JP6386483B2 - Liquid resin composition for electronic components and electronic component device - Google Patents

Description

  The present invention relates to a liquid resin composition for electronic components suitable for sealing electronic components and an electronic component device sealed thereby.

  Conventionally, in the field of element sealing for 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). In recent years, as a method for mounting display driving ICs such as liquid crystal, it has been used in a mounting form (flip chip connection method) in which a semiconductor element is directly bump-connected to a wiring board, and a liquid resin composition for electronic components used for this mounting. Is known as an underfill material.

  The underfill material is filled in a space generated between the wiring board and the semiconductor device for the purpose of sealing for maintaining insulation between the bumps and maintaining mechanical strength in the semiconductor mounting method using the flip-chip connection method. . Therefore, the underfill material has (1) a low-viscosity liquid at room temperature, and (2) a resin composition containing no solvent in order to avoid generation of bubbles in the thermosetting process of the resin after filling. (3) Avoid the inclusion of solid components such as fillers as much as possible to avoid an increase in viscosity and a decrease in permeability. (4) In the case of containing a solid component, in the liquid resin composition for electronic components It is an item that requires conditions such as maintaining a uniform dispersibility of the solid component and maintaining a suitable particle size distribution and filling amount that do not impair the viscosity, fluidity, and permeability.

  In the wiring board and the semiconductor device described above, the distance between the wirings is narrowed, and some of the most advanced flip chip semiconductor devices have a wiring pitch of 30 μm or less. When a high voltage is applied between the wirings with a narrow pitch, the migration phenomenon has become a big problem as one of the defective phenomena that impairs the insulation reliability of the liquid resin composition for electronic parts. In particular, the deterioration of the resin and the wiring metal is promoted under high temperature and high humidity, so that migration is likely to occur, and there is a tendency for further concern about the occurrence of defects in the semiconductor device.

  In order to avoid such defects, measures have been taken for the purpose of suppressing migration of resin compositions used for electronic parts. For example, as a metal ion scavenger, a resin composition containing an inorganic ion exchanger (for example, see Patent Documents 1 to 4), a benzotriazine, a benzotriazole or a resin composition containing these isocyanuric acid adducts (for example, Patent Documents 5 to 10), a resin composition in which a compound containing a borate salt is blended in a curing accelerator (for example, see Patent Document 11), and a resin composition in which an antioxidant is blended (for example, Patent Documents 12 to 12). 13) is known as a resin composition for use in applications such as sealing materials, adhesives, and prepregs.

  Among the known examples, in the resin composition containing the antioxidant exemplified in Patent Documents 12 to 13, in the resin composition for printed circuit boards represented by prepreg, in addition to the effect of preventing the deterioration of the resin, migration resistance It is known that the properties are particularly excellent. In the resin composition for printed circuit boards, since a solvent such as methyl ethyl ketone (MEK) or toluene is used at the time of blending, generally various solid (powder) antioxidants are mixed with an epoxy resin, a curing agent and a curing accelerator at room temperature. Any antioxidant can be selected depending on the application and characteristics.

JP-A-6-158492 JP 9-314758 A JP 2000-183470 A JP 2007-63549 A JP 2001-6769 A JP 2001-203462 A Patent No. 3881286 JP-A-2005-72275 JP-A-2005-333085 Japanese Patent No. 3633422 JP 2008-7777 A JP-A-3-39320 Japanese Patent Application Laid-Open No. 10-279979

  On the other hand, in the liquid resin composition for electronic parts used as the underfill material, as described above, no solvent is used in order to avoid the generation of bubbles (voids) in the thermosetting process of the resin after filling. For this reason, a conventionally known antioxidant is uniformly dissolved in a solvent-free liquid resin composition for electronic parts, and has low viscosity, high fluidity, high permeability, fast curing, low water absorption, and high adhesion. It has been difficult to obtain a liquid resin composition for electronic parts that is excellent in migration resistance without impairing various properties essential as an underfill material, such as properties.

  Currently, migration resistance is improved by reducing impurities in the liquid resin composition for electronic components. However, for example, COF (Chip On Film), which is a representative semiconductor device with remarkable thinning and narrowing of pitch, requires further improvement in migration resistance, and it can be handled only by increasing the purity of the liquid resin composition for electronic parts. Is becoming difficult.

  The present invention has been made in view of such a situation, and provides a liquid resin composition for electronic components which has excellent migration resistance and is excellent in other moldability and reliability, and an electronic component device sealed thereby. Is.

  As a result of intensive studies to solve the above problems, the present inventors have good adhesion between an electronic component such as a semiconductor element and a wiring board, a low water absorption, and a low viscosity that suppresses oxidative degradation. The present inventors have found that the above object can be achieved by applying a high-purity liquid resin composition for electronic parts that is excellent in fluidity, and have completed the present invention.

  The present invention relates to the following (1) to (14).

