 1 to 30% by weight, and in the range of 2 to 20% by weight of the total amount excluding the (D) inorganic filler from the entire liquid resin composition for electronic component sealing. It is more preferable that If the blended amount of the rubber particles is less than 1% by weight, the effect of reducing the stress tends to be low, and if it exceeds 30% by weight, the viscosity of the liquid resin composition for sealing electronic parts rises and moldability (flow characteristics) is improved. There is a tendency to be inferior.

(Surfactant)
In the liquid resin composition for sealing electronic parts of the present invention, various surfactants can be blended from the viewpoint of reducing the generation of voids during molding and improving the adhesive strength by improving the wettability to various adherends. . The surfactant is not particularly limited, but is preferably a nonionic surfactant. Specific examples include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid. Ester, Polyoxyethylene sorbitol fatty acid ester, Glycerin fatty acid ester, Polyoxyethylene fatty acid ester, Polyoxyethylene alkylamine, Alkyl alkanolamide, Polyether modified silicone, Aralkyl modified silicone, Polyester modified silicone And surfactants such as polyacrylic compounds. The said surfactant may be used individually by 1 type, and may be used in combination of 2 or more type. 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. The silicone-modified epoxy resin is preferably liquid at normal temperature. Examples of the organosiloxane having a functional group that reacts with the epoxy group include dimethylsiloxane, diphenylsiloxane, and methylphenylsiloxane each having at least one amino group, carboxyl group, hydroxyl group, phenolic hydroxyl group, mercapto group, and the like in one molecule. Etc. The weight average molecular weight of the organosiloxane having a functional group that reacts with the epoxy group is preferably 500 to 5,000. When the weight average molecular weight is less than 500, the compatibility with the resin system becomes too good and the effect as an additive is hardly exhibited. When the weight average molecular weight exceeds 5000, the silicone-modified epoxy resin is molded because it becomes incompatible with the resin system. Occasionally, separation and exudation occur, and the adhesiveness and appearance tend to be impaired.

  The epoxy resin for obtaining the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin system of the liquid resin composition for electronic component sealing, and is generally used for the liquid resin composition for electronic component sealing. It is possible to use an epoxy resin. Specific examples of the epoxy resin include glycidyl ether type epoxy resins obtained by the reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like and epichlorohydrin; orthocresol novolac type epoxy resins A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by condensing or co-condensing phenols and aldehydes; a glycidyl ester-type epoxy resin obtained by reaction of a polybasic acid such as phthalic acid or dimer acid with epichlorohydrin Glycidylamine-type epoxy resin obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; obtained by oxidizing olefinic bonds with peracids such as peracetic acid That linear aliphatic epoxy resins; alicyclic epoxy resins; and the like, among these, the liquid epoxy resin at room temperature is preferred. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The blending amount of the surfactant is preferably in the range of 0.01 to 1.5% by weight, more preferably in the range of 0.05 to 1% by weight of the whole liquid resin composition for sealing electronic components. preferable. If the blending amount of the surfactant is less than 0.01% by weight, a sufficient addition effect cannot be obtained. If the blending amount exceeds 1.5% by weight, exudation from the surface of the cured product occurs at the time of curing and the adhesive strength is lowered. Tend.

(Coupling agent)
In the liquid resin composition for sealing an electronic component of the present invention, a coupling agent is blended for the purpose of strengthening the interfacial adhesion between the resin and the inorganic filler or the resin and the component of the electronic component device as necessary. be able to. There is no restriction | limiting in particular as a coupling agent, A conventionally well-known thing can be used. Coupling agents include silane compounds having primary and / or secondary and / or tertiary amino groups, various silane compounds such as epoxy silane, mercapto silane, alkyl silane, ureido silane, vinyl silane, titanium compounds, aluminum Chelates, aluminum / zirconium compounds and the like can be mentioned. Specific examples thereof include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-amino Propyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Orchid, 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) aminopropyl Methyldimethoxysilane, 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, isopropyltri Isostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl Bis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as The said coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.

