KR20100109476A - Liquid resin composition for electronic component and electronic component device - Google Patents

Abstract

PURPOSE: A liquid phase resin composition and an electronic component device are provided to secure the adhesive property with a wiring board and electronic components including a semiconductor device. CONSTITUTION: A liquid phase resin composition for electronic components contains an epoxy resin, liquid cyclic acid anhydride, a coupling agent, and an antioxidant. The antioxidant includes either a phenolic compound having one alkyl group at an ortho location of a phenol nucleus, or a phenolic compound having one methyl group at the ortho location of the phenol nucleus.

Description

Liquid resin composition for electronic components and electronic component apparatus {LIQUID RESIN COMPOSITION FOR ELECTRONIC COMPONENT AND ELECTRONIC COMPONENT DEVICE}

This invention relates to the liquid resin composition for electronic components suitable for sealing of electronic components, and the electronic component apparatus sealed by this.

Conventionally, in the field of element sealing for electronic component devices such as transistors and ICs, resin sealing has become 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 adhesion to insert products. In a bare chip-mounted semiconductor device such as COB (Chip on Board), COG (Chip on Glass), TCP (Tape Carrier Package), the liquid resin composition for electronic components is a sealing material. It is widely used as. In recent years, as a mounting method of display drive ICs, such as a liquid crystal, it is used for the mounting form (flip chip connection system) which bump-connects a semiconductor element directly to a wiring board, and the liquid resin composition for electronic components used for this mounting is an underfill material. 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 the insulation between the bumps and maintaining the mechanical strength in the semiconductor mounting method by the flip chip connection method. Therefore, in the underfill material, (1) a liquid having a low viscosity at room temperature, (2) a resin composition is a solvent-free in order to avoid bubbles (voids) generation during the thermosetting process of the resin after filling, and (3) a viscosity In order to avoid an increase and a decrease in permeability, to avoid containing solid components, such as a filler as much as possible, (4) When it contains a solid component, it maintains the uniform dispersibility of the solid component in the liquid resin composition for electronic components, Conditions such as particle size distribution that does not impair viscosity, fluidity, permeability, and the like and appropriate formulations for managing the filling amount are required items.

In the above-mentioned wiring board and semiconductor device, the space | interval between wiring became narrow and it turned out that wiring pitch is 30 micrometers or less in the flip-chip semiconductor device of the uppermost stage. In addition, when a high voltage is applied between the narrow-pitched wirings, the migration phenomenon has become a major problem for the liquid resin composition for electronic components as one of the poor phenomena which impairs the insulation reliability. In particular, under high temperature and high humidity, deterioration of the resin and the wiring metal is promoted, so that migration is likely to occur, and there is a tendency that the fear of defects in the semiconductor device is further increased.

In order to avoid such a defect, the countermeasure aimed at suppressing migration has been made about the resin composition already used for an electronic component previously. For example, as a metal ion supplement, the resin composition which mix | blended the inorganic ion exchanger (for example, refer patent documents 1-4), resin which mix | blended benzotriazine, benzotriazole, and these isocyanuric acid adducts Resin (for example, refer patent documents 5-10), the resin composition which mix | blended the compound containing a borate salt with a hardening accelerator (for example, refer patent document 11), and the resin composition which mix | blended antioxidant (for example, And Patent Documents 12 to 13) and the like are known as resin compositions to be used for applications such as sealing materials, adhesives and prepregs.

Among the well-known examples, in the resin composition in which the antioxidants exemplified in Patent Documents 12 to 13 are blended, in the resin composition for a printed circuit board represented by a prepreg, in addition to the effect of preventing the deterioration of the resin, the migration resistance is particularly excellent. It is known that. In the resin composition for printed circuit boards, solvents such as methyl ethyl ketone (MEK) and toluene are used at the time of blending, so that various solid (powder-shaped) antioxidants are usually mixed and dissolved together with an epoxy resin, a curing agent, and a curing accelerator at room temperature. It is possible to select any antioxidant according to the use and the characteristic.

Japanese Patent Publication No. 6-158492 Japanese Patent Publication No. 9-314758 Japanese Patent Laid-Open No. 2000-183470 Japanese Patent Laid-Open No. 2007-63549 Japanese Patent Laid-Open No. 2001-6769 Japanese Patent Laid-Open No. 2001-203462 Japanese Patent No. 3881286 Japanese Patent Laid-Open No. 2005-72275 Japanese Patent Laid-Open No. 2005-333085 Japanese Patent No. 3633422 Japanese Patent Laid-Open No. 2008-7577 Japanese Patent Laid-Open (Pat.) 3-39320 Japanese Patent Laid-Open No. 10-279779

On the other hand, in the liquid resin composition for electronic components used as an underfill material, in order to avoid generation | occurrence | production of air bubbles (pores) in the thermosetting process of resin after filling as mentioned above, a solvent is not used. For this reason, the conventionally well-known antioxidant is melt | dissolved uniformly in the liquid resin composition for solvent-free electronic components, and it is essential as an underfill material, such as low viscosity, high fluidity, high permeability, fast curing, low water absorption, and high adhesiveness. It was difficult to obtain the liquid resin composition for electronic components excellent in the migration resistance, without damaging various characteristics.

Currently, the migration resistance is improved by reducing impurities in the liquid resin composition for electronic parts. However, for example, COF (Chip On Film), which is a representative semiconductor device with remarkable thinning and narrow pitch, is required to further improve migration resistance, and it is difficult to cope only with high purity of the liquid resin composition for electronic components. Is getting.

