KR19980042952A - Resin composition and semiconductor device using same - Google Patents

Abstract

The present invention relates to a resin composition and a semiconductor device using the same,

The said resin composition is comprised from the hardening | curing agent containing the (a) epoxy compound, (b) polysiloxane resin which has a phenolic hydroxyl group in a side chain, and (c) an inorganic filler. It is characterized by the above-mentioned.

Description

Resin composition and semiconductor device using same

The present invention relates to a resin composition which is excellent in moldability and heat resistance and which is suitable for use in encapsulation of a semiconductor device, and a resin-encapsulated semiconductor device sealed with the resin composition.

At present, there is a tendency to increase the integration of semiconductor devices, and the reduction of various functional units of the devices and in particular the expansion of devices are rapidly progressing. In order to seal the said semiconductor element with a resin composition, the epoxy resin composition comprised from a thermoplastic epoxy resin as a main component and a phenol resin as a hardening | curing agent is used widely.

For example, a surface mount package typified by a so-called ASIC (Application Specific IC) gate array or a standard cell LSI has been produced using the above epoxy resin composition as a sealing resin. In the method of mounting the above semiconductor device on a substrate, various methods such as vapor phase reflux, infrared reflux, and solder dipping have been used. In the mounting method, the package is usually exposed to a high temperature of 215 to 260 ° C. to rapidly evaporate traces of water penetrated into the package, causing cracks in the sealing resin.

When the crack extends to the outer surface of the encapsulating resin, the moisture resistance of the resin-encapsulated semiconductor device causes serious problems and will be damaged. Moreover, when cracks are generated in the sealing resin, the resin causes deformation of the package, making it difficult to mount the package on the substrate.

Moreover, when the package is installed on a substrate, various problems including cracks occur in the semiconductor element sealed with resin. For example, PSG (phosphosilicate glass) or SiN (silicon nitride) used as a surface stabilization film for the metallic intermediate wire layer formed of aluminum is decomposed or cracking of the gold bond wire occurs.

In order to solve the above problem, there are various demands as described below, particularly in the manufacture of large-scale resin-encapsulated semiconductor devices, which are mainly related to sealing resins.

(1) The stress that the internal device receives by the sealing resin is minimized, and the adhesion between the sealing resin and a film or a lead frame such as a PSG film, SiN film or polyimide film formed on the semiconductor element should be improved.

(2) The sealing resin must be excellent in heat resistance such as high temperature strength under high temperature strength or moisture absorption to withstand the mounting temperature of the package. At the same time, the hygroscopicity of the sealing resin should be as low as possible.

On the other hand, in order to minimize the mounting area of the semiconductor chip due to the popularization of notebook personal computers and mobile phones, the mounting of flip chip that can directly attach a bare chip on the substrate is widely used. In order to mount the flip chip, it is required to use a liquid sealing resin having excellent reliability such as low hygroscopicity and excellent adhesion.

With the above requirements, a method of using a resin composition containing silicone oil has been developed while minimizing the stress that the internal device receives from the sealing resin and improving the adhesion between the sealing resin and the lead frame. However, the addition of silicone oils causes the silicone to seep into the surface of the molded article, causing the appearance of the article to degrade or contaminate the metal mold.

Usually, conventional epoxy resin compositions contain amine compounds or acid anhydrides as hardeners. However, the resin composition containing the said hardening | curing agent has high hygroscopicity, and it is difficult to obtain the sealing resin which has reliable moisture-proof property.

As described above, resin compositions that not only provide all kinds of features required when used as sealing resins but also exhibit low water absorption and avoid contamination of metal molds have not yet been used.

An object of the present invention is to provide a resin composition which is excellent in moldability and heat resistance, and at the same time has low water absorption, so that a semiconductor device can be enclosed.

Another object of the present invention is to provide a resin-sealed semiconductor device which is excellent in heat resistance and thermal shock resistance and at the same time high in moisture resistance.

1 is a cross-sectional view showing an example of a resin-enclosed semiconductor device of the present invention;

2 is a cross-sectional view showing another example of the resin-enclosed semiconductor device of the present invention; And

3 is a cross-sectional view illustrating an example of a manufacturing step of the resin-enclosed semiconductor device disclosed in FIG. 2.

* Explanation of symbols for main parts of the drawings

1: semiconductor device 2, 21: substrate

3: mating pad 4: lead frame

5: bonding wire 6,22: resin layer

10,20: semiconductor device 23: bump

24: semiconductor chip 25: resin composition

According to the present invention, the resin composition comprises: (a) an epoxy compound; (b) a curing agent containing a polysiloxane resin having a phenolic hydroxyl group in the side chain; And (c) an inorganic filler.

In addition, according to the present invention, the resin composition is (a) an epoxy compound; (b) a curing agent comprising a polysiloxane resin having a repeating unit according to PS1 of Formula 1 and / or PS2 of Formula 2 below; And (c) an inorganic filler.

(R ¹ in the formula (I) is an alkyl group, a vinyl group, an allyl group, is selected from the consisting of a substituted or unsubstituted aryl group and a substituted or unsubstituted siloxy group having from 1 to 10 carbon atoms; R ² to R ⁶ may be the same or different, and when at least one of R ² to R ⁶ is a hydroxyl group, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a carboxyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkoxy group, allyl Individually selected from the group consisting of oxy groups, allyl groups and substituted or unsubstituted aryl groups)

R ⁷ in Formula 2 is a group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and a substituted or unsubstituted siloxy group. R ⁸ to R ¹² may be the same or different, and when at least one of R ⁸ to R ¹² is a group having a phenolic hydroxyl group or a phenolic hydroxyl group, a hydrogen atom, a halogen atom, a substitution Or unsubstituted alkyl, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkoxy, acyloxy, allyloxy, allyl, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, amide groups and imides Is selected from a group consisting of

According to the present invention, there is also provided a resin-enclosed semiconductor device comprising a substrate, a semiconductor element mounted on a surface of the substrate, and a resin layer for sealing the semiconductor element, wherein the resin layer is formed of one of the resin compositions. To form a cured material.

Additional objects and advantages of the invention will be described in detail below, and can be seen by the examples of the invention. The objects and advantages of the invention can be obtained by the combination and the utility indicated in the appended claims below.

The following drawings, which form part of the specification, illustrate preferred embodiments of the invention, and the general description set forth above and the preferred embodiments set forth below are provided to illustrate the principles of the invention.

The invention will also be described in detail with reference to the following preferred examples.

As for the component (a) composed of the epoxy compound in the resin composition of the present invention, the epoxy compound may be used as long as there are two or more epoxy groups in its molecule. Examples of such compounds include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether and its derivatives of biphenyl ether, diglycidyl ether and its derivatives of biphenyl, phenol no Epoxy resin derived from epoxidation of condensation of phenol type novolak type epoxy resin, cresol novolak type epoxy resin, naphthol novolak epoxy resin, bisphenol A novolak epoxy resin, hydroxybenzaldehyde and phenol or alkylphenol, epoxidized tris Hydroxyphenyl) alkanes, epoxidized tetra (hydroxyphenyl) alkanes, tetraglycidyl ethers of 2,2 ', 4,4'-tetrahydroxybenzophenones, N, N-glycidylamino-4-glycids Doxybenzene, 1,3,5-triglycidoxybenzene, 2,2 ', 4,4'- tetraglycidoxy biphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethyl biphenyl, N, N, N ′, N′-tetraglycidylaminodipe Methane and has its condensate, a cycloaliphatic epoxy resin and halogenated epoxy resin.

