JP5938417B2 - One-part epoxy resin composition - Google Patents

Description

  The present invention relates to a one-pack type epoxy resin composition used as an underfill material for a flip chip mounting body, and more particularly to an epoxy resin composition suitable for use as a pre-feed type underfill material.

The flip chip mounting body has a structure in which an electrode portion on a substrate and a chip or a package as a semiconductor element are connected via a bump electrode, and the connecting portion of both is reinforced with an underfill. . The underfill material can be supplied by connecting the chip or package and the electrode part on the substrate, and then applying (dispensing) a post-feed type underfill material along the outer periphery of the chip or package, and then the capillary tube. Utilizing this phenomenon, a capillary flow that fills the gap between the two with an underfill material, and a portion that is reinforced with an underfill material on a substrate using a flip chip bonder device (specifically, electrode portions on the substrate and There is a compression flow in which a pre-feed type underfill material is applied (dispensed) in advance to the periphery thereof, and the chip or package is pressed from above, thereby connecting the chip or package to the substrate. In either case, the connection portion between the two is reinforced by heat-curing the underfill material.
For the purpose of shortening the process time or reducing voids, the underfill material is dispensed on a preheated substrate (for example, 60 ° C. to 120 ° C.) in any method. The fill material is required to have stability in a medium temperature range of 60 ° C to 120 ° C.

In both cases of the pre-feed type and the post-feed type, a one-pack type epoxy resin composition is usually used as the underfill material because it is easy to store and handle.
However, since the one-pack type epoxy resin composition has low stability in the middle temperature range, the curing reaction may proceed when dispensing the underfill material on the substrate. There was a problem.

  For the purpose of improving the storage stability in the normal temperature range while maintaining the rapid curability of the one-pack type epoxy resin composition, attempts have been made to latentize the curing accelerator contained in the epoxy resin composition. As the means, microencapsulation of a curing accelerator (see Patent Document 1), inclusion of a curing accelerator into an inclusion compound (see Patent Documents 2 and 3), and the like have been proposed. However, in any case, when the stability in the middle temperature range of 60 ° C. to 120 ° C. is increased, the fast curability is impaired. For example, when the content of the curing accelerator is reduced in order to control the curability of the epoxy resin composition and increase the stability in the middle temperature range of 60 ° C. to 120 ° C., the time required for curing becomes longer. , Fast curability is impaired.

JP 2005-344046 A JP 2007-39449 A JP 2010-180337 A

  In order to solve the above-described problems in the prior art, the present invention provides a one-pack type epoxy resin composition that maintains high curability at 150 ° C. or higher and has high stability in the middle temperature range of 60 ° C. to 120 ° C. The purpose is to provide.

In order to achieve the above object, the present invention provides (a) a liquid epoxy resin, (b) an acid anhydride curing agent or a phenol curing agent, (c) a latent curing accelerator, (d) 5-hydroxyisophthalate. acid, 5-nitro-isophthalic acid or the look-containing mixtures thereof, wherein the (c) a latent curing accelerator, a microcapsule-type latent curing accelerator and core amine adduct compound, or amine adduct A one-pack type epoxy resin composition which is a latent curing agent is provided.

  In the one-pack type epoxy resin composition of the present invention, it is preferable that the (c) latent curing accelerator is solid at room temperature.

  In the one-pack type epoxy resin composition of the present invention, the mass ratio ((d) / (c)) of (c) and (d) is preferably 0.01 to 5.

  The one-pack type epoxy resin composition of the present invention may further contain an inorganic filler.

  The present invention also provides an underfill material comprising the one-pack type epoxy resin composition of the present invention.

Further, the present invention is a method for manufacturing a semiconductor device in which a semiconductor chip is mounted on a wiring board by a flip chip bonding method,
A step of heating the wiring board and maintaining it at 60 ° C. to 120 ° C .;
Applying the underfill material of the present invention on the wiring board;
A step of aligning and pressing a semiconductor chip on a portion of the wiring board to which the underfill has been applied; and
Curing the underfill material at 150 ° C. to 200 ° C .;
The manufacturing method of the semiconductor device containing this is provided.