(Ion trap agent)
The liquid resin composition for encapsulating electronic components of the present invention is represented by the following composition formulas (I) and (II) from the viewpoint of improving migration resistance, moisture resistance and high-temperature storage characteristics of a semiconductor element such as an IC. An ion trapping agent can be blended.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (I)
(0 <X ≦ 0.5, m is a positive number)
BiOx (OH) y (NO ₃ ) z (II)
(0.9 ≦ x ≦ 1.1, 0.6 ≦ y ≦ 0.8, 0.2 ≦ z ≦ 0.4)
As an ion trap agent represented by the above formula (I), a product name “DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd. is available as a commercial product. Further, as the ion trapping agent represented by the above formula (II), a trade name “IXE500” manufactured by Toagosei Co., Ltd. is available as a commercial product.

  The blending amount of the ion trapping agent is preferably in the range of 0.1 to 3.0% by weight, and in the range of 0.3 to 1.5% by weight of the entire liquid resin composition for sealing electronic components. Is more preferable.

  The average particle size of the ion trapping agent is preferably 0.1 to 3.0 μm, and the maximum particle size is preferably 10 μm or less.

  If necessary, other anion exchangers can be blended. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Specific examples of the anion exchanger include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like. These anion exchangers may be used alone or in combination of two or more.

  The liquid resin composition for encapsulating electronic parts of the present invention may contain other additives such as dyes, colorants such as carbon black, diluents, leveling agents, antifoaming agents and the like as necessary. .

  The liquid resin composition for encapsulating electronic components of the present invention can be prepared by any method as long as the above components can be uniformly dispersed and mixed. As a general method, it can be obtained by weighing each component of a predetermined blending amount, mixing and kneading using a raking machine, a mixing roll, a planetary mixer or the like, and defoaming as necessary.

  The viscosity at 25 ° C. of the liquid resin composition for sealing an electronic component of the present invention is preferably 5 to 200 Pa · s, more preferably 10 to 100 Pa · s. The viscosity at 25 ° C. of the liquid resin composition for sealing electronic parts can be determined by measuring using an E-type viscometer (cone angle 3 °, rotation speed 10 rpm).

  Moreover, the gel time of the liquid resin composition for electronic component sealing of this invention becomes like this. Preferably it is 500 seconds or less, More preferably, it is 300 seconds or less. The gel time can be determined by measuring the time (seconds) until gelation starts after a suitable amount of the liquid resin composition for sealing electronic components is placed on a hot plate at 165 ° C. using a gelling tester. .

  Moreover, the amount of heating weight reduction of the liquid resin composition for encapsulating electronic parts of the present invention is preferably 3% by weight or less, more preferably 2% by weight or less. The weight loss by heating was determined by using a thermogravimetric measuring device “TGA-Q500” (TA Instruments) and heating 20 mg of the liquid resin composition for encapsulating electronic components in air from room temperature to 165 ° C. It can be determined by measuring the amount of weight loss (% by weight) when heated in minutes and held at 165 ° C. for 1 hour.

(Electronic component equipment)
An electronic component device according to the present invention includes an electronic component sealed with the liquid resin composition for sealing an electronic component according to the present invention. Such electronic component devices include, for example, lead frames, wired tape carriers, rigid and flexible wiring boards, glass, silicon wafers and other support members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors Examples thereof include electronic parts such as a passive element such as a body, a resistor array, a coil, and a switch, which are sealed with the liquid resin composition for sealing electronic parts of the present invention. Among these, a semiconductor device in which a semiconductor element is directly bump-connected on a wiring board is preferable, and flip chip bonding in which a semiconductor element is directly bump-connected to a rigid and flexible wiring board or a wiring board formed on glass. A semiconductor device is particularly preferred. Specific examples include semiconductor devices such as flip-chip BGA (Ball grid array), LGA (Land Grid Array), and COF (Chip On Film).

  The liquid resin composition for sealing electronic parts of the present invention is suitable as an underfill material for flip chip mounting semiconductor devices having excellent reliability. The field of flip chip mounting in which the liquid resin composition for sealing electronic components of the present invention is particularly suitable is that the material of the bump connecting the wiring board and the semiconductor element is not a conventional lead-containing solder, but Sn-Ag-Cu type This is a flip-chip mounted semiconductor device using lead-free solder. Compared to conventional lead-containing solder, the liquid resin composition for sealing electronic components of the present invention has good reliability even for flip chip mounting semiconductor devices that are bump-bonded using lead-free solder that is brittle in physical properties. Can be secured. Furthermore, the liquid resin composition for sealing an electronic component of the present invention is suitable for a large element having a long side length of 5 mm or more of the electronic component. An electronic component device that exhibits good fluidity and filling properties even for Philip chip connection in a narrow gap where the distance between bump connection surfaces of electronic components is 60 μm or less, and excellent reliability such as moisture resistance and thermal shock resistance Can be provided. A more preferable long side length of the electronic component is 5 to 30 mm, and a more preferable distance between the wiring board and the bump connection surface of the electronic component is 30 to 60 μm.