The epoxy compound may be appropriately selected depending on the component (b) used as the curing agent in the resin composition of the present invention. In addition, the total amount of the component (b) and the epoxy resin composed of the curing agent in the resin composition of the present invention can be measured by adjusting the thermal expansion coefficient and the melt viscosity of the molded article. For example, when the resin composition is used to enclose a semiconductor element, the total amount of the epoxy resin and the curing agent is preferably limited to the range of 5 parts by weight to 50 parts by weight based on the resin compound.

The (b) component in the resin composition of this invention is a hardening | curing agent for hardening | curing (a) component comprised from said epoxy composition, and contains the polysiloxane resin which has a phenolic hydroxyl group in a side chain. For the polysiloxane resin having a phenolic hydroxyl group in the side chain, it is preferable to use a polysiloxane resin having a repeating unit according to PS1 of Formula 1 or PS2 of Formula 2 below.

(Formula 1)

(R ¹ in the formula (I) is an alkyl group, a vinyl group, an allyl group, is selected from the consisting of a substituted or unsubstituted aryl group and a substituted or unsubstituted siloxy group having from 1 to 10 carbon atoms; R ² to R ⁶ may be the same or different, and when at least one of R ² to R ⁶ is a hydroxyl group, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a carboxyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkoxy group, allyl Individually selected from the group consisting of oxy groups, allyl groups and substituted or unsubstituted aryl groups)

(Formula 2)

R ⁷ in Formula 2 is a group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and a substituted or unsubstituted siloxy group. R ⁸ to R ¹² may be the same or different, and when at least one of R ⁸ to R ¹² is a group having a phenolic hydroxyl group or a phenolic hydroxyl group, a hydrogen atom, a halogen atom, a substitution Or unsubstituted alkyl, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkoxy, acyloxy, allyloxy, allyl, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, amide groups and imides Individually selected from a group of groups)

Examples of the alkyl group having 1 to 10 carbon atoms in PS 1 of Formula 1 include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n -Octyl, n-nonyl and n-decanyl groups. Examples of the substituted or unsubstituted aryl group in PS1 of Chemical Formula 1 include phenyl, o-hydroxyphenyl, p-hydroxyphenyl, o-methylphenyl, p-methylphenyl, β-naphthyl and p-chlorophenyl do.

On the other hand, for the alkyl group having 1 to 10 carbon atoms in PS2 of Formula 2, the same kind as mentioned above is used. As for the substituted aryl groups as well as the above examples, o-methoxyphenyl, p-methoxyphenol and 9-anthranyl groups can be used. R ⁸ or R ⁹ in PS 2 of Formula 2 may be connected to one of R ¹⁰ , R ¹¹ and R ¹² to form a closed ring.

When the above formula (1) of PS1 in R ¹ in the general formula 2 of the PS2 within R ⁷ is configured by a, or an unsubstituted substituted siloxy group, the group can be coupled to a substituted or unsubstituted siloxy group next to the repeating unit And a two-dimensional or three-dimensional structure is formed through the following (-Si-O-Si-) bond. Furthermore, R ¹ and R ⁷ composed of siloxy groups are linked to substituted or unsubstituted siloxy groups of other molecules besides the siloxy group next to the repeating unit and form a two-dimensional or three-dimensional structure as described above.

For the repeating units according to PS1 of Formula 1 and / or PS2 of Formula 2, Chemical Formulas 1 to 34 below are examples of the repeating units.

Compounds having a repeating unit according to PS1 of Chemical Formula 1 may be prepared by the method described below. In particular, trichlorophenylsilane is mixed with ethanol in a molar ratio of 1: 2 and the resulting mixture is reacted to give diethoxyphenylsilane. Hydroxychlorobenzene on the other hand is reacted with trimethylchlorosilane to give trimethylsilyloxychlorobenzene. The resulting trimethylsilyloxychlorobenzene is reacted with dimethoxyphenylsilane in the presence of metallic sodium to give condensed trimethylsilyloxyphenyldiethoxyphenylsilane through hydrolysis.

On the other hand, the composition having a repeating unit according to PS2 of the formula (2) can be prepared by the method disclosed in Japanese Patent Laid-Open No. H / 62-229136. In particular, the process uses a platinum catalyst to react a composition having an unsaturated bond formed by protecting the phenol with trimethylsilyl or alkylether mono-substituted dichlorosilane or mono-substituted diethoxysilane, and through hydrolysis Condensation reaction of the resulting reaction product.

Melt viscosity and melting point of the compound having a repeating unit according to PS2 of Formula 2 as well as the compound having a repeating unit according to PS1 of Formula 1 are dichlorosilane such as dimethyldichlorosilane, methylphenyldichlorosilane and diphenyldichlorosilane. The hydroxy group is protected by mixing with dichlorosilane with phenol, and the resulting mixture can be controlled by preparing the copolymer by the method in which the resulting mixture is condensed through hydrolysis.

For example, a polysiloxane resin having a high glass transition point can be obtained by copolymerizing dichlorosilane having a phenyl group such as phenylmethyldichlorosilane and diphenyldichlorosilane with dichlorosilane having a protected phenolic hydroxyl group. . In addition, a polysiloxane resin having a high glass transition point may be obtained by adding a phenyl group or a naphthyl group to R ^{1 of} Formula ¹ or R ⁷ of Formula 2.

Meanwhile, a polysiloxane resin having a low melt viscosity may be obtained by copolymerizing a repeating unit according to PS1 of Formula 1 and / or a repeating unit according to PS2 of Formula 2 with dimethylsiloxane. In addition, a polysiloxane resin having a low melt viscosity may be obtained by adding a methyl group or an ethyl group to R ^{1 of} Formula ¹ or R ⁷ of Formula 2. Usually, the obtained polysiloxane has a relatively small molecular weight, so that a polysiloxane resin having a low melt viscosity can be obtained without emulsifying with dimethylsiloxane.

Melting point and melt viscosity of the polysiloxane resin used for this invention can be suitably measured depending on the obtained resin composition and the shaping | molding method of the resin composition. For example, if the intended resin composition is a liquid, about 0.01 to 10 Pa · S is preferred when the melt viscosity of the polysiloxane resin is measured at the molding temperature. On the other hand, if the intended resin composition is a solid, the melt viscosity of the polysiloxane resin is preferably about 5 to 500 Pa · S when measured at the molding temperature.

300-50,000 are preferable and, as for the molecular weight of the said polysiloxane resin, 500-30,000 are more preferable. When the molecular weight is 300 or less, the heat resistance and thermal shock resistance of the polysiloxane resin are inferior. On the other hand, when said molecular weight exceeds 50,000, the moldability of polysiloxane resin will fall.

According to the present invention, it is also possible to mix a compound known as a curing agent for an epoxy compound, as well as the polysiloxane having a phenolic hydroxyl group in the side chain, as well as the component (b). Examples of such compounds include amines, acid anhydrides and phenols.

Specific examples of the amine include diethylene triamine, triethylene tetraamine, diethylamino propylamine, N-aminoethyl piperazine, benzyl dimethylamine, tris (dimethylaminomethyl) phenol, metaphenylene diamine, diaminodiphenyl Methane, diaminodiphenyl sulfone, polyamide resin (amine number: 200 to 350), dicyandiamide, boron trifluoride, monoethylamine, methane diamine, xylene diamine, bisaminopropyl tetraoxaspirodedecane adduct and ethyl Methylimidazole. Specific examples of the acid anhydride include phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride , Benzophenone tetracarboxylic anhydride, dichloro succinic anhydride and chloric anhydride.

Specific examples of such phenols include novolac phenol resins. In this case, the kind of novolak-type phenol resin can be used as long as it contains two or more phenolic hydroxyl groups in one molecule. For example, phenol novolak resins, cresol novolak resins, t-butylphenol novolak resins, nonylphenol novolak resins, phenol aralkyl resins and dicyclopentadienephenol novolak resins can be used. Among these phenolic resins, phenol novolak resins are preferred because of their mechanical strength and moldability.

