JP2012117033A - Liquid sealing material, and electronic component using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid sealing material excellent in injection property, adhesion, curability, storage stability or the like, not generating void, and further excellent in moisture resistance of a sealed portion, thermal cycle resistance, reflow resistance, crack resistance, warpage resistance or the like, and to provide an electronic component whose sealing portion is sealed by using the liquid sealing material.SOLUTION: This liquid sealing material contains (A) an epoxy resin, (B) an aromatic amine curing agent, (C) a metal complex, (D) a coupling agent and (E) a silica filler, wherein the (D) component coupling agent contains at least vinyltrimethoxysilane, and (E) component silica filler is previously surface-treated by a silane coupling agent.

Description

  The present invention relates to a liquid sealing material used as an underfill. Moreover, this invention relates to the electronic component formed by sealing a sealing part using this liquid sealing material.

As electronic devices become smaller, lighter, and have higher performance, the semiconductor mounting form has changed from a wire bond type to a flip chip type.
A flip chip type semiconductor device has a structure in which an electrode portion on a substrate and a semiconductor element are connected via a bump electrode. In the semiconductor device having this structure, when heat application such as a temperature cycle is applied, a stress is applied to the bump electrode due to a difference in coefficient of thermal expansion between the substrate made of an organic material such as an epoxy resin and the semiconductor element. It is a problem that defects such as cracks occur. In order to suppress the occurrence of this defect, a sealing agent called underfill is used to seal the gap between the semiconductor element and the substrate and fix them together, thereby improving the thermal cycle resistance. Widely done.

  The liquid sealant used as the underfill is required to have excellent injectability, adhesiveness, curability, storage stability, and the like, and no voids are generated. Moreover, it is calculated | required that the site | part sealed with the liquid sealing material is excellent in moisture resistance, thermal cycle resistance, reflow resistance, crack resistance, warpage resistance, etc.

  In order to satisfy the above-described requirements, as a liquid sealing material used as an underfill, an epoxy resin-based material is widely used (see Patent Documents 1 to 5).

Japanese Patent Laid-Open No. 61-218624 Japanese Patent Laid-Open No. 8-104795 JP 2008-255178 A JP 11-315189 A JP 2003-268206 A

In order to improve the moisture resistance and thermal cycle resistance, particularly the thermal cycle resistance of the part sealed with the liquid sealing material, a filler made of an inorganic substance such as silica filler (hereinafter referred to as “filler”). It is effective to control the difference in thermal expansion coefficient between the substrate made of an organic material such as an epoxy resin and the semiconductor element or to reinforce the bump electrode by adding to the liquid sealing material. Are known.
In the inventions described in Patent Documents 1 to 3, for the purpose of improving the moisture resistance and thermal cycle resistance of the sealed portion, a filler such as a silica filler is used as an epoxy resin composition and a liquid resin described in these documents. It is neither described nor suggested to be added to the encapsulant.
In particular, Patent Document 2 discloses a negative description regarding addition of a silica filler to a liquid resin sealing material as described below.
[In general, it is known to increase the glass transition temperature (Tg) by increasing the crosslinking density in order to improve the heat resistance, moisture resistance and electrical properties of the cured resin. However, if such an effect is expected and (Tg) is increased too much, this results in an increase in the elastic modulus of the cured resin. Since stress is generally considered to be proportional to the product of the coefficient of thermal expansion and the elastic modulus, even if an inorganic filler such as silica is added to reduce the coefficient of thermal expansion, the result is a decrease in stress strain. In other words, there have been problems in that the adhesiveness between the resin and the base material (semiconductor chip or polyimide tape) is reduced due to stress, and cracks occur in the cured product. ]
For this reason, when the epoxy resin composition and the liquid resin sealing material described in Patent Documents 1 to 3 are used as an underfill, the moisture resistance and thermal cycle resistance of the part sealed with the liquid sealing material, particularly the thermal resistance It is thought that it is inferior in cycle property.

In the case of the invention described in Patent Document 2, it is a liquid sealing resin composition used for TAB (Tape Automated Bonding) (see paragraph [0001] in the same document). In the case of the described invention, since it is a COF (chip-on-film) type epoxy resin composition for semiconductor encapsulation (see [Summary] [Problem], paragraph number [0001], etc.) of the same document], sealing It is considered that the necessity of adding a filler such as a silica filler to the liquid resin encapsulating resin composition and the epoxy resin composition was not recognized for the purpose of improving the thermal cycle resistance of the part.
In the case of TAB and COF, since a flexible wiring board having flexibility is used, even if heat application such as a temperature cycle is applied, stress is applied to the bump electrode due to the difference in thermal expansion coefficient between the substrate and the semiconductor element. There is no. For this reason, in the case of TAB and COF, it is not necessary to add a filler such as a silica filler to the liquid resin encapsulating resin composition and the epoxy resin composition to reinforce the bump electrode.