Further, the present invention is a method for manufacturing a semiconductor device in which a semiconductor chip is mounted on a wiring board by a flip chip bonding method,
Connecting a semiconductor chip to a wiring board;
A step of heating the wiring substrate and maintaining the temperature at 60 ° C. to 120 ° C .;
Provided is a method for manufacturing a semiconductor device, which includes a step of filling an underfill material of the present invention in a gap between the wiring board and the semiconductor chip, and a step of curing the underfill material at 150 ° C. to 200 ° C.

  The one-pack type epoxy resin composition of the present invention has a fast curing property at 150 ° C. or higher, and has a high stability in an intermediate temperature range of 60 ° C. to 120 ° C. Suitable as an underfill material. By using the one-pack type epoxy resin composition of the present invention as an underfill material, workability at the time of flip chip mounting is improved.

Hereinafter, the present invention will be described in detail.
The one-pack type epoxy resin composition of the present invention contains the following components (a) to (d) as essential components.

(A) Component: Liquid Epoxy Resin The liquid epoxy resin (a) is a component that forms the main component of the one-pack type epoxy resin composition of the present invention.
In the present invention, the liquid epoxy resin means an epoxy resin that is liquid at room temperature.
As the liquid epoxy resin in the present invention, a bisphenol A type epoxy resin having an average molecular weight of about 400 or less; a branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy resin; phenol novolac type epoxy resin having an average molecular weight of about 570 or less; vinyl (3,4-cyclohexene) dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) methyl, adipic acid Alicyclic epoxy resins such as bis (3,4-epoxy-6-methylcyclohexylmethyl), 2- (3,4-epoxycyclohexyl) 5,1-spiro (3,4-epoxycyclohexyl) -m-dioxane ; 3, 3 ' Biphenyl type epoxy resin such as 5,5′-tetramethyl-4,4′-diglycidyloxybiphenyl; glycidyl ester such as diglycidyl hexahydrophthalate, diglycidyl 3-methylhexahydrophthalate, diglycidyl hexahydroterephthalate Type epoxy resins; glycidyl amine type epoxy resins such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, tetraglycidyl bis (aminomethyl) cyclohexane; and 1,3 -Hydantoin type epoxy resin such as diglycidyl-5-methyl-5-ethylhydantoin; naphthalene ring-containing epoxy resin is exemplified. Moreover, an epoxy resin having a silicone skeleton such as 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane can also be used. Furthermore, diepoxide compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether; trimethylolpropane triglycidyl Examples include ethers and triepoxide compounds such as glycerin triglycidyl ether.
Among these, a liquid bisphenol type epoxy resin, a liquid aminophenol type epoxy resin, a silicone-modified epoxy resin, and a naphthalene type epoxy resin are preferable. More preferred are liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, p-aminophenol type liquid epoxy resin, and 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane.
(A) The liquid epoxy resin as a component may be individual or may be used together 2 or more types.
Moreover, even if it is an epoxy resin solid at normal temperature, it can be used when it shows liquid as a mixture by using together with a liquid epoxy resin.

(B) Component: Acid anhydride type curing agent or phenol type curing agent (b) The component is a curing agent for the epoxy resin of component (a).
In the present invention, the storage stability at room temperature, the fluidity when used as an underfill material, excellent curability, and the balance of physical properties of the cured product. Therefore, as an epoxy resin curing agent, an acid anhydride curing agent or A phenolic curing agent is used.
Specific examples of acid anhydride curing agents include phthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, benzophenone tetracarbanoic acid dianhydride Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1,2-dicarboxylic anhydride, 1-isopropyl-4-methylbicyclo [2.2.2] Oct-5-ene-2,3-dicarboxylic anhydride.
Among these, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1,2-dicarboxylic anhydride, 1- Isopropyl-4-methylbicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride and mixtures thereof are preferred.
Specific examples of phenolic curing agents include monomers, oligomers, and polymers in general having a phenolic hydroxyl group. For example, phenol novolak resins and alkylated products or allylated products thereof, cresol novolak resins, phenol aralkyl (including phenylene and biphenylene skeletons) ) Resin, naphthol aralkyl resin, triphenol methane resin, dicyclopentadiene type phenol resin and the like.
Among these, allylphenol novolac resins are preferable because the viscosity of the composition can be reduced.
In addition, any 1 type may be used among said hardening | curing agents, and 2 or more types may be used together.
Moreover, the hardening | curing agent as (b) component can be suitably selected according to the characteristic requested | required. An acid anhydride-based curing agent is excellent in injectability when used as an underfill material because it is easy to lower the viscosity of the composition. The phenolic curing material can obtain a cured product with low stress.