This invention is made | formed in view of such a situation, and is providing the liquid resin composition for electronic components excellent in migration resistance, other moldability, and reliability, and the electronic component apparatus sealed by this.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a result, the adhesiveness of electronic components, such as a semiconductor element, and a wiring board is favorable, the water absorption is small, and low viscosity and fluidity which suppressed oxidative degradation By applying the excellent liquid resin composition for electronic components of high purity, it discovered that the said objective can be achieved and came to complete this invention.

The present invention relates to the following (1) to (15).

(1) Liquid resin composition for electronic components containing (A) epoxy resin, (B) cyclic acid anhydride of normal temperature liquid, (C) coupling agent, and (D) antioxidant.

(2) The liquid resin composition for an electronic component according to the above (1), wherein (D) the antioxidant contains a phenol compound having at least one alkyl group at the ortho position of the phenol nucleus.

(3) The liquid resin composition for an electronic component according to the above (1), wherein (D) the antioxidant contains a phenol compound having one methyl group at the ortho position of the phenol nucleus.

(4) The liquid resin composition for an electronic component according to the above (2) or (3), wherein the antioxidant (D) has a saturated dissolution amount of 5% by weight or more with respect to the bisphenol F-type epoxy resin.

(5) The liquid resin composition for an electronic component according to the above (1), wherein the (D) antioxidant contains dicyclohexylamine or a derivative thereof.

(6) The liquid resin composition for electronic components in any one of said (1)-(5) which further contains an inorganic filler and whose compounding quantity of an inorganic filler is 10 mass% or less.

(7) The liquid resin composition for electronic components in any one of said (1)-(6) which further contains rubber particle.

(8) The liquid resin composition for electronic components in any one of said (1)-(7) which contains a silicone modified epoxy resin further.

(9) The liquid resin composition for electronic components in any one of said (1)-(8) which further contains an ion trap agent.

(10) The liquid resin composition for electronic components in any one of said (1)-(9) which further contains the latent hardening accelerator which promotes reaction of (A) and (B).

(11) The liquid resin composition for an electronic component according to any one of (1) to (10), wherein an organic solvent content is further 1% or less.

(12) The liquid resin composition for an electronic component according to any one of (1) to (11), wherein the anhydride equivalent of the cyclic acid anhydride of the (B) room temperature liquid is 200 or more.

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

(14) The liquid resin composition for electronic components in any one of said (1)-(13) used for the electronic component apparatus which bump-connected the electronic component directly on the wiring board which uses a film.

(15) The electronic component device sealed using the liquid resin composition for electronic components in any one of said (1)-(14).

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, low water absorption, and excellent fluidity at low viscosity, which suppresses oxidative degradation. Since it is a liquid resin composition for high purity electronic components, its industrial value is large. In particular, it is especially useful as a semiconductor device which flip-chip-bonded a semiconductor element by bump connection to the rigid wiring board, the flexible wiring board, and the wiring formed on glass, specifically, as an underfill material for semiconductor devices, such as flip chip BGA and COF.

FIG. 1A is a diagram showing the vicinity of the anode and the wiring width before the test in the migration resistance evaluation, and FIG. 1B is a diagram showing the vicinity of the anode and the wiring width after migration has occurred. .

The epoxy resin (A) 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 curable molecule, and epoxy resins generally used in liquid resin compositions for electronic components can be used. If it is a liquid phase, you may use either a solid, a liquid phase, or may use both together. For example, glycidyl ether type epoxy resin obtained by reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalenediol, hydrogenated bisphenol A, and epichlorohydrin, an orthocresol novolak-type epoxy resin, etc. Glycidyl ester type epoxy resin obtained by reaction of polybasic acids, such as a novolak-type epoxy resin which epoxidized the novolak-type resin obtained by condensation or co-condensation of phenols and aldehydes, phthalic acid, dimer acid, and epichlorohydrin, dia Glycidylamine type epoxy resin obtained by reaction of polyamines, such as a minodiphenylmethane and isocyanuric acid, and epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing an olefin bond with peracids, such as peracetic acid, alicyclic epoxy Resins and the like, and these may be used alone or in combination of two or more thereof. May be available.

Especially, a liquid epoxy resin is preferable from a viewpoint of low viscosity, and a bisphenol-type liquid epoxy resin is more preferable from a viewpoint of reactivity with cyclic acid anhydride.

Moreover, these epoxy resins are fully refined and it is preferable that there are few ionic impurities. For example, it is more preferable that free Na ions and free Cl ions are 500 ppm or less.

There is no restriction | limiting in particular as cyclic acid anhydride of (B) normal temperature liquid used by this invention, For example, phthalic anhydride, maleic anhydride, methylhymic acid anhydride, a hymic acid anhydride, succinic anhydride, tetrahydro phthalic anhydride, hexahydro Phthalic anhydride, chloric anhydride, methyltetrahydro phthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydromaleic anhydride maleic acid adduct, methylhexahydrophthalic acid, benzophenonetetracarb Trialkyltetrahydro anhydride which is obtained by a Diels-Alder reaction from an acid anhydride, trimellitic anhydride, pyromellitic anhydride, methyltetrahydro phthalic anhydride, methyl hydride anhydride, maleic anhydride, and a diene compound, and has a plurality of alkyl groups. Various cyclic acid anhydrides, such as a phthalic acid and a dodecenyl succinic anhydride, are mentioned.

"Cyclic acid anhydride" means that two carbon atoms C of "-CO-O-CO-" chemically bond with two other carbon atoms and become cyclic as represented by phthalic anhydride. In addition, "anhydride equivalent" is represented by (molecular weight of acid anhydride) / (number of anhydride groups in an acid anhydride molecule).