  (1) A liquid resin composition for electronic parts comprising an epoxy resin, a normal-temperature liquid cyclic acid anhydride, a coupling agent, and a phenol compound having at least one alkyl group at the ortho position of the phenol nucleus.

  (2) The liquid resin composition for electronic parts according to claim 1, wherein the phenol compound having at least one alkyl group at the ortho position of the phenol nucleus contains a phenol compound having one methyl group at the ortho position of the phenol nucleus. object.

  (3) The phenol compound having at least one alkyl group at the ortho position of the phenol nucleus has a saturated dissolution amount in a bisphenol F-type epoxy resin of 5% by weight or more, for electronic components according to (1) or (2) Liquid resin composition.

  (4) A liquid resin composition for electronic parts comprising an epoxy resin, a cyclic acid anhydride at room temperature, a coupling agent, and an antioxidant, wherein the antioxidant comprises an antioxidant that is liquid at room temperature.

  (5) The liquid resin composition for electronic components according to any one of (1) to (4), further containing an inorganic filler, and the blending amount of the inorganic filler is 10% by mass or less.

  (6) The liquid resin composition for electronic parts according to any one of (1) to (5), further containing rubber particles.

  (7) The liquid resin composition for electronic parts according to any one of (1) to (6), further containing a silicone-modified epoxy resin.

  (8) The liquid resin composition for electronic parts according to any one of (1) to (7), further comprising an ion trap agent.

  (9) The liquid resin composition for electronic parts according to any one of (1) to (8), further comprising a latent curing accelerator that promotes the reaction between the epoxy resin and the cyclic acid anhydride of the room temperature liquid. .

  (10) The liquid resin composition for electronic parts according to any one of (1) to (9), wherein the organic solvent content is 1% or less.

  (11) The liquid resin composition for electronic parts as described in any one of (1) to (10), wherein the cyclic acid anhydride of the room temperature liquid has an acid anhydride equivalent of 200 or more.

  (12) The liquid resin composition for electronic parts according to any one of (1) to (11), wherein the viscosity at 25 ° C. using an EMD type rotational viscometer is 1.2 Pa · s or less.

  (13) The liquid resin composition for electronic components according to any one of (1) to (12), which is used in an electronic component device in which an electronic component is directly bump-connected on a wiring board having a film as a base material.

  (14) An electronic component device sealed with the liquid resin composition for electronic components according to any one of (1) to (13).

  The liquid resin composition for an electronic component according to the present invention has good migration resistance, good adhesion between an electronic component such as a semiconductor element and a wiring board, a low water absorption rate, and low oxidation deterioration. Since it is a high-purity liquid resin composition for electronic parts that is excellent in viscosity and fluidity, its industrial value is great. Particularly useful as an underfill material for semiconductor devices such as flip-chip BGA and COF, in which semiconductor elements are flip-chip bonded to rigid wiring boards, flexible wiring boards, and wiring formed on glass by bump connection. It is.

(A) is a figure which shows the anode vicinity and wiring width before a test in migration resistance evaluation, (b) is a figure which shows the anode vicinity and wiring width after migration generate | occur | produced.

  The (A) epoxy resin used in the present invention is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule that can be cured, and is generally used in a liquid resin composition for electronic parts. An epoxy resin can be used. If the composition is liquid, either solid or liquid may be used, or both may be used in combination. For example, phenols and aldehydes such as glycidyl ether type epoxy resin, orthocresol novolac type epoxy resin obtained by reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like with epichlorohydrin Novolak type epoxy resin obtained by epoxidizing novolak resin obtained by condensation or co-condensation with glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diaminodiphenylmethane, isocyanuric acid, etc. Glycidylamine-type epoxy resin obtained by reaction of polyamines with epichlorohydrin, linear aliphatic epoxy obtained by oxidizing olefinic bonds with peracids such as peracetic acid Butter, and the like alicyclic epoxy resins may be used in combination of two or more even with these alone.

  Among these, a liquid epoxy resin is preferable from the viewpoint of reducing the viscosity, and a bisphenol liquid epoxy resin is more preferable from the viewpoint of reactivity with the cyclic acid anhydride.

  In addition, these epoxy resins are preferably sufficiently purified and have few ionic impurities. For example, free Na ions and free Cl ions are more preferably 500 ppm or less.

  There is no particular limitation on the cyclic acid anhydride (B) used in the present invention as a normal temperature liquid cyclic acid anhydride. For example, phthalic anhydride, maleic anhydride, methyl hymic anhydride, highmic anhydride, succinic anhydride, tetrahydrophthalic anhydride Acid, hexahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, methylhexahydro It is obtained by Diels-Alder reaction from phthalic acid, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, methyltetrahydrophthalic anhydride, hydrogenated methylnadic anhydride, maleic anhydride and diene compound. Having an alkyl group of Kill tetrahydrophthalic anhydride, various cyclic acid anhydride such as dodecenyl succinic anhydride and the like.