Specific examples of phenol novolak resins include Shoolol BRG-555 (Showa High Polymer Co., Ltd. softening point: 68 ° C, 125 ° C melt viscosity: 2.4 Pa.S), Shool BRG-556 (Showa High Polymer Co.) Softening point: 1.8 Pa.S) at 80 ° C and 150 ° C Melon viscosity: 1.8 Pa.S), Shool BRG-558 (Softening point at Showa High Polymer Co., Ltd .: 97 Pa, 150 ° C: 6.2 Pa.S) , Barcam TD-2131 (Dainippon Ink Chemicals Inc. softening point: 80 Pa, 150 ℃ melt viscosity: 30 Pa.S), Bacam TD-2093 (Dainippon Ink Chemicals Inc. softening point: 100 ℃, 150 ℃ melt viscosity : 30 Pa · S). It is also possible to use phenolic resins having allyl groups such as SH-140A (Mitsubishi Petrochemical Co., Ltd.), SH-150A (Mitsubishi Petrochemical Co., Ltd.) and XPSF-4488 (Gunei Chemical Industry Co., Ltd.). have.

The mixing ratio of component (b) consisting of a polysiloxane resin which is a curing agent and has a phenolic hydroxyl group in the side chain and optionally the compound known as a curing agent for an epoxy resin is measured under the following conditions. That is, the total epoxy group resin constituting the component (a) and the component (b) is 5 to 90% by weight based on the total resin composition, and at the same time the epoxy group (EP) of the component (a) and the phenolic hydroxyl group in the component (b) ( The ratio between phOH) (EP / phOH) is 1 / 1.2 to 1 / 0.2.

When the total amount of the component (a) and the component (b) is less than 5% by weight, the flow rate of the resin composition is lowered, causing dislocation of the bed or movement of the bonding wire in the case of molding. On the other hand, when the total amount exceeds 90% by weight or more, the coefficient of thermal expansion of the cured product is high, and sufficient heat resistance is not obtained. Furthermore, when the ratio between the epoxy group of component (a) and the phenolic hydroxyl group in component (b) is outside the above range, the heat resistance of the cured product may be lowered, or the curing rate of the resin composition may be too low. It is difficult to shape the resin composition.

Moreover, it is preferable that the mixing ratio of the hardening agent which comprises (b) component is limited to 5-100 weight part per 100 weight part of (a) component under said conditions. When the mixing ratio of the component (b) is 5 parts by weight or less, it is difficult to obtain sufficient heat resistance or the melt viscosity of the resin composition becomes too high, resulting in poor moldability of the resin composition. On the other hand, when the mixing ratio of (b) component exceeds 100 weight part, the water absorption of hardened | cured material becomes too high and the reliability of a molded product will fall.

(C) Component composed of the inorganic filler of the resin composition according to the present invention, quartz glass, crystalline silica, fused silica, zircon, alumina, calcium silicate, barium sulfate, magnesite, clay, kaolin, talc, mica, glass fiber, Ceramic fibers, carbon silicate, nitrogen silicate, aluminum nitride, titanium white, calcium carbonate and gypsum can be used. Quartz glass, crystalline silica and fused silica are more preferred as inorganic fillers to obtain a resin composition exhibiting low moisture absorption and low melt viscosity. For crystalline silica and fused silica, two forms such as pulverized silica and spherical silica can be used by appropriately mixing them.

The mixing ratio of the inorganic filler is preferably 10 to 95% by weight, more preferably 40 to 90% by weight based on the total resin composition. If the above mixing ratio is 10% by weight or less, the thermal expansion coefficient of the cured material is too large to obtain sufficient thermal shock resistance. On the other hand, when the content exceeds 95% by weight, the fluidity of the resin composition is too low, causing the bed toilet seat occurs in the movement of the bonding wire or forming step.

If the resin composition of the present invention is used to seal a flip chip in which an IC or LSI is mounted directly on a substrate, the space between the substrate and the semiconductor element can be easily filled with the resin composition, which is preferable. Therefore, it is preferable that the maximum particle diameter as well as the average particle diameter of (c) component which comprises an inorganic filler are limited to a predetermined range. For example, 50 micrometers or less are preferable and, as for the largest particle diameter of an inorganic filler, 30 micrometers or less are more preferable. Since the height of the space between the semiconductor and the substrate is usually between 50 μm and 150 μm, a resin composition containing an inorganic filler having a maximum particle diameter of 50 μm or more cannot be injected therebetween so that the resin composition is filled non-uniformly and thus incomplete insulators. Create a package crack, and cause package cracking under some circumstances. On the other hand, the average particle diameter of the inorganic filler is preferably in the range of 0.5 µm to 50 µm. When the average particle diameter of an inorganic filler is 0.5 micrometer or less, the viscosity of a resin composition will increase greatly, the speed | rate which fills a resin composition will decrease, and work efficiency will fall. On the other hand, when the average particle diameter of an inorganic filler exceeds 50 micrometers, filling property will fall to the space between a semiconductor and a board | substrate.

The resin composition of the present invention may include a curing catalyst to promote a curing reaction between the component (a) composed of an epoxy compound and the component (b) composed of a curing agent. For example, base compounds, organic phosphine compounds, imidazole compounds or derivatives thereof, DBU (1,8-diazabicyclo (5,4,0) undecene-7) or salts of DBU can be used.

Examples of basic compounds include tertiary amines such as benzyl dimethylamine, α-methylbenzyldimethylamine, dimethylaminomethyl phenol, tris-dimethylaminomethyl phenol complexes and salts thereof.

Examples of organic phosphines include trimethyl phosphine, triethyl phosphine, tributyl phosphine, triphenyl phosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, methyldiphenyl phosphine, dibutyl Phenyl phosphine, tricyclohexyl phosphine, 1,2-bis (diphenylphosphine) ethane and bis (diphenylphosphine) methane.

Examples of imidazole compounds include imidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4methyl. Midazole and 2-heptadecylimidazole.

Examples of phenol salts of DBU include SA-853 (sanapro).

As a curing catalyst, Novacure HX-3722, HX-3721, HX-3748, HX-3741, HX-3742 and HX-3088 (Asahi Chemical Industry Co., Ltd.) or MY-25 (Ajinomoto Co. It is possible to use a potential catalyst such as).

The mixing ratio of the curing catalyst in the resin composition according to the present invention is preferably between 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the component (a) composed of the epoxy compound and the component (b) composed of the curing agent. When the content of the curing agent is 0.1 parts by weight or less, the curing of the resin composition occurs insufficiently, so that the heat resistance and the like fall in the encapsulated resin-molded product which is the resulting cured product. On the other hand, when the content of the curing catalyst exceeds 10 parts by weight, the heat resistance, moisture resistance and electrical properties of the resulting cured product is inferior. A preferred mixing ratio of the curing catalyst is 0.5 to 5 parts by weight per 100 parts by weight of the total amount of the component (a) and the component (b).

The resin composition according to the present invention includes an adhesion-promoting agent to improve adhesion of the resin composition after curing and curing the substrate. Examples of the adhesion-promoting agent include thermosetting resins such as amino resins, polyurethane resins and unsaturated polyesters; Isocyanate compounds; Rubber; Silane compounds and metallic chelate compounds.

Among the above compounds, the metallic chelate compound has an effect of improving adhesion to semiconductor elements as well as water resistance of the cured resin. Examples of metallic chelate compounds include Zr chelates, Ti chelates and Al chelates.