  In recent years, an interlayer insulating film having a low dielectric constant has been formed on a semiconductor element as the speed of the semiconductor element has been increased. However, the interlayer insulating film having a low dielectric constant has a low mechanical strength and breaks down due to external stress. Tends to occur. Such a tendency becomes more prominent as the semiconductor element becomes larger, and a stress reduction effect by the underfill material is required. The liquid resin composition for sealing an electronic component of the present invention has a long side length of 5 mm or more of the electronic component, and the electronic component has a dielectric layer having a dielectric constant of 3.0 or less. Can exhibit an excellent stress reduction effect and can provide a highly reliable semiconductor device. A more preferable long side length of the electronic component is 5 to 30 mm, and a more preferable dielectric constant of the electronic component is 2.7 or less.

  Examples of a method for sealing an electronic component using the liquid resin composition for sealing 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 component sealing, 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 (Ball Grid Array) were used as semiconductor devices used for impregnation time, void observation, and reliability evaluation.

(A) Non low-k flip chip BGA
Chip size 20 × 20 × 0.55 tmm (circuit: daisy chain connection of aluminum, passivation: polyimide film manufactured by Hitachi Chemical DuPont Microsystems, trade name “HD4000”), bump: solder ball (Sn—Ag—Cu, Φ80 μm, 7,744 pin), bump pitch: 190 μm, substrate: FR-5 (Solder resist manufactured by Hitachi Chemical Co., Ltd., trade name “SR7000”, 60 × 60 × 0.8 tmm), distance between substrate and bump connection surface : 50μm
(B) Low-k flip chip BGA
Chip size 20 × 20 × 0.55 tmm (Three dielectric layers with a dielectric constant of 2.7 are formed. Circuit: Daisy chain connection of aluminum, Passivation: Polyimide film manufactured by Hitachi Chemical DuPont Microsystems, Inc. Name “HD4000”), bump: solder ball (Sn—Ag—Cu, Φ80 μm, 7,744 pin), bump pitch: 190 μm, substrate: FR-5 (solder resist manufactured by Hitachi Chemical Co., Ltd., trade name “SR7000”) ”, 60 × 60 × 0.8 tmm), distance between substrate and bump connection surface: 50 μm
The semiconductor device used for the following evaluation tests (8) to (11) uses a liquid resin composition for sealing electronic components as an underfill material to seal the semiconductor element by a dispensing method, and is heated at 165 ° C. for 2 hours. It was prepared by curing under conditions. Moreover, the hardening conditions of the various test pieces used for the following evaluation tests (5) and (6) were also performed under the same conditions.

(1) Viscosity The viscosity at 25 ° C. of the liquid resin composition for sealing electronic parts was measured using an E-type viscometer (cone angle 3 °, rotation speed 10 rpm).

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

(3) Heated weight reduction amount Using a thermogravimetric measuring device “TGA-Q500” (TA Instruments), 20 mg of a liquid resin composition for sealing electronic components was heated from room temperature to 165 ° C. in air, at a rate of temperature increase of 10 ° C. The weight loss (% by weight) was measured when the sample was heated at 1 min / min and held at 165 ° C. for 1 hour.

(4) Tg
Using a thermomechanical analyzer “TMA4000SA” (manufactured by Mac Science), Tg of a test piece (3 mm × 3 mm × 20 mm) prepared by curing a liquid resin composition for sealing electronic components at 165 ° C. for 1 hour, a load of 15 g The measurement was performed under the conditions of a measurement temperature of 0 ° C. to 200 ° C. and a heating rate of 10 ° C./min.

(5) Adhesive strength to solder resist (SR adhesive strength)
On the surface of the solder resist “SR7000” (manufactured by Hitachi Chemical Co., Ltd.), a test piece was prepared by molding a liquid resin composition for sealing electronic components to a diameter of 3 mm and a height of 1 mm, and a bond tester “DS100 type” (DAGE 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 / second and 25 ° C.