  “Cyclic anhydride” means that two carbon atoms C of “—CO—O—CO—” are chemically bonded to the other two carbon atoms to form a ring as represented by phthalic anhydride. It shows what has become. The “acid anhydride equivalent” is expressed by (molecular weight of acid anhydride) / (number of hydroxyl groups in the acid anhydride molecule).

  As a compound having an acid anhydride equivalent of 200 or more, for example, a product name jER Cure YH306 manufactured by Japan Epoxy Resin Co., Ltd. having an acid anhydride equivalent of 234 is commercially available.

  When the acid anhydride has an acid equivalent of less than 200, the amount of ester bonds in the cured product increases, so that it is susceptible to hydrolysis at high temperatures and high humidity, which tends to cause a decrease in moisture resistance, particularly migration resistance. . Further, when the acid anhydride equivalent of the acid anhydride is less than 200, the water absorption is also increased due to the influence of the ester group, which also causes a decrease in migration resistance. That is, since the cyclic acid anhydride having a large acid anhydride equivalent has a lower ester group concentration than the cyclic acid anhydride having a small acid equivalent equivalent, the cured product has a low water absorption rate. The amount of ionic impurities can be reduced.

  The acid anhydride equivalent is preferably 200 to 400, more preferably 200 to 300.

  The structure of the cyclic acid anhydride of component (B) is not particularly limited, but it is preferable that the molecule does not contain halogen atoms such as chlorine and bromine and ester bonds from the viewpoint of migration resistance.

  In the present invention, curing agents other than the component (B) can be used as appropriate, and those generally used as curing agents for epoxy resins can be used. For example, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4 -Aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, laromine, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine mixture, N-aminoethylpiperazine, etc. Amine compounds, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyano Til) -2-ethyl-4-methylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1)) ethyl-s-triazine, 2-phenylimidazoline, 2,3-dihydro-1H- Examples include imidazole compounds such as pyrrolo (1,2-a) benzimidazole, tertiary amines, DBU, dicyandiamide, organic acid dihydrazide, and N, N-dimethylurea derivatives. Of these, amine compounds are preferred from the viewpoint of viscosity reduction.

  The blending amount of the room temperature liquid cyclic acid anhydride as the component (B) is preferably 30% by mass or more, more preferably 40% by mass or more based on the total amount of the curing agent containing the component (B) in order to exhibit its performance. 60 mass% or more is more preferable.

  The equivalent ratio of the (A) epoxy resin and the total curing agent including the cyclic acid anhydride of the room temperature liquid of the component (B) is not particularly limited, but in order to suppress each unreacted component to a small amount, It is preferable to set a hardening | curing agent in the range of 0.6-1.6 equivalent, 0.7-1.4 equivalent is more preferable, 0.8-1.2 equivalent is further more preferable. When deviating from the range of 0.6 to 1.6 equivalents, the curing reaction is insufficient and the reliability tends to be lowered. Here, the equivalent is a reaction equivalent. For example, an acid anhydride equivalent of an acid anhydride is calculated as one acid anhydride group reacts with one epoxy group, and an equivalent of a phenol resin is one epoxy group. Is calculated as one phenolic hydroxyl group reacts, and the equivalent of aromatic amine is calculated as one amino group active hydrogen reacts with one epoxy group.

  There is no restriction | limiting in particular as (C) coupling agent used in this invention, Although a conventionally well-known thing can be used, For example, the silane compound which has a primary and / or secondary and / or tertiary amino group, Examples thereof include various silane compounds such as epoxy silane, mercaptosilane, alkyl silane, ureido silane, 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.

  (C) The total amount of coupling agent is preferably 0.037 to 5.0% by mass, more preferably 0.05 to 4.75% by mass, based on the liquid resin composition. More preferably, it is 0.1-2.5 mass%. If the amount is less than 0.037% by mass, the adhesion between the substrate and the cured product of the liquid resin composition tends to decrease, and if it exceeds 5.0% by mass, the physical properties such as glass transition temperature and bending strength tend to decrease.