Specific examples of Zr chelate include tetrakisacetylacetonato zirconium, monobutoxytrisacetylacetonato zirconium, dibutoxybisacetylacetonato zirconium, tributoxyacetylacetonato zirconium, tetrakisethylacetylacetate zirconium, butoxytrisethylacetyl Acetate zirconium, tributoxy monoethyl acetylacetate zirconium, tetrakisethyl lactate zirconium, dibutoxybisethyl lactate zirconium, bisacetylacetonato bisethylacetylacetonato zirconium, monoacetylacetonato trisethylacetylacetonato zirconium, mono Acetylacetonato bisethylacetylacetonato zirconium and bisacetylacetonatobisethyl lactonato zirconium. For Ti chelates and Al chelates, compounds having ligands such as β-diketones, hydroxycarboxylic acids, ketoesters, ketoalcohols and glycols are used.

When a thermosetting resin or rubber is used as the adhesion-promoting agent in the resin composition of the present invention, the mixing ratio of the thermosetting resin or rubber is preferably 0.2 to 20% by weight based on the resin composition. If the mixing ratio is 0.2% by weight or less, a sufficient effect of the adhesion-promoting agent cannot be obtained. On the other hand, when the mixing ratio exceeds 20% by weight, the absorption of water of the cured material becomes too large or the heat resistance of the molded product is inferior. When the metallic chelate is used as the adhesion-promoting agent in the resin composition of the present invention, the mixing ratio of the metallic chelate is preferably 0.01 to 5% by weight based on the resin composition. If the said mixing ratio is less than 0.01 weight%, sufficient effect of a metallic chelate will not be acquired. On the other hand, when the mixing ratio exceeds 5% by weight, the electrical insulation of the molded product is inferior when the intermediate wire of the semiconductor element is corroded by ionic impurities or when the resin composition is used in the resin-encapsulated semiconductor device.

Also flame retardants such as antimony trioxide, phosphorus compounds and halogen-containing compounds; Release agents such as natural waxes, synthetic waxes, linear fatty acids or metal salts thereof, acid amides, esters and paraffins; Pigments such as carbon black and titanium dioxide; And other additives such as surface treating agents such as silane binders may be added to the resin composition of the present invention. Moreover, stress-reducing agents such as silicone rubber, silicone oil, various kinds of plastic powder, engineering plastic powder, ABS resin powder and MBS resin powder can be added to the resin composition of the present invention.

There is a high possibility that the component (a) composed of an epoxy resin and component (b) composed of a polysiloxane resin may be contaminated with impurities such as alkali metal ions or halogen ions in the resin composition of the present invention. Also unreacted alkyl halides, aryl halides or chlorosilanes may remain in the resin composition or halide compounds may be produced in side reactions. When the resin composition containing the above impurity is used for sealing the semiconductor element, the intermediate wire may be cut by corrosion or deterioration of moisture resistance of the aluminum wire. Therefore, the removal of impurities from the resin composition is strongly required.

The resin composition containing the impurity is dissolved in a water-soluble polar solvent such as N-methylpyrrolidone, N, N-dimethylacetoamide, tetrahydrofuran (THF), acetone or ethanol to form a resin solution, The impurities can be easily removed by immersing in an aqueous solution of dilute organic acid such as water or oxalic acid, and the resulting precipitated polymer is collected by filtration. In addition, the resin composition containing the impurity is dissolved in an organic solvent which cannot be mixed with water such as diethyl ether, ethyl acetate or chlorine-based organic solvent, and water or dilute organic acid aqueous solution is added to the resin solution, and the resulting mixture is mixed. After the solution is shaken and left, the mixed solution may be separated into an organic solvent phase and an aqueous solution phase, an organic solvent phase may be collected, and the impurities may be removed by a process of removing the impurities.

The above process can be repeated until the concentration of alkali metal or halogen impurities is reduced to a predetermined acceptable concentration. That is, the concentration of the alkali metal contained as impurities in the synthesized resin is preferably limited to 50 ppm or less, particularly preferably 20 ppm or less, particularly preferably 5 ppm or less. On the other hand, the concentration of the halogen compound contained as impurities in the resin is preferably 500 ppm or less, particularly preferably 300 ppm or less, and particularly preferably 100 ppm.

If an LC or LSI is mounted directly to the substrate, the sealed material requires liquid. It is possible to obtain a liquid resin composition having high reliability by combining the component (a) having a low melting point with the component (b) having a low melting point according to the present invention. For example, when the (a) component such as liquid or oil at room temperature and the (b) component such as liquid or oil at room temperature are combined, a liquid resin composition can be obtained. If the liquid resin composition is used as a liquid sealing material, the viscosity of the resin composition is preferably 5 Pa · S or less at a temperature of 100 ° C. When the viscosity of the said resin composition exceeds 5 Pa * S, it is difficult to fill a space between a board | substrate and a semiconductor element, and it takes a long time to fill a resin composition. Moreover, when the viscosity of the resin composition exceeds 5 Pa.S, an unfilled portion can be formed in the resin-encapsulated semiconductor device, and the semiconductor device can be easily separated from the substrate as well as the incomplete insulation of the device is exhibited. . Therefore, 20 Pa.S or less is preferable and, as for the preferable viscosity of a resin composition at room temperature, 10 Pa.S or less is especially preferable. Although the viscosity of the resin composition is limited to the lower limit, when the viscosity of the resin composition becomes too low, the viscosity of the resin composition is 1 mPa · S or more at a temperature of 100 ° C. because burrs occur on the cured product.

An organic solvent or reactive diluent may be used to adjust the viscosity of the resin composition of the present invention as desired. Non-limiting examples of organic solvents that can be used in the above cases include ketone type solvents such as cyclohexanone, acetone, methyl ethyl ketone and methyl isobutyl ketone; Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate; And ester solvents such as ethyl acetate, butyl acetate, isoamyl acetate and ethyl lactate. The solvent may be used singly or in mixture of two or more kinds.

For reactive diluents, low molecular weight compounds having epoxy monomers or crosslinkable unsaturated carbon-carbon bonds can be used. Specific examples of epoxy monomers include glycidol, 1,2,7,8-diepoxy octane, 1,4-butanediol glycidyl ether, cyclohexane oxide, 2,3-epoxynorbornene, 4-vinylcyclohexane On monooxide, limonene oxide, cyclododecane oxide, 4-vinylcyclohexane dioxide, 1,2,5,6-diepoxycyclooctane, cyclooctane oxide, pinene oxide, 1,2-epoxy -5,9-cyclododecadiene, 1,2-epoxyethylbenzene, stilbene oxide, glycidylphenyl ether, p-tert-butylphenylglycidyl ether, 2,3-epoxypropyl-p-meth Oxyphenyl ether and o-biphenylglycidyl ether.

Specific examples of low molecular weight compounds having a crosslinkable unsaturated carbon-carbon bond include diethylene glycol diallyl ether, N, N'-methylenebisacryl amide, diallyl chlordate, diallyl hexahydrophthalate, triallyl trimellitate, 4-allyl-2,6-di-tert-butylphenol, diallyl isophthalate, diallyl phthalate, divinylbenzene, styrene, allylbenzene, divinylsulfone, allylbenzene carboxylate, 4-vinylphenyl, triallyl -1,3,5-benzene tricarboxylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonyl Phenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydroperfuryloxyhexanolide acrylate, ε-caprolactone adduct acrylate of 1,3-dioxane alcohol, 1,3 Dioxolane acrylate, hexanediol acrylate, neopentylglycol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalic neopentyl glycol diacrylate, Neopentylglycol adipate diacrylate, hydroxypivalic neopentylglycol ε-caprolactone adduct diacrylate, 2 (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5- Ethyl-1,3-dioxane diacrylate, tricyclodecanedimethylol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, trimethylolpropane triacrylate, propionic dipentaerythritol tri Acrylate, propionic dipentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, propionic dipentaerythritol penta Additional methacrylate, dipentaerythritol hexaacrylate and dipentaerythritol hexaacrylate ε- caprolactone, water.