As a compound whose anhydrous acid equivalent is 200 or more, Japan Epoxy Resin Co., Ltd. brand name jER Cure YH306 etc. whose anhydride equivalent is 234 are available as a commercial item, for example.

When the acid anhydride equivalent of an acid anhydride is less than 200, since ester bonds in hardened | cured material increase, it is easy to be influenced by hydrolysis under high temperature, high humidity, and it is easy to produce the fall of moisture resistance, especially migration resistance. Moreover, when the acid anhydride equivalent of an acid anhydride is less than 200, a water absorption becomes high under the influence of an ester group, and this also becomes a cause of the fall of migration resistance. That is, since the cyclic acid anhydride having a large anhydride equivalent has a lower ester group concentration than the cyclic acid anhydride having a small anhydride equivalent, the cured product has a lower water absorption, thereby reducing the amount of ionic impurities such as Cl eluted in water. You can.

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

Although the structure of the cyclic acid anhydride of (B) component does not have a restriction | limiting in particular, It is preferable from a viewpoint of migration resistance that halogen atoms, such as chlorine and a bromine, are not contained in a molecule | numerator.

In this invention, hardening agents other than (B) component can be used suitably, and what is generally used as a hardening | curing agent of an epoxy resin 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, Amine compounds such as polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine mixture, N-aminoethylpiperazine, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2 -Cyanoethyl) -2-ethyl-4-methylimidazole, 2,4-diamino-6- (2-methylimidazoyl- (1)) ethyl-s-triazine, 2-phenylimida Imidazole compounds such as sleepy, 2,3-dihydro-1H-pyrrolo (1,2-a) benzimidazole, tertiary amines, DBU, dicyandiamide, organic acids Dihydrazide, N, N-dimethyl urea derivatives, and the like. Especially, an amine compound is preferable from a viewpoint of low viscosity.

30 mass% or more is preferable with respect to the hardening | curing agent whole quantity containing (B) component, and, as for the compounding quantity of the cyclic acid anhydride of the normal temperature liquid of (B) component, 40 mass% or more is more preferable, 60 Mass% or more is more preferable.

Although the equivalence ratio of (A) epoxy resin and all the hardening | curing agents containing the cyclic acid anhydride of the normal temperature liquid of (B) component is not restrict | limited, In order to restrain each unreacted powder, 0.6 to- It is preferable to set in the range of 1.6 equivalent, 0.7-1.4 equivalent is more preferable, 0.8-1.2 equivalent is still more preferable. If it deviates from the range of 0.6-1.6 equivalent, there exists a tendency for hardening reaction to become inadequate and reliability falls. Equivalent is a reaction equivalent, For example, the anhydride equivalent of an acid anhydride is computed as one acid anhydride group reacts with respect to one epoxy group, and the equivalent of a phenol resin is one phenolic hydroxyl group reacting with one epoxy group. The equivalent of aromatic amine is calculated as one active hydrogen of amino group reacts with one epoxy group.

There is no restriction | limiting in particular as (C) coupling agent used by 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, an epoxysilane, a mer Various silane compounds, such as captosilane, alkylsilane, ureidosilane, and vinyl silane, a titanium compound, aluminum chelates, an aluminum / zirconium compound, etc. are mentioned.

Examples thereof include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxy Silane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ -(N, N-dimethyl) aminopropyltrimethoxysilane, 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) aminopropyltriethoxysilane, γ- (N-methyl) Anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) amino Propylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropylmethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimeth Methoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltri Silane coupling agents, such as methoxysilane, hexamethyldisilane, vinyltrimethoxysilane, (gamma)-mercaptopropylmethyldimethoxysilane, and isopropyl triisos Aroyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2, 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl tree Octanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctylphosphate) titanate And titanate-based coupling agents such as isopropyl tricumylphenyl titanate and tetraisopropylbis (dioctylphosphite) titanate. You may use these 1 type individually or in combination of 2 or more types.

(C) It is preferable that the total compounding quantity of a coupling agent is 0.037-5.0 mass% with respect to a liquid resin composition, It is more preferable that it is 0.05-4.75 mass%, It is further more preferable that it is 0.1-2.5 mass%. If it is less than 0.037 mass%, there exists a tendency for the adhesiveness of the hardened | cured material of a board | substrate and a liquid resin composition to fall, and when it exceeds 5.0 mass%, physical properties, such as glass transition temperature and bending strength, will fall.