  The invention described in Patent Document 4 is a resin composition for sealing a semiconductor device containing an epoxy resin, a curing agent, and an inorganic filler, and the inorganic filler contains silica containing a hydroxyl group on the surface thereof, and In a hydroxyl group-containing silica, when trimethoxysilane is dealcoholized, the amount of trimethoxysilane involved in the reaction is 0.05 mmol / g or more. .

  In Patent Document 4, it is said that a curing catalyst for accelerating the curing reaction between the epoxy resin and the curing agent may be used. As the curing catalyst, 2-methylimidazole, 2,4-dimethylimidazole, 2-methyl- Imidazole compounds such as 4-methylimidazole and 2-heptadecylimidazole, triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol , Tertiary amine compounds such as 1,8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5, zirconium tetramethoxide, zirconium tetrapropoxide, tetrakis (Acetylacetonato) zirconium, tri (a Organometallic compounds such as tylacetonato) aluminum and triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine / triphenylborane, tetraphenylphosphorus Examples include organic phosphine compounds such as nium tetraphenylborate (paragraph number [0025] in the same document).

  Patent Document 4 states that the inorganic filler of the sealing resin composition can be subjected to surface treatment with a silane coupling agent as necessary. γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltridimethoxysilane, γ-methacryloxypropylsilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltri Examples include methoxysilane, methyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, and vinyltrimethoxysilane (paragraph numbers [0032] and [0033] in the same document).

  The invention described in Patent Document 5 includes an epoxy resin (A), a curing agent (B), a filler (C), 2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1, Benzene ring having a specific structure such as 2,3-trihydroxybenzene, 1,3,5-trihydroxybenzene, 3,4,5-trihydroxybenzoic acid, 1,2,4-trihydroxybenzene An epoxy resin composition containing a compound (D), wherein the filler (C) is contained in the epoxy resin composition in an amount of 80% by weight or more. .

  In Patent Document 5, it is said that a curing catalyst may be used to accelerate the curing reaction between the epoxy resin (A) and the curing agent (B). As the curing catalyst, 2-methylimidazole and 2,4-dimethylimidazole are used. , Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, triethylamine, benzyldimethylamine, α-methylbenzylmethylamine, 2- ( Tertiary amine compounds such as dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 and salts thereof, zirconium tetramethoxide , Zirconium tetrapropoxide, tetrakis (a Organometallic compounds such as tylacetonato) zirconium and tri (acetylacetonato) aluminum and their salts, and triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine Organic phosphine compounds and salts thereof, 1,8-diazabicyclo (5,4,0) undecene-7 · tetraphenylborate, tetraphenylphosphonium · tetraphenylborate, adducts of triphenylphosphine and p-benzoquinone, etc. Is exemplified (paragraph number [0014] in the same document).

  In Patent Document 5, it is preferable that the epoxy resin composition contains a coupling agent. As the coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldibenzoate are used. Ethoxysilane, N- (2-aminoethyl) γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane Silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, isopropyl Tris Le pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate coupling agents such as titanate, aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate is illustrated. These coupling agents may be surface-treated on the filler in advance, but may be added only to the epoxy resin composition (paragraph numbers [0026] and [0027] in the same document).

As described above, in order to improve the moisture resistance and thermal cycle resistance of the sealed portion, it is effective to add a filler such as a silica filler to the liquid sealing material.
However, when a filler such as a silica filler is added to the liquid sealing material, the injectability of the liquid sealing material tends to decrease.
In recent years, due to the progress of narrowing gaps in semiconductor devices, liquid sealing materials used as underfills are strongly required to have improved injectability.

  In order to solve the above-mentioned problems of the prior art, the present invention is excellent in injectability, adhesiveness, curability, storage stability, etc., does not generate voids, and further has moisture resistance at the sealed site. An object of the present invention is to provide a liquid sealing material excellent in thermal cycle resistance, reflow resistance, crack resistance, warpage resistance, and the like, and an electronic component in which a sealing portion is sealed using the liquid sealing material And

  In order to achieve the above object, the present invention provides a liquid containing (A) an epoxy resin, (B) an aromatic amine curing agent, (C) a metal complex, (D) a coupling agent, and (E) a silica filler. A sealing material, wherein the coupling agent of component (D) contains at least vinyltrimethoxysilane, and the silica filler of component (E) is surface-treated with a silane coupling agent in advance. A liquid sealing material is provided.

  In the liquid sealing material of the present invention, the silica filler as the component (E) is preferably surface-treated in advance with a silane coupling agent containing at least one of a trimethoxysilane compound and a triethoxysilane compound. .