  This measurement was performed immediately after producing the test piece and immediately after treating the test piece for 150 hours under the condition of 130 ° C. and 85% RH HAST (Highly Accelerated Temperature and Humidity Stress Test).

(6) Adhesive strength to polyimide (PI adhesive strength)
On the surface of photosensitive polyimide “HD4000” (manufactured by Hitachi Chemical DuPont Microsystems Co., Ltd.), a test piece was prepared by molding a liquid resin composition for sealing electronic components to a diameter of 3 mm and a height of 1 mm. ”(Manufactured by DAGE) was subjected to shear stress under the conditions of a head speed of 50 μm / second and 25 ° C., and the strength at which the test piece peeled from the photosensitive polyimide was measured.

  This measurement was performed immediately after preparing the test piece and immediately after treating the test piece for 150 hours under HAST conditions of 130 ° C. and 85% RH.

(7) 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 sealing electronic components is dropped on the side surface (one side) of the semiconductor element using a dispenser. The time (seconds) until the liquid resin composition for component sealing penetrates into the opposing side surfaces of the semiconductor element was measured.

(8) Presence of voids Ultrasonic flaw detector “AT-5500” (Hitachi Construction Machinery Co., Ltd.) inside a semiconductor device manufactured by sealing a semiconductor element using a liquid resin composition for sealing electronic components as an underfill material (Manufactured by company) and examined for the presence of voids.

(9) Reflow resistance A semiconductor device produced by encapsulating a semiconductor element using a liquid resin composition for encapsulating electronic components as an underfill material was heated and dried at 120 ° C. for 12 hours, and then 85 ° C. and 60% RH. After absorbing moisture for 168 hours and passing through a far-infrared heating type reflow furnace (preheating 150 ° C. to 180 ° C. for 50 seconds, peak temperature 260 ° C., heating time of 250 ° C. or higher for 40 seconds) three times, The inside is observed with an ultrasonic flaw detector “AT-5500” (manufactured by Hitachi Construction Machinery Co., Ltd.), and the presence or absence of peeling between the cured resin and the semiconductor element, peeling between the cured resin and the substrate, or cracking of the cured resin is confirmed. The number of defective packages / the number of evaluation packages was evaluated.

(10) Temperature resistance cycle resistance A semiconductor device produced by encapsulating a semiconductor element using a liquid resin composition for encapsulating electronic components as an underfill material is -50 ° C to 150 ° C at a heat cycle of 30 minutes for each 1000 minutes. A cycle treatment was conducted, a continuity test was performed to check for the presence of disconnection of the aluminum wiring and the pad, and the evaluation was made based on the number of defective packages / number of evaluation packages.

(11) Moisture resistance A semiconductor device fabricated by encapsulating a semiconductor element using a liquid resin composition for encapsulating electronic components as an underfill material is treated for 150 hours under 130 ° C. and 85% RH HAST conditions, and then conductive. A test was conducted to determine whether the aluminum wiring and the pads were disconnected, and the evaluation was made based on the number of defective packages / number of evaluation packages.

Examples 1-8, Comparative Examples 1-7
The following components were blended in the compositions (parts by weight) shown in Tables 1 and 2 below, kneaded and dispersed with a three roll and vacuum crusher, and then the electrons of Examples 1 to 8 and Comparative Examples 1 to 7 A liquid resin composition for component sealing was produced.

  The liquid resin compositions for sealing electronic components of Examples 1 to 8 and Comparative Examples 1 to 7 were evaluated by the various characteristic tests of the above (1) to (11). The evaluation results are shown in Tables 1 and 2 below. Note that the blank in the table indicates no blending.

  Each component in the table was as follows.