  A conventionally well-known thing can be used as (D) antioxidant used in this invention. For example, as a compound having a phenol compound antioxidant and having at least one alkyl group at the ortho position of the phenol nucleus, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 3,9-bis [2- [3- (3-t-butyl -4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 4,4'-butylidenebis- (6- t-butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), tetrakis [methylene-3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate] methane, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 4,6-bis (dodecylthiomethyl) -o-cresol, bis (3,5-di-) t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, 2,4-1bis [(octylthio) methyl] -o-cresol, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4 8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl ) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2,2'-methylenebis -(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, Trier Lenglycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, diethyl [[3 5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 2,5,7,8-tetramethyl-2 (4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6 -Ol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like. As dicyclohexylamine, trade name D-CHA-T manufactured by Shin Nippon Rika Co., Ltd. is available as a commercial product, and derivatives thereof include dicyclohexylamine ammonium nitrite and N, N-di (3-methyl-cyclohexylamine). N, N-di (2-methoxy-cyclohexyl) amine, N, N-di (4-bromo-cyclohexyl) amine, and the like. Organic sulfur compound-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityltetrakis (3-lauryl thiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,2 -Thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,6-bis (dodecylthiomethyl) -o-cresol, 2,4-1bis [( Octylthio) methyl] -o-cresol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylani Lino) -1,3,5-triazine, etc. As amine compound-based antioxidants, N, N′-diallyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, octylation Tris as a phosphorus compound type antioxidant such as diphenylamine, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine Nonylphenyl phosphite, triphenyl phosphite, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris (2,4-di-tert-butylphenyl) phosphite, 2- [[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] -N, N-bis [2-{[2,4,8,10-tetrakis (1,1 dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine -6-yl] oxy} -ethyl] ethanamine, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [ d, f] [1,3,2] dioxaphosphine, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, and the like. One of these may be used alone, or two or more may be used in combination. In addition, in the said phenol compound type antioxidant, in addition to the phenol hydroxyl group, the compound which contains at least 1 or more of a phosphorus atom, a sulfur atom, and an amine in the same molecule was mentioned repeatedly.

  Among the antioxidants, phenol compound-based antioxidants having at least one alkyl group at the ortho position of the phenol nucleus and dicyclohexylamine are more preferable from the viewpoint of improving migration resistance. In the phenolic compound-based antioxidant having at least one alkyl group at the ortho position of the phenol nucleus, since the alkyl group at the ortho position is an electron donating group, the electron concentration is increased at the unpaired electron site of the oxygen atom of the phenol hydroxyl group, Antioxidant is coordinated to the surface of the anode metal, and in dicyclohexylamine, the unpaired electron site of the nitrogen atom of the amine is coordinated to the surface of the anode metal, so that the antioxidant coordinated to the metal surface is the metal. It is thought that oxidative degradation is suppressed and migration resistance is improved.

  Furthermore, in the phenolic compound-based antioxidant having at least one alkyl group at the ortho position of the phenol nucleus, a solid, powdery compound is generally known, but as a liquid resin composition for electronic parts, viscosity, permeability, In order to avoid a decrease in fluidity, the cured product of the liquid resin composition for electronic parts is dissolved to the extent that it has sufficient migration resistance with respect to the epoxy resin (A), which is a component of the liquid resin composition for electronic parts. More preferably. Specifically, the saturated dissolution amount with respect to a general epoxy resin, for example, a well-known bisphenol F type epoxy resin used as a liquid epoxy resin in the present invention is preferably 5% by mass or more, and a more preferable range is 10% by mass or more. It is. The reason for this is that the phenolic compound-based antioxidant having a saturated dissolution amount in the preferred range is dissolved in the epoxy resin, so that the phenolic compound-based antioxidant is uniformly dispersed in the liquid resin composition for electronic components. This is because migration resistance is improved. Here, the saturated dissolution amount is a value at room temperature in consideration of the stability of the liquid composition since application of the liquid resin composition is usually performed at room temperature. Among the phenolic compound antioxidants having at least one alkyl group at the ortho position of the phenol nucleus, examples of the phenolic compound antioxidants having such solubility include 4,4′-butylidenebis- (6- t-butyl-3-methylphenol), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- [3- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  Furthermore, among the phenol compound antioxidants dissolved in the epoxy resin, a phenol compound antioxidant having one methyl group at the ortho position of the phenol nucleus is more preferable. This is presumably because the methyl group has little steric hindrance and is an electron donating group, and the unpaired electrons of the phenolic hydroxyl group of the antioxidant are more easily coordinated to the anode metal surface. As such a phenolic compound-based antioxidant, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  In addition, dicyclohexylamine is liquid at room temperature, and has the advantage of being uniformly dispersed without impairing the viscosity, permeability, and fluidity of the liquid resin composition for electronic components compared to solid and powder antioxidants. is there.

  0.1-10 mass% is preferable with respect to (A) epoxy resin, and, as for the compounding quantity of the said phenolic compound type antioxidant, More preferably, it is 0.5-5.0 mass%. If it is less than 0.1% by mass, the effect of suppressing migration is reduced, and if it exceeds 10% by mass, the fluidity of the liquid resin composition for electronic parts tends to be reduced. In addition, 0.1-D mass% is preferable, and, as for the compounding quantity in case the saturated dissolution amount D with respect to (A) epoxy resin of the said phenolic compound type antioxidant is 5 mass% <D <10 mass%, More preferably, Is 0.5-5.0 mass%.