  In the liquid sealing material of the present invention, the silica filler as the component (E) is a silane coupling agent containing at least one of 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane. It is preferable that the surface treatment is performed in advance.

  In the liquid sealing material of the present invention, the silica filler as the component (E) preferably has an average particle size of 0.05 to 10 μm.

  In the liquid sealing material of the present invention, the content of the silica filler as the component (E) is preferably 40 to 80 wt%.

  In the liquid sealing material of the present invention, the metal complex of the component (C) is preferably at least one selected from the group consisting of aluminum triacetylacetonate and aluminum bisethylacetoacetate / monoacetylacetonate.

  In the liquid sealing material of the present invention, the ratio of the aromatic amine curing agent of the component (B) is 0.7 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin of the component (A). It is preferable.

  In the liquid sealing material of the present invention, the content of vinyltrimethoxysilane as the coupling agent of the component (D) is preferably 0.2 to 2.0 wt%.

  Moreover, this invention provides the electronic component formed by sealing a sealing site | part using the liquid sealing material of this invention.

The liquid sealing material of the present invention is excellent in injectability, adhesiveness, curability, storage stability and the like, and does not generate voids. Further, the moisture resistance of the sealed part, thermal cycle resistance, Excellent reflow resistance, crack resistance and warpage resistance.
The liquid encapsulant of the present invention has an addition reaction (curing) of the epoxy resin of component (A) by the interaction between vinyltrimethoxysilane contained in component (D) and the metal complex of component (C). By acting as a promoting catalyst component, it is possible to prevent appearance defects such as generation of wrinkles on the surface of the cured product of the liquid sealing material.
Since the electrical component of the present invention is excellent in the moisture resistance of the sealing portion, there is no insulation deterioration or short circuit between wirings. In addition, because of the excellent thermal cycle resistance of the sealing part, bumping is caused by the difference in thermal expansion coefficient between the substrate made of an organic material such as epoxy resin and the semiconductor element by adding heat such as temperature cycle. Stress is not applied to the electrodes, and defects such as cracks do not occur in the bump electrodes.

FIG. 1 is a photograph showing the appearance of a cured product of the liquid sealing material of Example 1. FIG. 2 is a photograph showing the appearance of a cured product of the liquid sealing material of Comparative Example 2.

Hereinafter, the present invention will be described in detail.
The liquid sealing material of the present invention contains the following components (A) to (E) as essential components.

(A) Component: Epoxy Resin The epoxy resin (A) is a component that forms the main component of the liquid sealing material of the present invention.
The epoxy resin of component (A) is preferably liquid at normal temperature, but even if it is solid at normal temperature, it should be diluted with another liquid epoxy resin or diluent and used as a liquid. Can do.

Specifically, bisphenol type epoxy resins that are glycidyl ethers such as bisphenol A and bisphenol F: liquid glycidyl amine type epoxy resins such as diglycidyl aniline, diglycidyl orthotoluidine, paraaminophenol type epoxy resin; (3 ′, 4 ′ An alicyclic epoxy resin such as -epoxycyclohexane) methyl-3,4-epoxycyclohexylcarboxylate, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4,1,0] heptane; Hydrogenated epoxy resins such as 2,2-bis (4-hydroxycyclohexyl) propane diglycidyl ether, 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane, etc. Cyclohexane oligomer having an epoxy group of Such as novolac type epoxy resin. Preferred are a liquid bisphenol type epoxy resin, a liquid glycidylamine type epoxy resin, and a cyclohexane oligomer having an epoxy group, and particularly preferred are a liquid bisphenol A epoxy resin, a liquid bisphenol F epoxy resin, a liquid paraaminophenol type epoxy resin, 3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane, hydride of liquid bisphenol A epoxy resin, (3 ′, 4′-epoxycyclohexane) methyl-3,4- Examples thereof include epoxy cyclohexyl carboxylate and 1,2: 8,9-diepoxyne.
As the epoxy resin as the component (A), any one of the above-described epoxy resins may be used, or two or more may be used in combination.

(B) Component: Aromatic amine curing agent The (A) component aromatic amine curing agent is a curing agent for the (A) component epoxy resin.
The aromatic amine curing agent as component (B) is preferably liquid at normal temperature, but may be solid at normal temperature. When it is solid at room temperature, it is preferably mixed with the epoxy resin of component (A) after being liquefied by heating.

  The aromatic amine curing agent as component (B) is preferably an aromatic amine having an alkylenedianiline structure, and is preferably an aromatic amine having at least one substituent on the aromatic ring. The substituent is preferably a lower alkyl group such as a methyl group or an ethyl group, or a lower alkoxy group such as a methoxy group. The aromatic amine curing agent (B) as the component (B) may contain an oligomer generated as a by-product when it is synthesized. The aromatic amine curing agent (B) can be used alone or in combination. Of course, other amine curing agents can be used in combination as long as the properties of the aromatic amine curing agent of component (B) are not impaired.