As (D) antioxidant used by this invention, a conventionally well-known thing can be used. For example, the compound having at least one alkyl group at the ortho position of the phenol nucleus in the phenolic compound antioxidant includes 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-t-butyl-3-methylphenol), tetrakis [methylene-3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propio Nate], N, N'-hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], isooctyl-3- (3,5-di-t-butyl 4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) bene Xen, 4,6-bis (dodecylthiomethyl) -o-cresol, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonic acid) calcium, 2,4-1 bis [(octyl Thio) methyl] -o-cresol, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 6- [3- (3- t-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-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-t- Pentylphenyl) ethyl] -4,6-di-t-pentylphenylacrylate, 2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 2,6-di-t-butyl- 4-ethylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-4-hydroxy -5-methylphenyl) propionate], tris (3,5-di-t-butyl-4hydroxybenzyl) isocyanurate, diethyl [[3,5-bis (1,1-dimethylethyl)- 4-hydroxyphenyl] methyl] phosphonate, 2,5,7,8- Tramethyl-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 the dicyclohexylamine, Shin Nippon Rica Co., Ltd. brand name D-CHA-T etc. can be obtained as a commercial item, As a derivative thereof, dicyclohexylamine ammonium nitrite, N, N-di (3-methyl-cyclohexyl Amines), N, N-di (2-methoxy-cyclohexyl) amine, N, N-di (4-bromo-cyclohexyl) amine, and the like. Examples of the organic sulfur compound-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate. Nate, pentaerythryltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thiobis ( 6-t-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 As an amine compound type antioxidant, such as -3, 5- di- t-butylanilino) -1, 3, 5- triazine, N, N'- diallyl- p-phenylenediamine, N, N'- Di-sec-butyl-p-phenylenediamine, octylated diphenylamine, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) As phosphorus compound type antioxidant such as -1,3,5-triazine, Tris Nonylphenyl phosphite, triphenyl phosphite, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) calcium, tris (2,4-di-t-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 (1,1dimethylethyl) 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. You may use these 1 type individually or in combination of 2 or more types. Moreover, in the said phenolic compound type antioxidant, the compound containing any one or more of a phosphorus atom, a sulfur atom, and an amine in the same molecule in addition to a phenolic hydroxyl group was mentioned repeatedly.

Among the above-mentioned antioxidants, in particular, a phenol compound-based antioxidant having at least one alkyl group at the ortho position of the phenol nucleus and dicyclohexylamine are more preferable from the viewpoint of improving the migration resistance. In the phenolic compound type antioxidant which has at least 1 alkyl group in the ortho position of a phenol nucleus, since the alkyl group of an ortho position is an electron donating group, an electron concentration becomes high at the hole electron site of the oxygen atom of a phenol hydroxyl group, and antioxidant is an anode metal In the case of cyclohexylamine, in the cyclohexylamine, the hole electron site of the nitrogen atom of the amine is coordinated to the anode metal surface, whereby the antioxidant coordinated to the metal surface suppresses the oxidation deterioration of the metal and the migration resistance is considered to be improved. .

Moreover, in the phenolic compound type | system | group antioxidant which has at least 1 alkyl group in the ortho position of the said phenol nucleus, the compound of a solid and powder-like compound is generally known, but in order to avoid the fall of viscosity, permeability, and fluidity as a liquid resin composition for electronic components, It is further more preferable to melt | dissolve so that the hardened | cured material of the liquid resin composition for electronic components may have sufficient migration resistance with respect to (A) epoxy resin which becomes one component of the liquid resin composition for electronic components. Specifically, it is preferable that the saturated dissolution amount in a general epoxy resin, for example, the well-known bisphenol F-type epoxy resin used also as a liquid epoxy resin, is 5 mass% or more, and a more preferable range is 10 mass% or more. For this reason, when the phenolic compound-based antioxidant having a saturated dissolution amount in the above preferred range is dissolved in an epoxy resin, the phenolic compound-based antioxidant can be uniformly dispersed in the liquid resin composition for electronic parts, resulting in high migration resistance. Because. Here, the said saturated dissolution amount is a value at room temperature in consideration of stability of the said liquid composition, since application | coating of a liquid resin composition is normally performed at room temperature. Of the phenolic compound-based antioxidants having at least one alkyl group at the ortho position of the phenol nucleus, examples of the phenolic compound-based 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].

Moreover, among the phenolic compound type antioxidant which melt | dissolves in the said epoxy resin, the phenolic compound type antioxidant which has one methyl group in the ortho position of a phenol nucleus is more preferable. It is considered that this is because the methyl group has little steric hindrance, is an electron donating group, and the hole electrons of the phenol hydroxyl group of the antioxidant are more likely to coordinate on the surface of the anode metal. Such phenolic compound-based antioxidants include 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 advantageous in that its properties at room temperature are liquid and uniformly dispersed without compromising the viscosity, permeability, and fluidity of the liquid resin composition for electronic components, compared to solid and powdered antioxidants.

As for the compounding quantity of the said phenolic compound type antioxidant, 0.1-10 mass% is preferable with respect to (A) epoxy resin, More preferably, it is 0.5-5.0 mass%. If it is less than 0.1 mass%, the inhibitory effect of migration will fall, and when it exceeds 10 mass%, there exists a tendency for the fluidity | liquidity of the liquid resin composition for electronic components to fall. Moreover, 0.1-D mass% is preferable, and, as for the compounding quantity when 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, it is 0.5- 5.0 mass%.

As for the compounding quantity of the said dicyclohexylamine, 0.1-30 mass% is preferable with respect to (A) epoxy resin, More preferably, it is 0.5-10 mass%. If it is less than 0.1 mass%, the inhibitory effect of migration will fall, and when it exceeds 30 mass%, there exists a tendency for the storage stability of the liquid resin composition for electronic components, and the glass transition temperature of hardened | cured material to fall.

In the case where the gap between wirings and bumps of the wiring board and semiconductor device to which the liquid resin composition for electronic component of the present invention is applied is 20 µm or less, it is insoluble in the liquid resin composition for electronic component in order to improve the filling and fluidity between the gaps. 10 mass% or less is preferable, and, as for the compounding quantity of a phosphorus solid compound, 5 mass% or less is more preferable. On the other hand, the gap between the wiring or bump between the wiring board and semiconductor device to which the liquid resin composition for an electronic component of the present invention is applied exceeds 20 µm, and furthermore, when the migration resistance needs to be improved, In order to compensate for thermal expansion coefficient aberration, it is possible to mix | blend an inorganic filler in the range which does not impair the filling property or fluidity between gaps. The inorganic filler is generally used in liquid resin compositions for electronic parts, and is not particularly limited. Examples thereof include silica such as fused silica, crystalline silica and synthetic silica, calcium carbonate, talc, clay, alumina such as alumina, silicon nitride, Silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, stearite, spinel, mullite, titania, or other powders such as spheres, beads, glass fibers, etc. Can be mentioned. Moreover, inorganic nanoparticles, such as nano silica obtained by the 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 thereof.