The content of the curing agent as the component (b) is determined by an equivalent ratio with respect to the epoxy group contained in the liquid epoxy resin as the component (a).
In the case of an acid anhydride curing agent, the curing agent is preferably 0.6 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the liquid epoxy resin of component (a), and 0.7 to 1.0 equivalents It is more preferable that
In the case of a phenolic curing agent, the curing agent is preferably 0.6 to 1.2 equivalents, and 0.7 to 1.1 equivalents with respect to 1 equivalent of the epoxy group of the liquid epoxy resin of component (a). It is more preferable.
Here, when using together an acid anhydride type hardening | curing agent and a phenol type hardening | curing agent, the sum total of the equivalent of each hardening | curing agent is 0.6-1.2 equivalent with respect to 1 equivalent of epoxy groups of a liquid epoxy resin. It is preferable that it is 0.7-1.1 equivalent.

Component (c): Latent curing accelerator In the present invention, an epoxy resin is used in order to obtain a one-pack type epoxy resin composition having fast curability and high stability in a medium temperature range of 60 ° C to 120 ° C. A latent curing accelerator is used as the curing accelerator.

  The latent curing accelerator as the component (c) is preferably solid at room temperature because of excellent storage stability at room temperature.

  The component (c) is not particularly limited as long as it is a latent curing accelerator for an epoxy resin, and a known one can be used, but a microcapsule type latent curing accelerator or an amine adduct type latent curing can be used. The agent is preferable because a composition having excellent stability in a middle temperature range of 60 ° C. to 120 ° C. can be obtained by combination with the component (d).

  In the present invention, the microcapsule-type latent curing accelerator is an amine compound having a primary, secondary, or tertiary amino group, or an amine adduct compound obtained by a reaction between these amine compounds and an epoxy resin. As an amine compound, an imidazole derivative is preferable because it is a curing accelerator having a structure covered with a shell made of a synthetic resin or an inorganic oxide. Examples of imidazole derivatives include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl. Mention may be made of imidazole. Examples of the synthetic resin to be a shell include phenol resin, melamine resin, epoxy resin, urethane resin, and urea resin, and these resins can be used in combination. Examples of the inorganic oxide serving as the shell include silica, alumina, titania, and magnesia. Specific examples include NOVACURE manufactured by Asahi Kasei E-Materials Co., Ltd., in which a latent curing accelerator obtained by coating an imidazole derivative with a reaction product such as an epoxy resin is dispersed in a liquid epoxy resin. -3721, HX-3742, HX-3088, HX-3921, HX-3941 (all are trade names) and the like.

  In the present invention, the amine adduct type latent curing accelerator is a reaction product of an amine compound having a primary, secondary or tertiary amino group and an epoxy resin (amine-epoxy adduct system), an amine compound and an isocyanate compound or A reaction product with a urea compound (urea type adduct system), and further, those obtained by treating the surface of these curing agents with an isocyanate compound or an acidic compound. The amine compound is preferably an imidazole derivative. Specifically, the amine-epoxy adduct type Ajinomoto FineTechno Amicure PN-23, Amicure PN-40, and the amine-urea adduct type Fuji Cure Industry Fujicure FX. -1000, FXR-1121 (both are trade names) and the like.

  The latent curing accelerator as the component (c) is preferably 0.5 to 60 parts by mass, and 5 to 50 parts by mass with respect to 100 parts by mass of the liquid epoxy resin as the component (a). Is more preferable.

Component (d): 5-hydroxyisophthalic acid (HIPA), 5-nitroisophthalic acid (NIPA), 1,3,5-benzenetricarboxylic acid (BTCA) or a mixture thereof In the present invention, 5 as component (d) -Hydroxyisophthalic acid, 5-nitroisophthalic acid, 1,3,5-benzenetricarboxylic acid or a mixture thereof is a component that improves the stability in the middle temperature range of 60 ° C to 120 ° C of the one-pack type epoxy resin composition. is there.