If the compound having a crosslinkable unsaturated carbon-carbon bond can be used as a reactive diluent, a peroxide or azo compound can be used as a curing catalyst.

Examples of peroxides are diallyl peroxide, peroxide ester, diacyl peroxide, hydroperoxide, ketone peroxide and peroxyketal. Specific examples of the above include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, acetyl peroxide, methylethylketone peroxide, cyclohexanone peroxane Seed, bis (1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, t-butylhydroperoxide, p-mentanehydroperoxide, cumenehydroperoxide, 2,5-dimethylhexyl-2,5- Dihydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylethyloxy) hexane, 2,5-dimethylhexyl-2,5-di (Peroxybenzoate), t-butylperbenzoate, t-butylperacetate, t-butylperoctoate, t-butylperoxyisobutylate and di-t-butylperphthalate.

For azo compounds, azobisisobutylonitrile, 2,2'-azobispropane, m, m'-azoisostyrene or hydrazone can be used.

The resin composition of the present invention can be prepared as follows. That is, the whole components are thoroughly mixed internally using a Henschel mixer, melt-mixed using a hot roll or dual-axis compressor, the resulting melt is cooled to room temperature, and the hammer Grind using a mill mill. If the resin composition used is a liquid, the grinding treatment can be omitted.

In the method of sealing a semiconductor element with the resin composition of the present invention, a low pressure transfer molding usually used can be used. However, the sealing method is not limited to the above transfer molding, and other sealing methods such as compression molding, injection molding, casting molding or potting may be used to seal the semiconductor device. The term "sealing" (or encapsulation) as used above includes the one-side sealing in which the resin layer is sandwiched between the semiconductor element and the substrate. Thermal sealing after sealing is preferably carried out at a temperature of 150 ℃ or more. The type and size of the semiconductor element sealed with the cured material of the resin composition according to the present invention is not limited.

The resin composition according to the present invention can be used not only for sealing semiconductor elements but also for producing molded products having excellent heat resistance.

MEANS TO SOLVE THE PROBLEM The present inventor uses the polysiloxane resin which has a phenolic hydroxyl group in a side chain as a hardening | curing agent with respect to an epoxy compound, and obtains the resin composition suitable for sealing, and can overcome all the conventional problems, and can achieve this invention. I knew that. That is, in the present invention, the resin composition composed of a curing agent comprising an epoxy resin and a polysiloxane resin having a phenolic hydroxyl group in the side chain thereof reduces the stress that can be applied to the cured product without increasing the water absorption of the cured product. You can. Therefore, if the resin-sealed semiconductor device is manufactured using the resin composition according to the present invention, the moisture resistance of the device is not lowered. In addition, the resin-encapsulated semiconductor device obtained in accordance with the present invention is excellent in adhesion and thermal shock resistance. In addition, the desired liquid polysiloxane as well as the solid polysiloxane can be obtained by appropriately selecting the molecular weight and structure of the polysiloxane resin having a phenolic hydroxyl group in the side chain to appropriately adjust the melting temperature and viscosity of the resin composition. Thus, it is possible to obtain a liquid resin composition which is excellent in reliability and suitable for surface-mounting, such as in the manufacture of flip chips, CSP (chip size package) or BGA (ball grid array).

In addition, since the phenol in the polysiloxane resin reacts with the epoxy compound according to the resin composition of the present invention, when the silicone oil is added to the resin composition, it can prevent the silicone oil from seeping and staining the surface of the metal mold. Therefore, it is possible in the present invention to provide a resin composition having excellent properties suitable for sealing a semiconductor element.

The invention will also be described with reference to the following examples.

The resin composition is prepared as follows.

First, the inorganic filler is treated with the surface treatment agent in the Henschel mixer. And an epoxy compound, a polysiloxane resin, a curing catalyst, and a hardening | curing agent are mixed together according to the compounding ratio of Table 1 below. The mixture is then thermally fused and mixed homogeneously, cooled and comminuted. And, all the above components are mixed, heated to 60 to 160 ° to knead using a hot roll, to cool the resulting kneaded material, and various kinds of shown in Examples 1 to 3 and Comparative Example 1 It is ground to obtain a resin composition.

Example Comparative Example One 2 3 One (a) component A117.0 A26.7 A36.0 A27.7 (b) ingredients Polysiloxane resin B19.6 B22.5 B33.7 - Other curing agents - D12.4 D11.9 D13.9 (c) ingredient inorganic filler 70 85 85 85 Curing catalyst 0.2 0.2 0.2 0.2 Release agent 0.5 0.5 0.5 0.5 Pigment 0.4 0.4 0.4 0.4 Surface treatment agent 0.3 0.3 0.3 0.3 resist 2.0 2.0 2.0 2.0 Reactive diluent - - - -

The component (a) composed of the epoxy compounds A1 to A3 disclosed in Table 1 above represents the following compounds.

A1: o-cresol novolac epoxy resin (epoxy value: 197)

A2: Bisphenol A epoxy resin (epoxy number: 190)

A3: biphenyl type epoxy resin (epoxy number: 191)

The polysiloxane resins B1, B2 and B3 added to the component (b) composed of a curing agent each represent a resin having a repeating unit according to the above compounds (1), (9) and (18). The weight average molecular weight, softening point and phenol value of each polysiloxane resin are summarized in Table 2 below.

Repeat unit Weight average molecular weight Softening point / ℃ Phenolic Value B1 Compound (1) 4000 70 115 B2 Compound (9) 3500 50 256 B3 Compound (18) 5000 65 287

Curing agent D1 other than the polysiloxane resin represents the following compound.

D1: phenol novolak resin (phenol number: 104)

Other components used are as follows.

Reactive Diluent: 1,2-Epoxy-3-phenoxypropane

Curing Catalyst: Triphenyl Phosphine

Release Agent: Carnauba Wax

Pigment: Carbon Black

Flame Retardant: Antimony Trioxide

Inorganic filler: Cl fused silica powder (spherical; average particle diameter: 20 mu m; maximum particle diameter: 75 mu m)

Surface treatment agent: γ-glycidoxypropyltrimethoxy silane (A-187, Nippon Unicar Co., Ltd.)

In addition, the following compounds used as components (a), (b), (c) and other predetermined components are added, and the resulting mixture is prepared from Examples 4, 5 and 6 and Comparative Examples 2 and 3 and It is processed by the method described below to prepare a resin composition.

(a) Component:

A4: bisphenol F-type epoxy resin (epoxy number: 170)

A5: (3 ′, 4′-epoxycyclohexylmethyl) -3,4-epoxydicyclohexane carboxylate (epoxy value: 126)

(b) Ingredients:

B4: copolymer of siloxane and dimethyl siloxane having repeating units according to compound (27) (copolymerization ratio = 1: 5);

Weight average molecular weight: 800

B5: copolymers of siloxane and dimethyl siloxane having repeating units according to compound (11) (copolymerization ratio = 1: 8);

Weight average molecular weight: 1,200

B6: copolymers of siloxane and dimethyl siloxane having repeating units according to compound (27) (copolymerization ratio = 1: 2);

Weight average molecular weight: 550

The components B4, B5 and B6 are liquid at room temperature.