  0.1-30 mass% is preferable with respect to (A) epoxy resin, and, as for the compounding quantity of the said dicyclohexylamine, More preferably, it is 0.5-10 mass%. If the amount is less than 0.1% by mass, the effect of suppressing migration decreases, and if it exceeds 30% by mass, the storage stability of the liquid resin composition for electronic parts and the glass transition temperature of the cured product tend to decrease.

  When the gap between the wiring boards and the bumps of the semiconductor device to which the liquid resin composition for electronic parts of the present invention is applied is 20 μm or less, the gap between the gaps and the fluidity are improved. The amount of the solid compound insoluble in the resin composition is preferably 10% by mass or less, and more preferably 5% by mass or less. On the other hand, the wiring board to which the liquid resin composition for electronic parts of the present invention is applied and the gap between the wirings or bumps of the semiconductor device exceed 20 μm, and further when the migration resistance needs to be improved, the wiring board For the purpose of compensating for the difference in thermal expansion coefficient with the semiconductor device, an inorganic filler can be blended within a range that does not impair the filling property and fluidity between the gaps. The inorganic filler is generally used in liquid resin compositions for electronic parts and is not particularly limited. For example, silica such as fused silica, crystalline silica, synthetic silica, calcium carbonate, talc, clay, alumina oxide, etc. Alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc. And glass fiber. Furthermore, inorganic nanoparticles such as nano silica obtained by hydrolysis / condensation reaction of an alkoxide compound can also be used as a filler. These inorganic fillers may be used alone or in combination of two or more.

  The shape of the inorganic filler is preferably close to a spherical shape from the viewpoint of moldability such as fluidity. The average particle size of the inorganic filler is preferably in the range of 5 nm to 10 μm. When it exceeds 10 μm, filler sedimentation tends to occur, and the permeability / fluidity of the liquid resin composition for electronic parts to the fine gaps tends to decrease, which tends to cause voids / unfilled. Moreover, you may use what carried out the coupling process of the surface as needed for these fillers. The blending amount of the inorganic filler is preferably 10% by mass or less, and more preferably 5% by mass or less of the liquid resin composition for electronic components. When it exceeds 10 mass%, the linear expansion coefficient difference of the hardened | cured material of the liquid resin composition for electronic components and the flexible wiring board using a film board | substrate will become large, and it will become easy to produce peeling in both interface. On the other hand, when the amount of the inorganic filler is large, the viscosity of the liquid resin composition for electronic parts becomes high and the surface tension increases, so that the fluidity tends to decrease.

  In the liquid resin composition for electronic parts of the present invention, it is preferable to use a curing accelerator that accelerates the reaction of the epoxy resin as the component (A) and the curing agent containing the component (B) as necessary. As the curing accelerator, a latent curing accelerator is preferable in order to achieve both curability and pot life. The latent curing accelerator is a substance that exhibits a curing accelerating function under conditions such as a specific temperature. For example, a normal curing accelerator is protected by microcapsules or the like, or has a structure of a salt added with various compounds. Something that has become. In this case, when a specific temperature is exceeded, the curing accelerator is released from the microcapsules and adducts.

  Examples of latent curing accelerators include core-shell particles formed by coating a shell of a normal temperature solid epoxy compound with a normal temperature solid amino group-containing compound as a core. Amicure (manufactured by Ajinomoto Co., Inc.) is a commercially available product. , Registered trademark) and NovaCure (registered trademark, manufactured by Asahi Kasei Chemicals Corporation) in which a microencapsulated amine is dispersed in a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.

  Furthermore, it is a solid particle insoluble in the liquid resin composition system for electronic parts, and it is dissociated at the time of thermoforming, and an amine compound or a phosphorus compound salt that exhibits a curing accelerating action and an intramolecular formed by adding a compound having a π bond thereto. A compound having polarization can be used as a latent curing accelerator.

  For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8- Compounds having intramolecular polarization formed by adding a cycloamidine compound such as diaza-bicyclo (5,4,0) undecene-7 and a compound having a π bond, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamino Derivatives of tertiary amine compounds such as ethanol and tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl Derivatives of imidazole compounds such as imidazole, tributylphosphine, methyldiphenyl Organic phosphine compounds such as sphin, triphenylphosphine, diphenylphosphine, phenylphosphine, maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- Quinone compounds such as dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenol resin, etc. Phosphorus compounds having intramolecular polarization, and their derivatives, triphenylphosphine triphenylboron, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate , N-methyl Include phenyl boronic salts and derivatives thereof, such as morpholine tetraphenyl borate, it may be used in combination of two or more even with these alone.

  Among these, from the viewpoints of storage stability and fast curability, it is preferable to disperse a microencapsulated amine in a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.

  The blending amount of the curing accelerator is not particularly limited as long as the curing accelerating effect is achieved, but it is 0.1 to the total amount of (A) epoxy resin including the non-latent one. 40 mass% is preferable, More preferably, it is 0.5-30 mass%. If it is less than 0.1% by mass, it tends to be inferior in curability in a short time, and if it exceeds 40% 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 to.