  Specific examples of the aromatic amine curing agent (B) include metaphenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2, Aromatic amine curing agent having one aromatic ring such as 4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole; 2,4-diaminodiphenylmethane, 4,4-diaminodiphenyl Sulfone, 4,4-diaminodiphenylsulfone, 4,4′-methylenebis (2-ethylaniline), 3,3′-diethyl-4,4′-diaminophenylmethane, 3,3 ′, 5,5′-tetra Aroma of two aromatic rings such as methyl-4,4′-diaminophenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminophenylmethane Amine curing agent; hydrolysis condensate of the aromatic amine curing agent; aromatic amine curing agent such as polytetramethylene oxide di-p-aminobenzoate, polytetramethylene oxide diparaaminobenzoate; aromatic diamine and epichloro Examples thereof include condensates with hydrin and reaction products of aromatic diamines and styrene.

Preferred is an aromatic amine having an alkylenedianiline structure, and particularly preferred is liquid 4,4′-methylenebis (2-ethylaniline) from the viewpoint of reactivity.
Moreover, since a liquid sealing material with a low viscosity can be obtained, the combined use of 3,5-diethyl-2,4-diaminotoluene and 3,5-diethyl-2,6-diaminotoluene is preferable.

  The aromatic amine curing agent of the component (B) has a ratio of 0.7 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin (A). It mix | blends so that it may become. If it is outside the above range, problems such as a decrease in the adhesive strength of the liquid sealing material to the semiconductor element and a decrease in the glass transition point may occur.

(C) Component: Metal Complex The metal complex of the (C) component is a catalyst component that promotes the curing of the epoxy resin of the (A) component in cooperation with the coupling agent of the (D) component. The metal complex of component (C) is not particularly limited as long as it has a curing accelerating action, but it exhibits a curing accelerating action at a desired heating temperature, has good storage stability, and has excellent pot life. preferable.
Examples of the metal include aluminum, iron, zinc, indium, and magnesium, and aluminum is preferable.
Examples of the ligand include acetylacetonate, pyridine, triphenylphosphine, ethylenediamine, and ethylenediaminetetraacetic acid. Acetylacetonate is preferable. Particularly preferred is an acetylacetonate complex of aluminum.
Of course, two or more metal complexes of the component (C) can be used in combination. In addition, other metal complexes can be used in combination as long as the characteristics of the metal complex of component (C) are not impaired.

  Aluminum acetylacetonate complexes include aluminum trisacetylacetonate, aluminum tris (octadecylacetylacetonate), aluminum tris (hexadecylacetylacetonate), aluminum ethylacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate However, aluminum trisacetylacetonate and aluminum bisethylacetoacetate / monoacetylacetonate are preferable from the viewpoints of curability and storage stability. Of course, two or more of these may be used in combination.

  Since the metal complex of the component (C) acts as a catalyst in cooperation with the coupling agent of the component (D), the compounding amount cannot be uniquely determined, but the metal complex of the component (C) (C )) Is 0.1 to 2 parts by weight, preferably 0.2 to 0.2 parts by weight per 100 parts by weight of the total amount of the epoxy resin as the component (A) and the aromatic amine curing agent as the component (B). 1.8 parts by mass. If it is less than this range, the liquid encapsulant may be inferior in curability, and if it is more than this range, the storage stability of the liquid encapsulant may be deteriorated.

(D) Component: Coupling agent The coupling agent of (D) component is a catalyst component that promotes the addition reaction (curing) of the epoxy resin of (A) component by the aromatic amine curing agent of (B) component, It works in cooperation with the metal complex of component (C).
Specific examples of the coupling agent (D) include a silane coupling agent described later and a silicon compound represented by the following structural formula.
In the above structural formula, R is a linear or branched alkyl group having 1 to 10 carbon atoms, R 'is an alkyl group having 1 to 2 carbon atoms, and n is an integer of 1 to 3.

  Silane coupling agents include vinyl, glycidoxy, methacrylic, amino, mercapto, etc., but vinyl silane coupling agents are combined with (C) component metal complexes compared to other silane coupling agents. Is preferable because it does not cause appearance defects such as swelling of the cured liquid sealing material.

  Examples of the vinyl silane coupling agent include vinyl tris (β-methoxyethoxy) silane, vinyl trimethoxy silane, vinyl triethoxy silane, and the like, with vinyl trimethoxy silane being particularly preferred. These can be used in combination.

  Examples of the glycidoxysilane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Preference is given to 3-glycidoxypropyltrimethoxysilane.

  As aminosilane coupling agents, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ -Aminopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propylamine, N- (1,3-dimethylbutylidene) -2- (trimethoxysilyl) ) -1-propylamine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, N- (1,3-dimethylbutylidene) -2- (triethoxysilyl) ) -1-propylamine and the like, and their hydrolysis condensates. Preferred is N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine.