It is preferable that the shape of an inorganic filler is close to spherical from a moldability viewpoint, such as fluidity | liquidity. The average particle diameter of the inorganic filler is preferably in the range of 5 nm to 10 m. When it exceeds 10 micrometers, it will become easy to produce a settling of a filler, or the permeability and fluidity to the microgap of the liquid resin composition for electronic components will fall, and there exists a tendency which becomes easy to cause a space | gap and an unfilled. Moreover, these fillers can also use what couple | coated the surface as needed. 10 mass% or less of the liquid resin composition for electronic components is preferable, and, as for the compounding quantity of an inorganic filler, 5 mass% or less is more preferable. When it exceeds 10 mass%, the linear expansion coefficient difference between the hardened | cured material of the liquid resin composition for electronic components and a flexible wiring board using a film board | substrate becomes large, and peeling occurs easily at both interfaces. Moreover, when there is much inorganic filler amount, since the viscosity of the liquid resin composition for electronic components becomes high and surface tension becomes high, there exists a tendency for fluidity to fall.

It is preferable to use the hardening accelerator which accelerates | stimulates reaction of the hardening | curing agent containing the epoxy resin of (A) component and (B) component as needed for the liquid resin composition for electronic components of this invention. As a hardening accelerator, a latent hardening accelerator is preferable in order to make curability and a usable time compatible. A latent hardening accelerator expresses hardening accelerator function on conditions, such as specific temperature, and the thing of which a normal hardening accelerator is protected by a microcapsule, etc., or has a structure of various compounds and the added salt is mentioned, for example. In this case, the cure accelerator is opened from the microcapsules or adducts above a certain temperature.

Examples of the latent curing accelerator include core shell particles formed by coating a shell of an epoxy compound of a room temperature solid using a compound having an amino group of a room temperature solid as a core, and are commercially available products such as Amicure (manufactured by Ajinomoto Co., Ltd.). , Novacure (Asahi Kasei Chemicals Co., Ltd. make) which disperse | distributed microencapsulated amine to bisphenol-A epoxy resin, bisphenol F-type epoxy resin, etc. can be used.

Further, intramolecular polarization formed by adding salts of amine compounds or phosphorus compounds that dissociate at the time of heat molding from solid particles that are insoluble in the liquid resin composition system for electronic components and express hardening promoting action, and compounds having π bonds thereto are added. The compound which has can be used as a latent hardening accelerator.

Examples thereof include 1,8-diaza-bicyclo (5,4,0) undecene-7,1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino- A compound having an intramolecular polarization formed by adding a cycloamidine compound such as 1,8-diaza-bicyclo (5,4,0) undecene-7 and a compound having π bond, triethylenediamine, benzyldimethylamine , Derivatives of tertiary amine compounds such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 Derivatives of imidazole compounds such as -phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, and the like. 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 -Phosphorus compound which has intramolecular polarization formed by adding the compound which has (pi) bonds, such as quinone compounds, such as dimethoxy- 1, 4- benzoquinone, and phenyl- 1, 4- benzoquinone, diazophenylmethane, a phenol resin, etc. And phenylboron salts such as triphenylphosphinetriphenylboron, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, and derivatives thereof. These etc. can be mentioned, These 1 type can be used individually, or can also be used in combination of 2 or more type.

Especially, it is preferable to disperse | distribute microencapsulated amine to bisphenol-A epoxy resin and bisphenol-F epoxy resin from a viewpoint of storage stability and fast hardenability.

Although the compounding quantity of a hardening accelerator will not be restrict | limited especially if it is an amount which hardening acceleration effect is achieved, 0.1-40 mass% is preferable with respect to (A) epoxy resin in the total amount which included non-latent thing, More preferably, it is 0.5 To 30 mass%. If it is less than 0.1 mass%, there exists a tendency for the sclerosis | hardenability in a short time to fall, and when it exceeds 40 mass%, there exists a tendency for hardening rate to become too fast, and control becomes difficult, or storage stability, such as a usable time and shell life, is inferior.

It is preferable to mix | blend well-known various rubber particle with the liquid resin composition for electronic components of this invention, in order to aim at toughening of an epoxy resin hardened | cured material, and low elastic modulus. The said rubber particle is effective in reducing an elastic modulus, without incompatible with an epoxy resin, lowering the glass transition temperature (heat resistance) of hardened | cured material. Specifically, butadiene acrylonitrile styrene-based copolymers or modified copolymers having an epoxy group, an amino group, a carboxyl group, a hydroxyl group or the like on the terminal or side chain of the polymer, an epoxy group, an amino group, a carboxyl group, a hydroxyl group on the terminal or side chain Modified silicone elastomers etc. which have etc. are mentioned. It is preferable to use what disperse | distributed finely to an epoxy resin or a hardening | curing agent previously in fine powder form from a viewpoint of handleability and the dispersibility with a resin component. Since it can mix similarly in a resin composition, it is preferable that it is a rubber modified epoxy resin (The thing which heated-melted liquid epoxy resin and rubber particle) at normal temperature. By containing rubber particle, adhesiveness with the hardened | cured material of the liquid resin composition for electronic components, a board | substrate, etc. improves, and reliability improvement, such as high temperature, high humidity resistance, is attained.