  In the liquid resin composition for electronic parts of the present invention, it is preferable to blend various known rubber particles in order to increase the toughness and lower elastic modulus of the cured epoxy resin. The rubber particles that are incompatible with the epoxy resin are effective in lowering the elastic modulus without lowering the glass transition temperature (heat resistance) of the cured product. Specifically, for example, a butadiene / acrylonitrile / styrene copolymer, a modified copolymer having an epoxy group, amino group, carboxyl group, hydroxyl group or the like at the terminal or side chain of the polymer, an epoxy group at the terminal or side chain , Modified silicone elastomers having amino groups, carboxyl groups, hydroxyl groups, and the like. From the viewpoint of handleability and dispersibility with the resin component, it is preferable to use rubber particles that are finely powdered and finely dispersed in an epoxy resin or a curing agent in advance. Since it can mix uniformly in a resin composition, it is preferable that it is a liquid rubber-modified epoxy resin (what melt | dissolved and heated the liquid epoxy resin and the rubber particle) at normal temperature. Inclusion of rubber particles improves the adhesion between the cured resin composition for electronic parts and the substrate, and improves reliability such as high temperature and humidity resistance.

  In addition, the liquid resin composition for electronic components of the present invention may be provided with an ion trap agent as migration resistance, moisture resistance and high temperature as long as it does not impair the filling property and fluidity when applied to wiring boards and semiconductor devices. It is preferably contained from the viewpoint of improving the leaving characteristics. There is no restriction | limiting in particular as an ion trap agent, A conventionally well-known thing can be used, Especially the hydrotalcite represented by the following compositional formula (I) or the hydrous oxide of bismuth represented by (II) is preferable.

(Chemical formula 1)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (I)
(In formula (I), 0 <X ≦ 0.5, m is a positive number.)
(Chemical formula 2)
BiO _x (OH) _y (NO ₃ ) _z (II)
(In formula (II), 0.9 ≦ x ≦ 1.1, 0.6 ≦ y ≦ 0.8, 0.2 ≦ z ≦ 0.4)
The addition amount of these ion trapping agents is not particularly limited as long as it is an amount sufficient to trap anions such as halogen ions, but from the viewpoint of migration resistance, it is 0.1 to 0.1% relative to the liquid resin composition for electronic components. 3.0 mass% is preferable, More preferably, it is 0.3-1.5 mass%. 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. 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.

  Moreover, it is preferable to add a silicone modified epoxy resin to the liquid resin composition for electronic parts of this invention separately from the said (A) epoxy resin component as needed. Addition of the silicone-modified epoxy resin is effective in leveling properties, fillet-forming properties, and void reduction of the liquid resin composition for electronic parts. 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 weight average molecular weight of the organosiloxane is preferably in the range of 500 to 5000. 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 sufficiently exhibited, and if it exceeds 5000, it becomes incompatible with the resin system. This is because separation and oozing occur and the adhesiveness and appearance are impaired.

  The epoxy resin for obtaining the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin system of the liquid resin composition for electronic parts, and is generally used for the liquid resin composition for electronic parts. For example, glycidyl ether type epoxy resins, orthocresol novolac type epoxy resins obtained by the reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like with epichlorohydrin Glycidyl ester type obtained by reaction of a polybasic acid such as phthalic acid and dimer acid with epichlorohydrin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of phenols and aldehydes Glycidylamine type epoxy resin obtained by reaction of polyamine such as poxy resin, diaminodiphenylmethane, isocyanuric acid and epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, alicyclic epoxy Resins and the like can be mentioned, and these may be used alone or in combination of two or more, but those at room temperature are preferred.

  In the liquid resin composition for electronic parts of the present invention, as other additives, colorants such as dyes, carbon black, titanium oxide, and lead tan, flame retardants, diluents, other leveling agents, other stress relaxation agents Further, an antifoaming agent, an adhesion promoter, and the like can be blended as necessary within a range not impairing the filling property and fluidity when applied to the wiring board and the semiconductor device.

  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 Preferably selected from metal elements belonging to the alkaline earth metal elements, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M ² is selected from transition metal elements of groups IIIB to 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, butylphenyl 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.

  The electronic component device obtained by sealing the element with the liquid resin composition for electronic components obtained in the present invention includes a lead frame, a wired tape carrier, a rigid and flexible wiring board, a supporting member such as glass and a silicon wafer. In addition, an active element such as a semiconductor chip, transistor, diode, thyristor, etc., an element such as a passive element such as a capacitor, a resistor, a resistor array, a coil, or a switch is mounted on the liquid resin composition for electronic components of the present invention. Examples thereof include an electronic component device obtained by sealing with an object. In particular, it is preferably used for sealing an electronic component device in which an electronic component is directly bump-connected on a wiring board having a film as a base material. 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 and COF (Chip On Film). In particular, the liquid resin composition for electronic components obtained by the present invention is an underfill material for COF having excellent migration resistance. It is suitable as. Moreover, the liquid resin composition for electronic components of the present invention can also be used effectively for printed circuit boards.