  As the mercaptosilane coupling agent, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like are preferable.

  Examples of the silicon compound represented by the above structural formula include monoalkoxysilanes such as triphenylmethoxysilane, triphenylethoxysilane, and diphenylmethylmethoxysilane; dialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; tri (paramethoxy) Phenyl) silane, trialkoxysilane such as paramethylbenzyltrimethoxysilane. Preferred are dialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane. These can be used in combination. These silicon compounds can also be used in combination with the silane coupling agent described above.

(D) As a coupling agent of a component, 1 type in the silane coupling agent mentioned above and the silicon compound represented by the said structural formula, or 2 or more types can be used. However, for reasons such as prevention of wrinkles on the surface of the cured product, the coupling agent of component (D) contains at least vinyltrimethoxysilane.
The reason why the generation of wrinkles on the surface of the cured product can be prevented by the fact that the coupling agent of component (D) contains at least vinyltrimethoxysilane will be described below.

When an aromatic amine curing agent is used as the epoxy resin curing agent as in the liquid sealing material of the present invention, the acid acts as a catalyst component for promoting the addition reaction (curing) of the epoxy resin.
However, if an acid is contained in the liquid sealing material, the storage stability of the liquid sealing material is deteriorated. Therefore, a latent curing catalyst that generates an acid when the liquid sealing material is heated and develops a curing acceleration effect. Are preferably used.
As such a latent curing catalyst, a combination of a silane coupling agent and a metal complex is preferably used because it generates an acid at a desired heating temperature and exhibits a curing accelerating action.

When a combination of a silane coupling agent and a metal complex is used as the latent curing catalyst, when the liquid sealing material is heated, the hydrolysis of the silane coupling agent proceeds due to moisture in the atmosphere. The resulting Bronsted acid exhibits a curing accelerating action.
As the silane coupling agent, 3-glycidoxypropylmethoxysilane is usually used because it has an affinity with the epoxy resin, but since the hydrolysis rate is relatively slow, the surface layer of the liquid sealing material and the internal However, there is a difference in the hydrolysis rate. Specifically, the surface layer of the liquid sealing material has a faster hydrolysis rate than the inside of the liquid sealing material. As a result, the curing of the epoxy resin proceeds faster in the surface layer than the inside of the liquid sealing material, and a shrinkage reaction occurs when the epoxy resin is cured, so that wrinkles are generated on the surface of the cured liquid sealing material. Become.

  On the other hand, since vinyltrimethoxysilane is easily hydrolyzed, there is no difference in the hydrolysis rate between the surface layer of the liquid sealing material and the inside, or even if there is a difference, the difference is very small. As a result, there is no difference in the progress of curing of the epoxy resin between the inside of the liquid sealing material and the surface layer, and wrinkles are not generated on the surface of the cured product of the liquid sealing material.

In Patent Document 4, it is said that the inorganic filler of the sealing resin composition can be surface-treated with a silane coupling agent as necessary, but this is the liquid sealing of the present invention. It is used for the same purpose as the component (E) of the material, and there is no description or suggestion that a silane coupling agent is used as the latent curing catalyst component of the epoxy resin.
In this regard, in paragraph numbers [0007] to [0011] and [0034] of Patent Document 4, when an unreacted silane coupling agent is present in the sealing resin composition, It is also clear from the description that the alcohol reacts with the moisture and the silane coupling agent, and this alcohol causes voids and cracks.
In addition, in the liquid sealing material of the present invention, since the (C) component metal complex and the (D) component coupling agent are used in combination as a latent curing catalyst for epoxy resin, The problems described in paragraph numbers [0007] to [0011] and [0034] do not occur.

  Also for Patent Document 5, although it is said that the epoxy resin composition preferably contains a coupling agent, it is used for the same purpose as the component (E) of the liquid sealing material of the present invention, ie, filling. It is used for the purpose of surface treatment of materials. In paragraph [0027] of Patent Document 5, it is described that the coupling agent may be added to the epoxy resin composition, but it is used for the purpose of surface treatment of the filler. In this regard, it is not described at all that a coupling agent and a metal complex are used as a latent curing catalyst for an epoxy resin, or the filler is surface-treated with a coupling agent in advance. Further, it is also clear from the fact that no coupling agent is added to the epoxy resin composition.

In the liquid sealing material of the present invention, the content of vinyltrimethoxysilane as the coupling agent of the component (D) is preferably 0.2 to 2.0 wt%, and 0.3 to 1.5 wt%. It is more preferable that it is 0.5 to 1.0 wt%.
If the content of vinyltrimethoxysilane is less than 0.2 wt%, wrinkles may occur on the surface of the cured product. On the other hand, if the content of vinyltrimethoxysilane exceeds 2.0 wt%, voids may occur during curing.
In addition, the suitable range of the mixture ratio of (D) component coupling agent itself is mentioned later.