The liquid resin composition for electronic components of the present invention is also characterized in that the ion trapping agent is migrated, moisture-resistant, and high-temperature-resisting, if necessary, in a range that does not impair the filling properties and fluidity during application to wiring boards and semiconductor devices. It is preferable to contain from a viewpoint of improving this. 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 following formula (1) or the bismuth hydrous oxide represented by formula (2) is preferable.

(Where 0 <X≤0.5, m is positive)

(Wherein 0.9≤x≤1.1, 0.6≤y≤0.8, 0.2≤z≤0.4)

The addition amount of these ion trapping agents is not particularly limited as long as it is a sufficient amount capable of trapping anions such as halogen ions, but from the viewpoint of migration resistance, 0.1 to 3.0 mass% is preferable, and more preferable, from the liquid resin composition for electronic components. Preferably it is 0.3-1.5 mass%. The average particle diameter of the ion trapping agent is preferably 0.1 to 3.0 mu m, and the maximum particle diameter is preferably 10 mu m or less. In addition, the compound of the formula (1) can be obtained as a commercially available product under the trade name DHT-4A manufactured by Kyowa Kagaku Kogyo Co., Ltd .. In addition, the compound of the said Formula (2) can be obtained as a commercial item as a brand name IXE500 by Toagosei Co., Ltd .. Moreover, you may add another ion trap agent as needed. For example, a hydrous oxide of an element selected from magnesium, aluminum, titanium, zirconium, antimony and the like, and the like can be used alone or in combination of two or more thereof.

Moreover, it is preferable to add a silicone modified epoxy resin to the liquid resin composition for electronic components of this invention separately from the said (A) epoxy resin component as needed. By adding a silicone modified epoxy resin, it is effective in the leveling property, fillet formation property, and space | gap reduction of the liquid resin composition for electronic components. The silicone-modified epoxy resin can be obtained as a reactant of an organosiloxane having an functional group reacting with an epoxy group and an epoxy resin, but is preferably liquid at room temperature. The silicone-modified epoxy resin may be localized on the surface of the liquid to lower the surface tension of the liquid. Thereby, since wettability becomes high and it flows easily, it is effective in the improvement of permeability to a narrow gap, and reduction of a winding space | gap.

Examples of the organosiloxane having a functional group reacting with an epoxy group include dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane and the like having one or more amino groups, carboxyl groups, hydroxyl groups, phenolic hydroxyl groups, and mercapto groups in one molecule. have. As a weight average molecular weight of organosiloxane, the range of 500-5000 is preferable. For this reason, if it is less than 500, the compatibility with the resin system is too good, and the effect as an additive is not sufficiently exhibited. If it exceeds 5000, it is incompatible with the resin system. This is because it damages the appearance or appearance.

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 components, and epoxy resins generally used in the liquid resin composition for electronic components can be used, for example, bisphenols. Phenols and aldehydes, including glycidyl ether type epoxy resins and orthocresol novolac type epoxy resins obtained by the reaction of A, bisphenol F, bisphenol AD, bisphenol S, naphthalenediol, hydrogenated bisphenol A and epichlorohydrin Glycidyl ester type epoxy resin obtained by reaction of polybasic acids, such as a novolak-type epoxy resin which epoxidized the novolak resin obtained by condensation or cocondensation, phthalic acid, dimer acid, and epichlorohydrin, diamino diphenylmethane, Of polyamines and epichlorohydrin such as isocyanuric acid The linear aliphatic epoxy resin obtained by oxidizing the glycidylamine type | mold epoxy resin obtained by coagulation, an olefin bond with peracids, such as peracetic acid, an alicyclic epoxy resin, etc. are mentioned, These are used individually or in combination of 2 or more types Although it can use, it is preferable that it is a normal temperature liquid phase.

In the liquid resin composition for electronic parts of the present invention, other additives include colorants such as dyes, carbon black, titanium oxide, and podium, flame retardants, diluents, other leveling agents, other stress relaxation agents, antifoaming agents, adhesion promoters, and the like. It can mix | blend as needed in the range which does not impair filling property and fluidity at the time of application to a wiring board and a semiconductor device.

As the flame retardant, a brominated epoxy resin or antimony trioxide can be used, but non-halogen, antimony and flame retardant are preferably used. For example, phosphorus compounds such as phosphoric acid esters and triphenylphosphine oxides, melamine, melamine derivatives, melamine-modified phenolic resins, compounds having triazine rings, and cyanuric acid, which are coated with thermosetting resins such as red and phenol resins Nitrogen-containing compounds such as 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 zinc A metal oxide, such as a compound, iron oxide, molybdenum oxide, metal hydroxides, such as aluminum hydroxide and magnesium hydroxide, the composite metal hydroxide represented by following formula (3), etc. are mentioned.

(Wherein M ¹ , M ² and M ³ represent different metal elements, a, b, c, d, p, q and m are positive, r is 0 or positive)

M ¹ , M ² and M ³ in Formula 3 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 a third cycle, an alkaline earth metal element of group IIA, group IVB, group IIB , Group VIII, group IB, group IIIA and group IVA, M ² is preferably selected from transition metal elements of groups IIIB to IIB, and M ¹ is magnesium, calcium, aluminum, tin, titanium , Iron, cobalt, nickel, copper and zinc, and M ² is more preferably 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 ratios of p, q and r are not particularly limited, but r = 0, and it is preferable that p / q is 1/99 to 1/1. In addition, classification of a metal element was performed based on the long-period periodic table which makes a typical element A subgroup and a transition element B subgroup. Said flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type.