(Epoxy resin)
Epoxy resin 1: Liquid diepoxy resin having an epoxy equivalent of 160 obtained by epoxidizing bisphenol F (trade name “YDF-8170C” manufactured by Toto Kasei Co., Ltd.)
Epoxy resin 2: Trifunctional liquid epoxy resin having an epoxy equivalent of 95 obtained by epoxidizing aminophenol (trade name “E630” manufactured by JER)
(Curing agent)
Liquid amine 1: Diethyltoluenediamine having an active hydrogen equivalent of 45 (trade name “Epicure W” manufactured by JER)
Liquid amine 2: 3,3′-diethyl-4,4′-diamino-diphenylmethane having an active hydrogen equivalent of 63 (manufactured by Nippon Kayaku Co., Ltd., trade name “Kayahard AA”)
(Hydrazide compound)
Hydrazide compound 1: adipic acid dihydrazide having an average particle diameter of 1.5 μm and an active hydrogen equivalent of 43.5 (trade name “ADH-4S” manufactured by Otsuka Chemical Co., Ltd.)
Hydrazide Compound 2: Adipic acid dihydrazide having an average particle size of 15 μm and an active hydrogen equivalent of 43.5 (trade name “ADH” manufactured by Nippon Hydrazine Kogyo Co., Ltd.)
Hydrazide Compound 3: Isophthalic acid dihydrazide having an average particle size of 1.8 μm and an active hydrogen equivalent of 48.5 (trade name “IDH-S” manufactured by Otsuka Chemical Co., Ltd.)
(Inorganic filler)
Spherical fused silica with an average particle size of 1 μm (curing accelerator)
2-Phenyl-4-methyl-5-hydroxymethylimidazole (silane coupling agent)
γ-glycidoxypropyltrimethoxysilane (colorant)
Carbon black (trade name “MA-100”, manufactured by Mitsubishi Chemical Corporation)
(Ion trap agent)
Bismuth ion trapping agent (trade name “IXE-500” manufactured by Toagosei Co., Ltd.)
* 1 to * 3 in the table are as follows.

  * 1: The active hydrogen equivalent of the liquid amine curing agent is the equivalent of the active hydrogen equivalent of the curing agent when the total of the active hydrogen equivalent of the curing agent and the active hydrogen equivalent of the hydrazide compound is 1 equivalent per 1 equivalent of epoxy resin. Represents.

  * 2: The active hydrogen equivalent of the hydrazide compound represents the active hydrogen equivalent of the hydrazide compound when the sum of the active hydrogen equivalent of the curing agent and the active hydrogen equivalent of the hydrazide compound is 1 equivalent per 1 equivalent of epoxy resin. .

* 3: The content (% by weight) of the inorganic filler represents the content of the inorganic filler with respect to the entire liquid resin composition for sealing an electronic component.

  In Comparative Examples 1 and 2 that do not contain the hydrazide compound (C) and the curing accelerator in the present invention, voids occurred because the gel time was long and the heating weight loss was large. In addition, Comparative Examples 3 to 4 that contain a curing accelerator and do not contain the (C) component hydrazide compound and Comparative Examples 5 and 7 that contain the curing accelerator and (C) the component hydrazide compound powder are coarse have a gel time. The generation of voids could be prevented by shortening to some extent and reducing the weight loss by heating. However, since the reaction is insufficient in 1 hour curing, the Tg is low, and the adhesive strength with each adherend is small, so reflow resistance and temperature cycle resistance are extremely inferior in various reliability such as moisture resistance. It was. Further, Comparative Example 6 in which the ratio of the curing agent of the component (C) was increased with respect to Comparative Example 5, but the gel time was shortened and Tg was increased. However, the adhesive strength after the HAST 150 hour treatment was greatly reduced, so that the moisture resistance was improved. It got worse.

  On the other hand, Examples 1 to 8 show a high Tg and adhesive force because the gel time is short and the heating weight loss is small, there is no void generation during molding, and the reaction proceeds sufficiently by curing for 1 hour, It is excellent in productivity and further improved in the reliability after the HAST 150-hour treatment, and thus has excellent reliability such as reflow resistance, temperature cycle resistance and moisture resistance.

Claims (7)

  (A) an epoxy resin containing a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) a hydrazide compound having an average particle size of less than 2 μm, and (D) an inorganic filler having an average particle size of less than 2 μm. A liquid resin composition for sealing electronic parts, comprising:   The said hydrazide compound is at least 1 sort (s) chosen from a C2-C10 aliphatic polybasic acid dihydrazide compound and a C8-C15 aromatic polybasic acid dihydrazide compound. Liquid resin composition for sealing electronic parts.   The electronic component apparatus provided with the electronic component sealed with the liquid resin composition for electronic component sealing of Claim 1 or 2.   4. The electronic component device according to claim 3, wherein the electronic component is a semiconductor element, and the semiconductor element is directly bump-connected on a wiring board.   The electronic component device according to claim 4, wherein the bump is a metal containing no lead.   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 60 μm or less. The electronic component device described in 1.   The length of the long side of the electronic component is 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. Electronic component device.