Other curing agents:

D2: Methylhexahydrophthalic anhydride

D3: 3,3'-diallyl-4,4'-dihydroxy diphenyl methane

(c) Ingredients:

C2: silica (average particle diameter = 2.7 mu m; maximum particle diameter = 30 mu m)

C3: silica (average particle diameter = 5.1 mu m; maximum particle diameter = 30 mu m)

C4: silica (average particle diameter = 4.1 mu m; maximum particle diameter = 30 mu m)

C5: silica (average particle diameter = 52 mu m; maximum particle diameter = 100 mu m)

Curing catalyst: Novacure HX3088 from Asahi Chemical Industry Co., Ltd.

Reactive Diluent: Phenylglycidyl Ether

Pigment: Carbon Black

Dye: Black Dye

(Example 4)

(a) Component: A4 20.4 parts

(b) Component: B4 10.7 parts by weight

Other Curing Agents: D2 16.0 parts by weight

(c) Component: C2 50.0 parts by weight

Curing catalyst: 2.5 parts by weight

Pigment: 0.4 part by weight

First, (a) component, (b) component, (c) component, and a pigment are mixed together and knead | mixed by the rotary kneader (Shinky Co., Ltd .; HX201), and a mixture is obtained. Then, a curing catalyst is added to the mixture, and the resulting mixture is kneaded again using the above kneader to obtain a resin composition. The resin composition thus obtained is a liquid at room temperature, the viscosity of the resin composition is 3 Pa · S at room temperature, and 0.2 Pa · S at a temperature of 100 ° C.

(Example 5)

(a) Component: A4 21.8 parts by weight

(b) Component: B5 10.8 parts by weight

Other Curing Agents: D3 14.5 parts by weight

(c) Component: C2 50.0 parts by weight

Curing catalyst: 2.5 parts by weight

Dye: 0.4 parts by weight

First, (a) component, (b) component, (c) component, and dye are mixed together and knead | mixed by the three-roll mill to obtain a mixture. Then, a curing catalyst is added to the mixture, and the resulting mixture is kneaded again using the above mill to obtain a resin composition. The resin composition thus obtained is a liquid at room temperature, the viscosity of the resin composition is 7 Pa · S at room temperature, and 0.8 Pa · S at a temperature of 100 ° C.

(Example 6)

(a) Component: A5 14.6 parts by weight

(b) Component: B6 8.6 parts by weight

Other Curing Agents: D3 12.2 parts by weight

(c) Component: C4 60.0 parts by weight

4.0 parts by weight of reactive diluent

Curing catalyst: 0.2 part by weight

Dye: 0.4 parts by weight

First, (a) component, (b) component, (c) component, a reactive diluent, and dye are mixed together and knead | mixed by a 3-roll mill and a mixture is obtained. Then, a curing catalyst is added to the mixture, and the resulting mixture is kneaded again using the above mill to obtain a resin composition. The resin composition thus obtained is a liquid at room temperature, the viscosity of the resin composition is 6 Pa · S at room temperature, and 0.6 Pa · S at a temperature of 100 ° C.

(Comparative Example 2)

(a) Component: A4 40.8 parts by weight

(b) Component: B4 21.4 parts

Other Curing Agents: D2 32.0 parts by weight

(c) Component: 0.0 parts by weight

Curing catalyst: 5.0 parts by weight

Pigment: 0.8 parts by weight

First, (a) component, (b) component, and a pigment are mixed together and knead | mixed with a rotary kneader (Shinky Co., Ltd .; HX201), and a mixture is obtained. Then, a curing catalyst is added to the mixture, and the resulting mixture is kneaded again using the above kneader to obtain a resin composition. The resin composition thus obtained is a liquid at room temperature, the viscosity of the resin composition is 0.3 Pa · S at room temperature, and 0.01 Pa · S at a temperature of 100 ° C.

(Comparative Example 3)

(a) Component: A4 26.5 parts by weight

(b) Component: 0.0 parts by weight

Other Curing Agents: D3 20.6 parts by weight

(c) Component: C3 50.0 parts by weight

Curing catalyst: 2.5 parts by weight

Dye: 0.4 parts by weight

First, (a) component, a hardening | curing agent, (c) component, and dye are mixed together, it knead | mixes by a 3-roll mill and a mixture is obtained. Then, a curing catalyst is added to the mixture, and the resulting mixture is kneaded again using the above mill to obtain a resin composition. The resin composition thus obtained is a liquid at room temperature, the viscosity of the resin composition is 36 Pa · S at room temperature, and 4.4 Pa · S at a temperature of 100 ° C.

(Sample)

(a) Component: A4 20.4 parts

(b) Component: B4 10.7 parts by weight

Other Curing Agents: D3 16.0 parts by weight

(c) Component: C5 50.0 parts by weight

Curing catalyst: 2.5 parts by weight

Pigment: 0.4 part by weight

First, (a) component, (b) component, (c) component, and a pigment are mixed together and knead | mixed by the rotary kneader (Shinky Co., Ltd .; HX201), and a mixture is obtained. Then, a curing catalyst is added to the mixture, and the resulting mixture is kneaded again using the above kneading apparatus to obtain a resin composition. The resin composition thus obtained is a liquid at room temperature, the viscosity of the resin composition is 2.6 Pa · S at room temperature, and 0.1 Pa · S at a temperature of 100 ° C.

The characteristics of the resin composition thus obtained were evaluated as follows. First, the following evaluation tests were carried out in the resin compositions of Examples 1 to 3 and Comparative Example 1.

(1) A test piece (8 mm x 8 mm x 4 mm) of each resin composition was prepared by transfer molding for 3 minutes under the conditions of 175 占 폚, and the resulting shaping pieces were post-cured at 220 占 폚 for 4 hours. Flexural module, flexural strength, coefficient of thermal expansion, glass transition point and water absorption are measured on each specimen. In addition, each resin composition was molded on the frame material (42 alloys) to prepare a test piece, and the adhesion strength was measured on each test piece in the pulling direction. The results obtained in this test are described in Table 3 below.

(2) In order to investigate the moisture proof property of the said resin composition, the following PCT test is implemented. That is, each resin composition is used to manufacture a sealed test apparatus (8 mm x 8 mm) according to the TQFP package. Then, the test apparatus is subjected to post-curing at 220 ℃ for 4 hours or more to manufacture a resin-encapsulated semiconductor device. Each resin-encapsulated semiconductor device was left at a relative humidity of 85% and a temperature of 85 ° C. for 72 hours and subjected to a moisture absorption treatment. The resin-molded semiconductor device is then exposed to a fluorocarbon vapor atmosphere heated to 125 ° C. for 1 minute to investigate the rate of cracking in the package at this stage. In addition, the resin-encapsulated semiconductor device is left in saturated water vapor heated at 127 ° C. for a predetermined time, and the defect ratio is examined (defects due to leakage and defects due to initiation) to evaluate moisture resistance.

(3) In order to investigate the thermal shock resistance of the said resin composition, the following TCT test is implemented. That is, each resin composition can be used for the manufacture of a large test apparatus (8 mm x 8 mm) sealed according to the TQFP package for thermal shock resistance. Then, the test apparatus is post-cured at a temperature of 220 ° C. for 4 hours to manufacture a resin-encapsulated semiconductor device. Each resin-sealed semiconductor device performs a thermal shock cycle, and one cycle consists of -65 deg. C / room temperature / 150 deg. The cycle is repeated 50 to 400 times to determine the defect rate by searching the performance characteristics of the device.

The results of the PCT and TCT tests are summarized in Table 4 below.