  In the invention described in Patent Document 2, an imidazole dissolved in a solvent such as methanol in advance and an isophthalic acid compound dissolved in the solvent are heated and reacted to form an inclusion compound as a curing catalyst (curing accelerator). By using it, it is said that the epoxy resin can be effectively cured by suppressing the curing reaction at a low temperature and improving the stability of the one liquid and applying the heat treatment.

  In the invention described in Patent Document 3, the inclusion complex of 5-hydroxyisophthalic acid and 2-ethyl-4-methylimidazole is used as a curing agent or curing accelerator for an epoxy resin, thereby The storage stability is improved, the fluidity of the sealing material at the time of sealing is maintained, and an efficient curing rate of the sealing material by heat can be realized.

The inventions described in Patent Documents 2 and 3 both improve the stability of the curing accelerator by forming an inclusion compound (or inclusion complex) with imidazole as a curing accelerator and an isophthalic acid compound. In addition, it is intended that the clathrate dissociates during heating and a rapid curing reaction occurs. However, when the clathrate compound (or clathrate complex) is stably formed, the clathrate is dissociated during heating. Since it becomes difficult, gel time becomes long and quick curability is impaired.
Therefore, it is not possible to achieve both fast curability at 150 ° C. or higher and stability in the middle temperature range of 60 ° C. to 120 ° C.

  On the other hand, in the one-pack type epoxy resin composition of the present invention, a latent curing accelerator is used as the component (c), and HIPA, NIPA, BTCA or a mixture thereof is used as the component (d). In addition, it is possible to achieve both fast curability at 150 ° C. or higher and stability in a medium temperature range of 60 ° C. to 120 ° C.

In the one-pack type epoxy resin composition of the present invention, (c) a latent curing accelerator as component and (d) HIPA, NIPA, BTCA or a mixture thereof as component include an inclusion compound (or an inclusion compound). It is considered that no complex is formed.
(C) The latent curing accelerator as component and (d) HIPA, NIPA, BTCA or a mixture thereof as component do not form an inclusion compound (or inclusion complex). Even if the content of HIPA, NIPA, BTCA or a mixture thereof as a component is a small amount as will be described later, it can be estimated that the intended effect is exhibited.
Note that the latent curing accelerator as the component (c) and HIPA, NIPA, BTCA, or a mixture thereof as the component (d) do not form an inclusion compound (or inclusion complex) ( When the latent curing accelerator as the component c) is a microcapsule type latent curing accelerator, it is considered that the reason is that the curing accelerator component is covered with the coating layer. On the other hand, when the latent curing accelerator as the component (c) is an amine adduct type latent curing accelerator, it is considered that the reason is that the curing accelerator component has already reacted.
In addition, by using the latent curing accelerator as the component (c) and HIPA, NIPA, BTCA or a mixture thereof as the component (d), the one-pack type epoxy resin composition can be stored at room temperature. Stability is also improved.

In the one-component epoxy resin composition of the present invention, the mass ratio ((d) / () of the latent curing accelerator as (c) and HIPA, NIPA, BTCA or a mixture thereof as the component (d). It is preferable that c)) is 0.01 to 5 in order to achieve both fast curability at 150 ° C. or higher and stability in an intermediate temperature range from 60 ° C. to 120 ° C.
When the mass ratio of the two ((d) / (c)) is smaller than 0.01, the content of HIPA, NIPA or a mixture thereof as component (d) is latent curable as component (c). Since there is little with respect to content of an accelerator, the effect by addition of HIPA, NIPA, BTCA, or a mixture thereof as the component (d) is not sufficiently exhibited, and the one-pack type epoxy resin composition has a temperature of 60 ° C to 120 ° C. There is a risk that the stability in the middle temperature range will be reduced. Moreover, there exists a possibility that the storage stability at normal temperature of a one-pack type epoxy resin composition may fall.
On the other hand, when the mass ratio ((d) / (c)) of both is greater than 5, the content of HIPA, NIPA, BTCA as a component (d) or a mixture thereof is a potential as a component (c). Since it increases with respect to content of a sclerosing | hardenable accelerator, there exists a possibility that the quick curability in 150 degreeC or more of a one-pack type epoxy resin composition may be impaired. Moreover, since an acid remains in hardened | cured material, it is anticipated that it will have a bad influence on the moisture resistance reliability of the semiconductor device produced using the one-pack type epoxy resin composition as an underfill material.
In the one-pack type epoxy resin composition of the present invention, the mass ratio ((d) / (c)) of both is more preferably 0.012 to 1.5, and preferably 0.015 to 0.8. Is more preferable.