  Since the coupling agent of component (D) catalyzes in cooperation with the metal complex of component (D), its amount cannot be determined uniquely, but the coupling agent of component (D) The standard of the blending ratio is preferably 0.5 to 4 parts by mass, more preferably 0 with respect to 100 parts by mass of the total amount of the epoxy resin of component (A) and the aromatic amine curing agent of component (B). .8-3 parts by mass. If it is less than this range, the liquid encapsulant may be inferior in curability, and if it is more than this range, the storage stability of the liquid encapsulant may be deteriorated.

(E) Component: Silica Filler The silica filler of the (E) component is added to the liquid sealing material for the purpose of improving the moisture resistance and thermal cycle resistance of the sealed site, particularly the thermal cycle resistance.
However, as described above, when a filler such as a silica filler is added to the liquid sealing material, the injectability of the liquid sealing material tends to decrease.
In the liquid sealing material of the present invention, the silica filler of the component (E) is sealed without reducing the pouring property of the liquid sealing material by using a surface treated with a silane coupling agent in advance. Improve the moisture resistance and thermal cycle resistance, especially thermal cycle resistance of the affected part.

For the surface treatment of the silica filler, various silane coupling agents such as vinyl, glycidoxy, methacryl, amino and mercapto can be used. The silane coupling agent used for the surface treatment of the silica filler preferably contains at least one of a trimethoxysilane compound and a triethoxysilane compound because it is excellent in the effect of suppressing the deterioration of the injection property of the liquid sealing material. Moreover, it is excellent also in the dispersion stability of a silica filler, and is preferable also from the point of the storage stability of a liquid sealing agent.
In addition, the silane coupling agent used for the surface treatment of the silica filler may contain only one of the trimethoxysilane compound and the triethoxysilane compound, or may contain both of them. Specific examples of the trimethoxysilane compound and the triethoxysilane compound will be described later.

Specific examples of the trimethoxysilane compound include 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-aminopropyl. Examples include trimethoxysilane and 3-mercaptopropyltrimethoxylane.
Specific examples of the triethoxysilane compound include N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, vinyltriethoxysilane, and 3-aminopropyltriethoxysilane. The
Among these, 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane are preferable because they are excellent in the effect of suppressing a decrease in injectability of the liquid sealing material and in storage stability.

The method for surface-treating the silica filler with a silane coupling agent is not particularly limited, and can be carried out by, for example, a stirring method or a wet method.
The stirring method is a method in which a silane coupling agent and a silica filler are previously charged in a stirring device and stirred under appropriate conditions. As the stirring device, a mixer capable of stirring and mixing at high speed such as a Henschel mixer is used. Although it can be used, it is not particularly limited. Stirring conditions are not particularly limited. Specifically, for example, silica filler is charged into a Henschel mixer, premixed at 1000 rpm for 3 minutes, and then a silane coupling agent is dropped, and further at 1000 rpm for 5 minutes. The conditions of this mixing can be mentioned. In addition, what is necessary is just to select suitable conditions for the rotational speed and mixing time of the said preliminary mixing and this mixing according to the kind of silane coupling agent to be used, the content and amount of a silica filler and a silane coupling agent.
In the wet method, a sufficient amount of the silane coupling agent relative to the surface area of the silica filler to be surface-treated is dissolved in water or an organic solvent to hydrolyze the molecules of the compound forming the silane coupling agent. A surface treatment solution is used. The concentration of the surface treatment solution is not particularly limited, and for example, about 3% by mass can be mentioned. A silica filler is added to the obtained surface treatment solution and stirred so as to form a slurry. After sufficiently reacting the silane coupling agent and the silica filler by stirring, the silica filler is separated from the surface treatment solution by a method such as filtration or centrifugation, and then dried by heating.
In addition to the above stirring method and wet method, for example, an integral blend method in which the surface of the silica filler is modified by directly adding a silane coupling agent to a silica filler dispersion obtained by dispersing the silica filler in a solvent. Can also be suitably used.

The silica filler of component (E) preferably has an average particle size of 0.05 to 10 μm from the viewpoints of adjusting the viscosity of the liquid sealing material, injectability of the liquid sealing agent, preventing the generation of voids, and the like. More preferably, it is 1-5 micrometers, and it is still more preferable that it is 0.3-3 micrometers.
Here, the shape of the silica filler is not particularly limited, and may be any form such as granular, powder, and flakes. In addition, when the shape of a silica filler is other than a granular form, the average particle diameter of a silica filler means the average maximum diameter of a silica filler.