  Examples of a method for sealing an element using the liquid resin composition for electronic parts of the present invention include a dispensing method, a casting method, and a printing method.

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

(Examples 1-5 and comparative examples)
(A) As an epoxy resin, a bisphenol F type liquid epoxy resin having an epoxy equivalent of 160 (trade name YDF-8170C, manufactured by Toto Kasei Co., Ltd.),
Naphthalene-type epoxy resin having an epoxy equivalent of 140 (trade name HP-4032 manufactured by Dainippon Ink & Chemicals, Inc.)
As a rubber particle component, acrylonitrile / butadiene / methacrylic acid / divinylbenzene copolymer (trade name: XER-91P, manufactured by JSR Corporation) is preheated and melted into a bisphenol F type liquid epoxy resin (YDF-8170C) at a mass ratio of 1/4 in advance. , Finely dispersed rubber-modified epoxy resin,
As a leveling agent, a phenol-modified silicone having a hydroxyl equivalent weight of 750 (trade name BY16-799 manufactured by Toray Dow Corning Silicone) and a bisphenol F-type liquid epoxy resin (YDF-8170C) were heated and melted at a mass ratio of 1/1. Silicone-modified epoxy resin,
(B) A cyclic acid anhydride having a normal temperature liquid and an acid equivalent weight of 234 as a cyclic acid anhydride (trade name jER Cure YH306, manufactured by Japan Epoxy Resin Co., Ltd.)
(C) γ-glycidoxypropyltrimethoxysilane (trade name KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent,
(D) As an antioxidant, 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol) (trade name Yoshinox BB manufactured by API Corporation; antioxidant 1), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name Tominox TT manufactured by API Corporation; antioxidant 2),
3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] Undecane (trade name AO-80 manufactured by ADEKA Corporation; antioxidant 3),
Triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] (trade name Yoshinox 917 manufactured by API Corporation; antioxidant 4),
Dicyclohexylamine (trade name D-CHA-T manufactured by Shin Nippon Chemical Co., Ltd .; antioxidant 5),
2-ethyl-4-methylimidazole (trade name 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was used as a curing accelerator, and spherical synthetic silica having a specific surface area of 1 m ² / g and an average particle size of 4 μm was prepared as a filler.

  These were respectively blended in parts by mass shown in Table 1 below, kneaded and dispersed with a rough machine, and then vacuum degassed to prepare liquid resin compositions for electronic parts of Examples 1 to 5 and Comparative Example.

  The produced liquid resin compositions for electronic parts of Examples 1 to 5 and Comparative Example were evaluated by the following tests. The evaluation results are shown in Table 2 below.

(1) Viscosity For liquid resin compositions for electronic parts maintained at 25 ± 1 ° C. using an EMD type rotational viscometer (manufactured by Tokimec Co., Ltd.), Examples 1 to 5 and Comparative Examples were rotated at 100 rpm for 1 minute. The scale at that time was multiplied by a conversion factor of 0.0125 to obtain the viscosity.

(2) Gelation time 0.1 g of the liquid resin composition for electronic parts was dropped on a hot plate at 150 ° C. and stirred so as not to spread too much with a spatula. After dripping, the time until the viscosity of the liquid resin composition for electronic parts was increased and when the spatula was lifted up to break without stringing was defined as the gel time.

(3) Water Absorption Rate The liquid resin composition for electronic parts was cured at 150 ° C. for 2 hours to produce a 50 mm × 50 mm × 1 mm test piece. After measuring the initial weight W ₁ of this test piece, it was placed in a high-temperature and high-humidity tank at 85 ° C./85%, the weight W ₂ after 100 hours was measured, and the water absorption rate was obtained by the following equation.
(Water absorption) = {(W ₂ −W ₁ ) / W ₁ } × 100 (%)

(4) Adhesive force The liquid resin composition for electronic components was cured on a polyimide film (trade name Kapton, Toray DuPont Co., Ltd.) at 150 ° C. for 2 hours, and cut into strips having a width of 10 mm. Using a tensile tester (manufactured by Shimadzu Corporation), the peel strength at which the polyimide film was peeled upward by 90 degrees was defined as the adhesive strength.

(5) Invasion A SUS spacer having a thickness of 20 μm was sandwiched between two pieces of glass to form a channel having a width of 5 mm. This was placed horizontally on a hot plate at 70 ° C., and then the liquid resin composition for electronic parts was dropped, and the time for entering to 20 mm between the gaps was measured. Less than 3 minutes was judged as good and 3 minutes or more as bad.