Example Comparative Example One 2 3 One Yoggo module (GPa) 16 18 19 22 Yaw strength (MPa) 154 160 157 128 Coefficient of Thermal Expansion (1 / deg) × 10 ⁵ 1.5 1.2 1.2 1.2 Glass transition point (℃) 132 124 102 122 Water absorption (% by weight) 0.24 0.23 0.21 0.23 Adhesion Strength (MPa) 17 15 16 11

Example Comparative Example One 2 3 One PCT test The percentage of cracks generated after the hygroscopic test 0/20 0/20 0/20 0/20 Defect Ratio at Run 100 hours 0/20 0/20 0/20 0/20 200 hours 0/20 0/20 0/20 0/20 300 hours 0/20 0/20 0/20 1/20 400 hours 0/20 0/20 0/20 2/20 500 hours 0/20 0/20 0/20 5/20 TCT Exam 50 cycles 0/20 0/20 0/20 0/20 100 cycles 0/20 0/20 0/20 0/20 200 cycles 0/20 0/20 0/20 1/20 300 cycles 0/20 0/20 0/20 4/20 400 cycles 0/20 0/20 0/20 5/20

As can be seen in Table 3, the test piece of the resin composition according to the present invention (Examples 1 to 3) shows excellent adhesion strength and flexural strength compared to that of Comparative Example 1. In particular, it can be seen that the adhesion strength was improved by adding a curing agent containing a polysiloxane resin.

As can be seen from Table 4, in the resin-encapsulated semiconductor device according to Examples 1 to 3 of the present invention, no defects were found even when the resin-molded semiconductor device was left under high temperature and high humidity conditions for 500 hours. This shows the excellent moisture-proof property of the resin-sealed semiconductor device according to the present invention. On the other hand, in the case of the resin-encapsulated semiconductor device according to Comparative Example 1 in which a resin composition containing no polysiloxane having phenolic hydroxyl groups in the side chain was sealed, in several devices after 300 hours of testing A defect was found, one quarter of the devices were found after 500 hours of testing.

As can be seen from the results of the TCT test described in Table 4 above, even in a resin-molded semiconductor device according to an embodiment of the present invention, even when the resin-encapsulated semiconductor device undergoes 400 repeated thermal shock cycles, No specific defects were found. On the other hand, in the case of the resin-encapsulated semiconductor device according to Comparative Example 1, defects were found in several devices after 200 cycles of impact, and one quarter of the devices showed defects after 400 cycles of impact. As described above, the cured product of the resin composition according to the present invention shows excellent results in all respects including mechanical strength, which indicates that the resin-encapsulated semiconductor device sealed with the resin composition according to the present invention has high moisture resistance and thermal shock resistance. It can be seen that represents.

Therefore, staining due to leakage of polysiloxane does not adhere to the inside of the metal mold after molding of the resin composition according to Examples 1 to 3.

The liquid resin compositions obtained in Examples 4, 5, and 6 as well as Comparative Examples 2 and 3 and the samples were each molded into sheets having a thickness of 4 mm, and cured by heating at a temperature of 180 ° C. for 5 hours. 4 mm x 10 mm x 100 mm). Then, the yaw module and the yaw strength of the test piece are measured. At the same time, the coefficient of thermal expansion, glass transition point and water absorption of the test piece are measured after cutting the cured test piece to a suitable length. In addition, each resin composition is coated on a substrate formed of a BT resin, and a silicon wafer (3 mm x 3 mm) is placed on the substrate. The resin composition coated in the above manner is heated to 150 ° C. for 1 hour to cure the resin composition and prepare a test piece. Then, the adhesion strength in the compression direction is measured for each test piece. The results obtained by the test piece are shown in Table 5 below.

A resin-encapsulated semiconductor device can be produced as follows using the resin compositions obtained in Examples 4, 5 and 6 as well as Comparative Examples 2 and 3 and samples. First, a soul bump is formed in the pad portion of the LSI flip chip (10 mm x 10 mm; bump height: 50 mu m). The resulting chip is mounted on a circuit board and fixed by thermal compression coupling. On the other hand, the resin compositions obtained in Examples 4, 5 and 6 as well as Comparative Examples 2 and 3 and the samples were filled in an injector, respectively, and injected into one side of the chip heated on a hot plate heated to 60 ° C. The resin composition thus injected is injected into the space between the chip and the substrate by capillary action. In the case of the resin composition according to Examples 4 to 6 and Comparative Example 2, the resin composition was filled in 5 minutes, and in the case of the resin composition according to Comparative Example 3 and the sample, it took 12 minutes to fill, It takes 30 minutes. After filling the resin composition, the resin composition is cured by heating in an oven at 150 ° C. for 1 hour to obtain a flip chip semiconductor device.

And the flip chip semiconductor device thus obtained is evaluated by PCT and TCT tests conducted in the same manner as in the case of Examples 1-3. The results obtained are summarized in Table 6 below.

Example Comparative Example Sample 4 5 6 2 3 Yoggo module (GPa) 8.4 7.3 9.2 2.6 11.3 8.2 Yaw strength (MPa) 144 150 136 102 138 140 Coefficient of Thermal Expansion (1 / deg) × 10 ⁵ 3.3 3.2 2.8 7.2 3.4 3.5 Glass transition point (℃) 112 103 110 111 125 110 Water absorption (% by weight) 0.56 0.52 0.46 1.10 0.58 0.57 Adhesion Strength (MPa) 35 32 40 23 14 24

Example Comparative Example Sample 4 5 6 2 3 PCT test Rate of cracks generated after hygroscopic test 0/20 0/20 0/20 3/20 0/20 20/20 Defect Ratio at Run 100 hours 0/20 0/20 0/20 5/20 2/20 - 200 hours 0/20 0/20 0/20 12/20 2/20 - 300 hours 0/20 0/20 0/20 20/20 2/20 - 400 hours 0/20 0/20 0/20 - 2/20 - 500 hours 0/20 0/20 0/20 - 3/20 - TCT Exam 0 cycle (after curing) 0/20 0/20 0/20 5/20 5/20 20/20 50 cycles 0/20 0/20 0/20 20/20 8/20 - 100 cycles 0/20 0/20 0/20 - 13/20 - 200 cycles 0/20 0/20 0/20 - 20/20 - 200 cycles 0/20 0/20 0/20 - - - 400 cycles 0/20 0/20 0/20 - - -

As can be seen in Table 5, the test piece of the resin composition (Examples 4, 5 and 6) according to the present invention shows excellent bending strength and adhesion strength compared to that of the comparative example. If the quantification of the filler is from the comparison of the curvature module between the resin composition of Example 5 and the resin composition of Comparative Example 3, if the stress in the test piece of Example 5 is greatly reduced, the example containing polysiloxane as component (b) The resin composition of 5 shows a low curvature module compared with that of Comparative Example 3.

As can be seen from the results shown in Table 6, even if the resin-molded semiconductor device is under high temperature and high humidity conditions for 500 hours, defects are not found in the resin-encapsulated semiconductor device according to Examples 4 and 5 of the present invention. The resin-sealed semiconductor device of the present invention has excellent moisture resistance. On the other hand, in the case of the resin-encapsulated semiconductor device according to Comparative Example 2 in which the semiconductor device was sealed using a resin composition containing no inorganic filler, defects were found in all the devices after 300 hours of testing. In the case of a sample using a resin composition containing an inorganic filler having a large particle diameter, the resin composition could not be sufficiently injected therebetween, and defects were found in all devices immediately after curing of the resin composition.

As can be seen from the results of the TCT test of Table 6, it was found that no defects were found in the resin-molded semiconductor device according to the embodiment of the present invention after 400 cycles of impact, thereby exhibiting excellent thermal shock resistance. On the other hand, in the case of the resin-encapsulated semiconductor device according to Comparative Example 2 containing no inorganic filler, defects were found in several devices after 50 cycles of impact, and did not include component (b) composed of polysiloxane. In the case of the resin-encapsulated semiconductor device according to Comparative Example 3, a bond was found in several devices after 200 cycles of impact. In addition, in the case of the resin-encapsulated semiconductor device according to the sample to which the inorganic filler of large particle size is added, it can be found that the function deteriorates in all the devices immediately after curing of the resin composition.