  In the liquid sealing material of the present invention, the content of the silica filler of the component (E) is 40 to 80 wt%, reinforcing the bump electrode, a substrate made of an organic material such as an epoxy resin, a semiconductor element, It is preferable for reasons such as a reduction in the difference in thermal expansion coefficient, more preferably 50 to 70 wt%, and even more preferably 55 to 65 wt%.

  The liquid sealing material of this invention may contain the component described below as needed other than the said (A)-(E) component.

(Other ingredients)
The liquid sealing material of this invention may further contain components other than the said (A)-(E) component as needed.
As specific examples of such components, a leveling agent, a colorant, an ion trapping agent, an antifoaming agent, a flame retardant, and the like can be blended. The type and amount of each compounding agent are as usual. Further, thermosetting resins such as okitacene, acrylate, bismaleimide, thermoplastic resins, elastomers, and the like may be blended.

(Preparation of liquid sealing material)
The liquid sealing material of the present invention is prepared by mixing and stirring the components (A) to (E) and other compounding agents to be blended as necessary. Although mixing and stirring can be performed using a roll mill, of course, it is not limited to this. When the epoxy resin as the component (A) is solid, it is preferably liquefied or fluidized and mixed by heating.
Even if the components are mixed at the same time, some components may be mixed first, and the remaining components may be mixed later.

  In the liquid sealing material of the present invention, the aromatic amine curing agent used as the component (B) is easier to adjust the glass transition point (Tg) than phenol-based curing agents and acid anhydride-based curing agents. Although excellent, there is a problem that curing is slow and bleeding and creeping are likely to occur. In the present invention, by using a specific coupling agent as the component (D) and using a silica filler having a specific surface treatment as the component (E), the combined use of the metal complex as the component (C) can be achieved. This makes it possible to improve curability and consequently suppress bleed and creep, which are disadvantages.

Next, the usage method of the liquid sealing material of this invention is demonstrated.
When using the liquid sealing material of the present invention, the liquid sealing material of the present invention is applied to a portion to be sealed (surface to be sealed) using a dispenser, a printing machine, or the like. Here, the temperature during coating is preferably 70 to 120 ° C.
Thereafter, the sealing is completed by heat-curing at a predetermined temperature for a predetermined time, specifically, at 140 to 170 ° C. for 20 minutes to 3 hours.

  The electronic component of the present invention is obtained by sealing a sealed portion by the above procedure using the liquid sealing material of the present invention. The electronic component to be sealed here includes a semiconductor element, and is not particularly limited by an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, a capacitor, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

(Examples 1-5, Comparative Examples 1-5)
The components shown in Table 1 were weighed out in the amounts (parts by mass) shown in Table 1, and the mixture mixed at once was kneaded with a three-roll mill to obtain a uniform liquid sealing material. Next, the liquid sealing material was placed under a reduced pressure to remove bubbles in the liquid sealing material, and used as a sample for evaluation.
In addition, the symbol in a table | surface represents the following, respectively.
Epoxy resin (A): Bisphenol F type epoxy resin (epoxy equivalent 158)
Aromatic amine curing agent (B): 4,4′-diamino-3,3′-diethyldiphenylmethane metal complex (C): aluminum trisacetylacetonate coupling agent (D1): 3-glycidoxypropyltrimethoxy Silane coupling agent (D2): Vinyltrimethoxysilane silica filler (E1): 3-glycidoxypropyltrimethoxysilane surface-treated silica filler (average particle size 2 μm)
Silica filler (E2): 3-methacryloxypropyltrimethoxysilane surface-treated silica filler (average particle size 2 μm)
Silica filler (E3): Untreated surface silica filler (average particle size 2 μm)

  The following methods evaluated the sclerosis | hardenability of the liquid sealing material obtained by said procedure, pouring property, the external appearance of the hardened | cured material of this liquid sealing material, and thermal cycle resistance.

(Curable)
The sample for evaluation was dropped on a hot plate of 150 ± 2 ° C. to a size of about 5 mmφ, and the time until the stringing disappeared was measured with a stopwatch.

(Injectability)
A glass substrate is laminated with a gap of 50 μm, an evaluation sample is injected into the gap by capillary action, and an arrival time up to 20 mm is measured.

(appearance)
About 5 g of the sample for evaluation was weighed into a metal case (50 mmφ), heated at 150 ° C. for 90 minutes, and cured to prepare a test piece. The cured state (wax, void) of the test piece was visually observed.
A glass substrate was laminated with a gap of 50 μm, and a sample for evaluation was injected into the gap by capillary action, and then heated and cured at 150 ° C. for 90 minutes to prepare a test piece. The cured state of the injection part and fillet part of the test piece was visually observed to check for the presence of voids and wrinkles. In any case, the case where there were no wrinkles and voids was judged as acceptable (◯) when the appearance was good, and the case where there were wrinkles and voids on either side was regarded as a failure (×) when the appearance was bad.
For Example 1 and Comparative Example 2, a sample for evaluation was applied to a stainless steel plate to a thickness of about 250 μm, heated at 165 ° C. for 90 minutes, and cured to cure the test piece (wallet / flank). ) Was observed. FIG. 1 is a photograph showing the appearance of the test piece (cured material of liquid sealing material) of Example 1, and FIG. 2 shows the appearance of the test piece (cured material of liquid sealing material) of Comparative Example 2. It is a photograph.