As a diluent, you may mix the reactive diluent which has an epoxy group for viscosity adjustment. As a reactive diluent which has an epoxy group, n-butylglycidyl ether, a glycidyl ether of versatate, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, 1, 6- hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylol propane triglycidyl ether are mentioned. You may use these 1 type individually or in combination of 2 or more types.

Although the liquid resin composition for electronic components of this invention can be manufactured using what kind of method as long as it can disperse | distribute and mix said various components uniformly, it grind | pulverizes and mixes the component of a predetermined compounding quantity by a general method, It can obtain by mixing and kneading | mixing using a roll, a planetary mixer, etc., and defoaming as needed.

As an electronic component apparatus obtained by sealing an element with the liquid resin composition for electronic components obtained by this invention, it supports a semiconductor chip, a transistor, a support frame, such as a lead frame, a wiring completed tape carrier, a rigid and flexible wiring board, glass, a silicon wafer, An electronic component device obtained by mounting an element such as a passive element such as a diode, a thyristor, a capacitor, a resistor, a resistor array, a coil, a switch, and the like, and sealing a necessary portion with the liquid resin composition for an electronic component of the present invention. Can be mentioned. In particular, it is preferable to be used for sealing of the electronic component apparatus which bump-connected an electronic component directly on the wiring board based on a film. For example, the semiconductor device which flip-bonded the semiconductor element by bump connection to the wiring formed on the rigid, flexible wiring board, or glass is object. Specific examples include semiconductor devices such as flip chip BGA and Chip On Film (COF), and in particular, the liquid resin composition for electronic components obtained in the present invention is preferable as an underfill material for COF having excellent migration resistance. Moreover, the liquid resin composition for electronic components of this invention can also be used effectively for a printed circuit board.

As a method of sealing an element using the liquid resin composition for electronic components of this invention, a dispensing system, a casting system, a printing system, etc. are mentioned.

<Examples>

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

(Examples 1 to 5 and Comparative Examples)

(A) as epoxy resin

Bisphenol F type liquid epoxy resin (brand name YDF-8170C manufactured by Toto Kasei Kabushiki Kaisha) of epoxy equivalent 160,

Naphthalene type epoxy resin of epoxy equivalent 140 (Daninippon Ink Industries, Ltd. make brand name HP-4032),

As a rubber particle component

Acrylonitrile, butadiene, methacrylic acid, divinylbenzene copolymer (JSR-BK brand name XER-91P) was premixed by heating to a bisphenol F type liquid epoxy resin (YDF-8170C) at a mass ratio of 1/4, and not dispersed. Rubber modified epoxy resin,

As leveling agent

Silicone-modified epoxy resin obtained by heat-melting a phenol-modified silicone (trade name BY16-799 manufactured by Toray Dow Corning Silicone Co., Ltd. BYBY-7-799) and bisphenol F-type liquid epoxy resin (YDF-8170C) having a hydroxyl equivalent of 750 at a mass ratio of 1/1.

(B) as a cyclic acid anhydride

Cyclic acid anhydride of normal temperature liquid and anhydrous acidic equivalent 234 (Japan Epoxy Resin Co., Ltd. brand name jER cure YH306)

(C) as coupling agent

γ-glycidoxy propyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. make brand name KBM-403),

(D) as antioxidant

4,4'- butylidene bis- (6-t- butyl- 3-methyl phenol) (the brand name Yoshinox BB; antioxidant 1),

Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (manufactured by AP Co., Ltd. product name Tommy Knox TT; antioxidant 2),

3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5.5] undecane (trade name AO-80 manufactured by ADEKA; antioxidant 3), triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] ( Yoshinox 917; antioxidant 4)

Dicyclohexylamine (Shin-Nibbon Chemical Co., Ltd. brand name D-CHA-T; antioxidant 5),

As a curing accelerator

Spherical synthetic silica having a specific surface area of 1 m 2 / g and an average particle diameter of 4 μm was prepared as a 2-ethyl-4-methylimidazole (trade name 2E4MZ manufactured by Shikoku Chemical Co., Ltd.) and a filler.

These were each blended in the mass parts shown in Table 1 below, kneaded and dispersed in a pulverizer, and vacuum degassed to prepare liquid resin compositions for electronic components of Examples 1 to 5 and Comparative Examples.

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

(1) viscosity

Examples 1 to 5 and Comparative Examples of the liquid resin composition for an electronic component held at 25 ± 1 ° C. using an EMD type rotational viscometer (manufactured by Tokimek Co., Ltd.) at 100 rpm for 1 minute The scale was multiplied by a conversion factor of 0.0125, which was taken as the viscosity.

(2) gelation time

0.1g of the liquid resin composition for electronic components was dripped on the hotplate at 150 degreeC, and it mixed so that it might not spread too much with a spatula. After dripping, the viscosity of the liquid resin composition for electronic components became high, and when it lifts up a spatula up, the time until it cuts off like a thread was made into gelation time.

(3) water absorption

The liquid resin composition for electronic components was hardened on 150 degreeC and the conditions of 2 hours, and the test piece of 50 mm x 50 mm x 1 mm was produced. To then determine the initial weight W ₁ of the test piece, into a high-temperature and high-humidity bath of 85 ℃ / 85%, after 100 hours, measuring the weight W _2, the absorption rate was calculated by the equation (1).