As mentioned above, the liquid resin composition is possible in the present invention by appropriately selecting the mixing ratio and type of the components used. When the liquid resin composition is used, the filling time is shortened, and at the same time, a flip chip type semiconductor device having excellent moisture resistance and thermal shock resistance as described above is obtained. It is also possible to use the liquid resin composition of the present invention as a potting resin or an adhesive.

1 is a cross-sectional view showing an example of a resin-enclosed semiconductor device of the present invention. According to Fig. 1, in the resin-encapsulated semiconductor device 10 of the present invention, a semiconductor element 1 is mounted on a substrate 2, and a bonding pad 3 formed on the surface of the semiconductor element 1 is a bonding wire. It is electrically connected to the lead play 4 via (5). The structure is entirely sealed in the resin layer 6 composed of the cured material of the resin composition of the present invention.

The resin-encapsulated semiconductor device 10 of the present invention manufactured by the above method is excellent in heat resistance, thermal shock resistance and moisture resistance as mentioned above, and at the same time does not cause a problem that a specific component leaks out of the surface, and thus the appearance is not damaged. Do not.

2 is a cross-sectional view showing another example of the resin-sealed semiconductor device of the present invention. In the case of the semiconductor device shown in FIG. 2, the semiconductor chip 24 is mounted on the surface of the substrate 21 in a face-down style via bumps 23. The resin layer 22 composed of the cured material of the resin composition according to the present invention is sandwiched in the space between the substrate 21 and the semiconductor chip 24.

The flip chip type semiconductor device shown in FIG. 2 can be manufactured by injecting a resin composition into a space formed between a substrate and a semiconductor chip by using a capillary phenomenon or by applying pressure. One example of the manufacturing method is shown schematically in FIG. 3. Since the gap between the substrate 21 and the semiconductor chip 24 is smaller than 50 to 150 mu m, the resin composition 25 filled above requires low viscosity. When the resin composition of the present invention is a liquid, the resin composition can be easily introduced into the space between the substrate 21 and the semiconductor chip 24 as shown in Fig. 3, so that the resin composition of the present invention is a flip chip type semiconductor. It is particularly suitable for use in the manufacture of the device.

As described above, according to the present invention, it is possible to provide a resin composition having low hygroscopicity and excellent moldability and heat resistance. In addition, it can be used to seal the semiconductor element with the cured material of the resin composition according to the present invention, it is possible to provide a resin-encapsulated semiconductor device excellent in heat resistance, thermal shock resistance and moisture resistance. Therefore, the present invention is very useful from an industrial point of view.

Additional advantages and modifications may be readily apparent to those skilled in the art. Therefore, in its broader aspects the invention is not limited to the description and representative embodiments. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the claims appended hereto.

Claims (19)

A resin composition comprising (a) an epoxy compound, (b) a curing agent containing a polysiloxane resin having a phenolic hydroxyl group in the side chain, and (c) an inorganic filler. The method of claim 1, The viscosity of the said resin composition is 5 Pa * S or less at the temperature of 100 degreeC, The resin composition characterized by the above-mentioned. The method of claim 1, Resin composition characterized in that the quantification of the component (c) composed of the inorganic filler is 10 to 95% by weight based on the total resin composition. The method of claim 3, wherein Resin composition characterized in that the quantification of the component (c) composed of the inorganic filler is 40 to 90% by weight based on the total resin composition. The method of claim 1, The total amount of the component (a) composed of the epoxy resin and the component (b) composed of the curing agent is 5 to 90% by weight based on the total resin composition, and at the same time the epoxy group (EP) of the component (a) and the phenolic in the component (b) The ratio (EP / phOH) between hydroxyl groups (phOH) is between 1 / 1.2 and 1 / 0.2, The resin composition characterized by the above-mentioned. The method of claim 1, The maximum particle diameter of (c) component comprised with the said inorganic filler is 50 micrometers or less, and the average particle diameter of the said inorganic filler is 0.5-50 micrometers, The resin composition characterized by the above-mentioned. The method of claim 1, Resin composition, characterized in that the molecular weight of the polysiloxane resin contained in the component (b) is 300 to 50,000. The method of claim 7, wherein Resin composition characterized in that the molecular weight of the polysiloxane resin contained in the (b) component is 500 to 30,000. The method of claim 1, The resin composition is a resin composition, characterized in that composed of at least one curing agent selected from the group consisting of amines, acid anhydrides and phenols. (a) an epoxy compound, (b) a curing agent comprising a polysiloxane resin having a repeating unit according to PS1 of Formula 1 and / or a repeating unit according to PS2 of Formula 2 below, and (c) an inorganic filler. Resin composition made into. (Formula 1) (R ¹ in the formula (I) is an alkyl group, a vinyl group, an allyl group, is selected from the consisting of a substituted or unsubstituted aryl group and a substituted or unsubstituted siloxy group having from 1 to 10 carbon atoms; R ² to R ⁶ may be the same or different, and when at least one of R ² to R ⁶ is a hydroxyl group, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a carboxyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkoxy group, allyl Individually selected from the group consisting of oxy groups, allyl groups and substituted or unsubstituted aryl groups) (Formula 2) R ⁷ in Formula 2 is a group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and a substituted or unsubstituted siloxy group. R ⁸ to R ¹² may be the same or different, and when at least one of R ⁸ to R ¹² is a group having a phenolic hydroxyl group or a phenolic hydroxyl group, a hydrogen atom, a halogen atom, a substitution Or unsubstituted alkyl, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkoxy, acyloxy, allyloxy, allyl, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, amide groups and imides Individually selected from a group of groups) The method of claim 10, The viscosity of the said resin composition is 5 Pa * S or less at the temperature of 100 degreeC, The resin composition characterized by the above-mentioned. The method of claim 10, Resin composition characterized in that the quantification of the component (c) composed of the inorganic filler is 10 to 95% by weight based on the total resin composition. The method of claim 12, Resin composition characterized in that the quantification of the component (c) composed of the inorganic filler is 40 to 90% by weight based on the total resin composition. The method of claim 10, The total amount of the component (a) composed of the epoxy resin and the component (b) composed of the curing agent is 5 to 90% by weight based on the total resin composition, and at the same time the epoxy group (EP) of the component (a) and the phenolic in the component (b) The ratio (EP / phOH) between hydroxyl groups (phOH) is 1 / 1.2-1 / 0.2, The resin composition characterized by the above-mentioned. The method of claim 10, The maximum particle diameter of (c) component comprised with the said inorganic filler is 50 micrometers or less, and the average particle diameter of the said inorganic filler is 0.5-50 micrometers, The resin composition characterized by the above-mentioned. The method of claim 10, Resin composition, characterized in that the molecular weight of the polysiloxane resin contained in the component (b) is 300 to 50,000. The method of claim 16, Resin composition characterized in that the molecular weight of the polysiloxane resin contained in the (b) component is 500 to 30,000. The method of claim 10, The resin composition, characterized in that the resin composition is composed of at least one type of curing agent selected from the group consisting of amines, acid anhydrides and phenols. A resin-sealed semiconductor device comprising a substrate, a semiconductor element attached to a surface of the substrate, and a resin layer for sealing the semiconductor element, Wherein said resin layer forms a cured material of a resin composition comprising (a) an epoxy compound, (b) a polysiloxane resin having a phenolic hydroxyl group in the side chain, and (c) an inorganic filler. Resin-sealed semiconductor device.