(Thermal cycle resistance)
A PI passivation die (die size 10 mm × 10 mm × thickness 0.73 mm) and Sn5Pb95 bump (bump pitch 175 μm) are formed on an FR-4 substrate (substrate size 52.5 mm × 30.0 mm × thickness 0.73 mm). Using the test element group (TEG) (manufactured by Hitachi Ultra LSI Systems Co., Ltd.), the liquid encapsulant obtained by the above procedure is injected into the die part and heated at 165 ° C. for 120 minutes to obtain the liquid encapsulant The cured specimen was subjected to 260 ° C reflow once, JEDEC Lv3, 260 ° C reflow three times, and then a thermal cycle (-55 ° C / 30 min. To 125 ° C / 30 min.) Was performed. Then, it observed using the ultrasonic flaw detector and investigated the presence or absence of an internal crack and interface peeling, and resistance value change. When there is no internal crack and interface peeling and the resistance change is less than 10%, the internal crack and interface peeling area is 1% or more of the die area, or the resistance change is 10% or more. Was carried out up to 1000 cycles.

(Pot life, thickening ratio)
After measuring the viscosity of the prepared sample for evaluation using a rotational viscometer (50 rpm), the viscosity at the time when the sample for evaluation was placed in a sealed container and stored in an environment of 25 ° C. and 50% humidity for 24 hours was measured. The measurement was carried out in the same procedure, and the magnification with respect to the viscosity immediately after preparation was calculated.

  As for the liquid sealing material of Examples 1-5, sclerosis | hardenability, injectability, the external appearance, thermal cycle resistance, and the evaluation result of pot life were all favorable. On the other hand, as the component (E), the liquid sealing material of Comparative Example 1 using an untreated silica filler was inferior in injectability. Moreover, the liquid sealing material of the comparative examples 2 and 3 which does not contain vinyltrimethoxysilane (D2) as a coupling agent of (D) component was inferior in sclerosis | hardenability. In particular, the liquid sealing material of Comparative Example 2 containing the metal complex of component (C) but not containing vinyltrimethoxysilane (D2) as the coupling agent of component (D) is inferior in the appearance of the cured product. It was. Also, as shown in FIG. 1, the cured product of Example 1 did not generate wrinkles on the surface and had a good appearance, whereas the cured product of Comparative Example 2, as shown in FIG. The surface was wrinkled and the appearance was poor. Moreover, the liquid sealing material of the comparative example 4 which does not contain a silica filler ((E1)-(E3)) was inferior to thermal cycle resistance, and failed before reaching 250 cycles. Moreover, the liquid sealing material of the comparative example 5 which does not contain a metal complex (C) was inferior to sclerosis | hardenability.

Claims (9)

  A liquid sealing material comprising (A) an epoxy resin, (B) an aromatic amine curing agent, (C) a metal complex, (D) a coupling agent, and (E) a silica filler, wherein the component (D) A liquid sealing material, wherein the coupling agent contains at least vinyltrimethoxysilane, and the silica filler of the component (E) is surface-treated in advance with a silane coupling agent.   2. The liquid according to claim 1, wherein the silica filler of the component (E) is previously surface-treated with a silane coupling agent containing at least one of a trimethoxysilane compound and a triethoxysilane compound. Sealing material.   The silica filler as the component (E) is previously surface-treated with a silane coupling agent containing at least one of 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane. The liquid sealing material according to claim 2.   The liquid sealing material according to any one of claims 1 to 3, wherein an average particle diameter of the silica filler as the component (E) is 0.05 to 10 µm.   Content of the silica filler of the said (E) component is 40-80 wt%, The liquid sealing material in any one of Claims 1-4 characterized by the above-mentioned.   6. The metal complex of the component (C) is at least one selected from the group consisting of aluminum triacetylacetonate and aluminum bisethylacetoacetate / monoacetylacetonate. The liquid sealing material as described.   The proportion of the aromatic amine curing agent as the component (B) is 0.7 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin as the component (A). 6. The liquid sealing material according to any one of 6.   The liquid sealing material according to any one of claims 1 to 7, wherein a content of vinyltrimethoxysilane as a coupling agent of the component (D) is 0.2 to 2.0 wt%.   The electronic component formed by sealing a sealing part using the liquid sealing material in any one of Claims 1-8.