(4) adhesion

The liquid resin composition for electronic components was hardened on the polyimide film (Toray Dupont Co., Ltd. Kapton brand name) on conditions of 150 degreeC and 2 hours, and it cut | disconnected into the strip shape of width 10mm. The peel strength which peels a polyimide film 90 degree upward was made into the adhesive force using the tensile tester (made by Shimadzu Corporation).

(5) invasive

A 20-micrometer-thick spacer made of SUS was sandwiched with two pieces of glass, and a flow path having a width of 5 mm was produced. After placing this horizontally on a 70 degreeC hotplate, the liquid resin composition for electronic components was dripped, and the time which penetrates to 20 mm between gaps was measured. Less than 3 minutes was good and more than 3 minutes was bad.

(6) Migration resistance evaluation

The liquid resin composition for electronic components was apply | coated by the dispensing method to the counter electrode part of the flexible wiring board which formed the counter comb electrode of 15 micrometers of wiring width and 15 micrometers between wirings by the tin-plated copper wiring on the polyimide film, and 150 degreeC , Cured for 2 hours was used as a test piece. The test piece was subjected to a direct current of 60 V under a high temperature, high humidity of 120 ° C / 85%, and the resistance value was continuously measured. It was determined that leakage occurred at a time when the resistance value was 10 ⁶ Ω or less. The measurement was carried out up to 500 hours, and the liquid resin composition for electronic parts whose resistance value was not 10 ⁶ Ω or less was> 500 hours.

(7) appearance evaluation

The test piece in which the migration resistance evaluation was complete | finished was observed with the transmitted light of a stereomicroscope, and the corrosion degree of the copper wiring tin-plated on the polyimide film was observed. When migration occurs, the wiring metal is corroded on the anode wiring side, and the phenomenon of eluting in the resin is observed. For this reason, when observed with transmitted light, as shown in FIG. 1, the width | variety of an anode wiring is thick compared with before test, according to the progress of migration. The most corrosive wiring width was 1.0 to 1.1 times that of the wire width before the test,?, 1.1 to 1.2 times,?, 1.2 to 1.3 times,?, And 1.3 times or more.

Although Examples 1-5 are all liquid resin compositions for electronic components which mix | blended antioxidant, compared with the comparative example which does not mix | blend antioxidant, liquid resin for electronic components, such as viscosity, a gelation time, water absorption rate, adhesive force, and penetration property, etc. Migration resistance was able to be improved, without damaging the various characteristics which are essential as a composition. Among them, Examples 3 and 4 using an antioxidant having one methyl group in the ortho position have the highest insulation reliability and corrosion resistance, followed by Example 5 using dicyclohexylamine, which has excellent insulation reliability and corrosion resistance. , High migration resistance. This is because the compounding of the antioxidant prevents the oxidative deterioration of the cured resin in a high temperature and high humidity environment, the generation of impurity ions and the deterioration of the insulating property are suppressed, and the corrosion of the metal is suppressed by acting on the metal surface. I think.

The liquid resin composition for electronic components which becomes this invention is a liquid resin composition for electronic components excellent in migration resistance, other moldability, and reliability also, and its industrial value is large. In particular, it is useful as a semiconductor device which flip-chip-bonded a semiconductor element by bump connection to the wiring formed on rigid and flexible wiring boards, or glass, specifically, as an underfill material for semiconductor devices, such as flip-chip BGA and COF.

Claims (16)

Liquid resin composition for electronic components containing (A) epoxy resin, (B) cyclic acid anhydride of normal temperature liquid, (C) coupling agent, and (D) antioxidant. The liquid resin composition for electronic parts of Claim 1 in which (D) antioxidant contains the phenol compound which has at least 1 alkyl group in the ortho position of a phenol nucleus. The liquid resin composition for electronic components of Claim 1 in which (D) antioxidant contains the phenol compound which has one methyl group in the ortho position of a phenol nucleus. The liquid resin composition for electronic components of Claim 2 whose (D) antioxidant is 5 weight% or more of saturated dissolutions with respect to a bisphenol F-type epoxy resin. The liquid resin composition for electronic components of Claim 3 whose (D) antioxidant is 5 weight% or more of saturated dissolutions with respect to bisphenol F-type epoxy resin. The liquid resin composition for electronic parts of Claim 1 in which (D) antioxidant contains dicyclohexylamine or its derivative (s). The liquid resin composition for electronic components of any one of Claims 1-6 which further contains an inorganic filler and whose compounding quantity of an inorganic filler is 10 mass% or less. The liquid resin composition for electronic components of any one of Claims 1-6 which further contains rubber particle. The liquid resin composition for electronic components of any one of Claims 1-6 which further contains a silicone modified epoxy resin. The liquid resin composition for electronic components of any one of Claims 1-6 which further contains an ion trap agent. The liquid resin composition for electronic components of any one of Claims 1-6 which further contains the latent hardening accelerator which accelerates | stimulates the reaction of (A) and (B). The liquid resin composition for an electronic component according to any one of claims 1 to 6, wherein an organic solvent content is further 1% or less. (B) The anhydrous acid equivalent of the cyclic acid anhydride of a normal temperature liquid is 200 or more, The liquid resin composition for electronic components of any one of Claims 1-6 characterized by the above-mentioned. The liquid resin composition for an electronic component according to any one of claims 1 to 6, wherein the viscosity at 25 ° C using an EMD type rotational viscometer is 1.2 Pa · s or less. The liquid resin composition for electronic components of any one of Claims 1-6 used for the electronic component apparatus which bump-connected an electronic component directly on the wiring board which uses a film. The electronic component apparatus sealed using the liquid resin composition for electronic components in any one of Claims 1-6.

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