(6) Evaluation of migration resistance A liquid resin composition for electronic parts is dispensed on the counter electrode portion of a flexible wiring board in which a counter comb-shaped electrode having a wiring width of 15 μm and a wiring interval of 15 μm is formed by copper wiring tin-plated on a polyimide film. A test piece was prepared by coating at 150 ° C. for 2 hours. The resistance value of the test piece was continuously measured under a high temperature and high humidity of 120 ° C./85% by applying a DC voltage of 60 V, and it was determined that a leak occurred when the resistance value was 10 ⁶ Ω or less. . The measurement was performed up to 500 h, and the liquid resin composition for electronic parts whose resistance value did not become 10 ⁶ Ω or less was set to> 500 h.

(7) Appearance evaluation The test piece for which the migration resistance evaluation was completed was observed with transmitted light of a stereomicroscope, and the degree of corrosion of the copper wiring tin-plated on the polyimide film was observed. When migration occurs, there is a phenomenon in which the wiring metal corrodes from the anode wiring side and is eluted into the resin. Therefore, when observed with transmitted light, as shown in FIG. 1, the width of the anode wiring appears thicker than before the test according to the progress of migration. The most corroded wiring width is 1.0 to 1.1 times the wiring width before the test, ◎, the one 1.1 to 1.2 times is ○, 1.2 to 1 .Times.3 times, and .times.1.3 times or more x.

  Examples 1 to 5 are all liquid resin compositions for electronic parts containing an antioxidant, but compared with comparative examples not containing an antioxidant, viscosity, gelation time, water absorption, adhesive strength, penetration The migration resistance could be improved without impairing various properties essential for the liquid resin composition for electronic parts such as the property. Among them, Examples 3 and 4 using an antioxidant having one methyl group at the ortho position are most excellent in insulation reliability and corrosion resistance, and then Example 5 using dicyclohexylamine is insulation reliability and resistance. Excellent corrosion resistance and high migration resistance. This combination of antioxidants prevents oxidative degradation of the cured resin under high-temperature and high-humidity environment, suppresses the generation of impurity ions and decreases in insulation, and acts on the metal surface to prevent the metal from being deteriorated. This is thought to be due to the inhibition of corrosion.

  The liquid resin composition for electronic parts according to the present invention is a liquid resin composition for electronic parts that has good migration resistance and is excellent in other moldability and reliability, and has great industrial value. In particular, it is useful as an underfill material for a semiconductor device in which a semiconductor element is flip-chip bonded to a wiring formed on a rigid and flexible wiring board or glass by bump connection, specifically, a semiconductor device such as a flip-chip BGA or COF.

Claims (13)

Epoxy resins, cyclic acid anhydrides of liquid at normal temperature, and contains a phenol compound having at least one alkyl group coupling agents, the ortho 及 beauty phenol nucleus, the epoxy resin comprises a bisphenol F type epoxy resin, underfill Liquid resin composition for electronic parts.   The liquid resin composition for electronic components according to claim 1, wherein the phenol compound having at least one alkyl group at the ortho position of the phenol nucleus contains a phenol compound having one methyl group at the ortho position of the phenol nucleus.   3. The liquid resin composition for electronic parts according to claim 1, wherein the phenol compound having at least one alkyl group at the ortho position of the phenol nucleus has a saturated dissolution amount in a bisphenol F type epoxy resin of 5% by weight or more. object.   The liquid resin composition for an electronic component according to any one of claims 1 to 3, further comprising an inorganic filler, and the blending amount of the inorganic filler is 10% by mass or less.   Furthermore, the liquid resin composition for electronic components of any one of Claims 1-4 containing a rubber particle.   Furthermore, the liquid resin composition for electronic components of any one of Claims 1-5 containing a silicone modified epoxy resin.   Furthermore, the liquid resin composition for electronic components of any one of Claims 1-6 containing an ion trap agent.   Furthermore, the liquid resin composition for electronic components of any one of Claims 1-7 containing the latent hardening accelerator which accelerates | stimulates reaction of the said epoxy resin and the said cyclic acid anhydride of normal temperature liquid.   Furthermore, the organic solvent content rate is 1% or less, The liquid resin composition for electronic components of any one of Claims 1-8 characterized by the above-mentioned.   The liquid resin composition for electronic parts according to any one of claims 1 to 9, wherein the cyclic acid anhydride of the room temperature liquid has an acid anhydride equivalent of 200 or more.   11. The liquid resin composition for electronic parts according to claim 1, wherein the viscosity at 25 ° C. using an EMD type rotational viscometer is 1.2 Pa · s or less. The liquid resin composition for an electronic component according to any one of claims 1 to 11 , which is used in an electronic component device in which an electronic component is directly bump-connected on a wiring board having a film as a base material. Electronic component device sealed using the electronic component liquid resin composition according to any one of claims 1 to 12.