(E) Component: Inorganic Filler When the one-pack type epoxy resin composition of the present invention is used as an underfill material, it is preferable to contain an inorganic filler as the (e) component.
(E) By containing an inorganic filler as a component, when the one-pack type epoxy resin composition of the present invention is used as an underfill material, the moisture resistance and thermal cycle resistance of the sealed portion, Thermal cycle performance is improved. The reason why the thermal cycle resistance is improved by using the inorganic filler is that the expansion / contraction of the cured product of the underfill material due to the thermal cycle can be suppressed by lowering the linear expansion coefficient.
The inorganic filler is not particularly limited as long as it has an effect of lowering the linear expansion coefficient by addition, and various inorganic fillers can be used. Specific examples include amorphous silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, and the like.
Among these, silica, particularly amorphous spherical silica, is excellent in fluidity when the one-part epoxy resin composition of the present invention is used as an underfill material, and can reduce the linear expansion coefficient of the cured product. desirable.
In addition, the silica said here may have an organic group derived from a manufacturing raw material, for example, alkyl groups, such as a methyl group and an ethyl group.
The amorphous spherical silica is preferably colloidal silica from the viewpoint of ease of production.
Moreover, as a silica used as an inorganic filler, you may use the silica containing composition obtained by the manufacturing method as described in Unexamined-Japanese-Patent No. 2007-1976655.
The inorganic filler may be one that has been surface-treated with a silane coupling agent or the like. When an inorganic filler that has been subjected to surface treatment is used, an effect of preventing aggregation of the inorganic filler is expected. Thereby, the improvement of the storage stability of the one-pack type epoxy resin composition of the present invention is expected.

(E) As for the inorganic filler as a component, it is preferable that an average particle diameter is 0.01-20 micrometers, and it is more preferable that it is 0.1-5 micrometers.
Here, the shape of the inorganic filler is not particularly limited, and may be any shape such as a spherical shape, an indeterminate shape, and a flake shape. When the shape of the inorganic filler is other than spherical, the average particle diameter of the inorganic filler means the average maximum diameter of the inorganic filler.

When an inorganic filler is contained as the component (e), the content of the inorganic filler in the one-pack type epoxy resin composition of the present invention is preferably 30 to 80% by mass.
As used herein, the content of the inorganic filler is, in addition to the components (a) to (d), including any components described below, and is a mass% based on the total amount of the one-component epoxy resin composition-containing component of the present invention. It is.
When the content of the inorganic filler is less than 30% by mass, the effect of lowering the linear expansion coefficient due to the addition of the inorganic filler is insufficient, and the one-pack type epoxy resin composition of the present invention is used as an underfill material In addition, the effect of improving the thermal cycle resistance may be insufficient.
On the other hand, when the content of the inorganic filler is more than 80% by mass, the coating property when the one-pack type epoxy resin composition of the present invention is used as a pre-feed type underfill material, or the post-feed type underfill material When used as, there is a possibility that the filling property into the gap and the electrical connectivity will be lowered.

(Other ingredients)
The one-pack type epoxy resin composition of the present invention may further contain components other than the components (a) to (e) as necessary.
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 oxetane, acrylate, bismaleimide, thermoplastic resins, elastomers, and the like may be blended.

(Preparation of one-pack type epoxy resin composition)
The one-pack type epoxy resin composition of the present invention is prepared by mixing and stirring the above 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.
Even if the components are mixed at the same time, some components may be mixed first, and the remaining components may be mixed later.

  Since the one-pack type epoxy resin composition of the present invention has the characteristics described below, it is suitable for both a pre-feed type underfill material and a post-feed type underfill material.

(Initial viscosity, rheometer viscosity double viscosity increase time)
The one-pack type epoxy resin composition of the present invention has an initial viscosity, specifically, a viscosity at 25 ° C. of 0.5 to 200 Pa · s.
Since the one-component epoxy resin composition of the present invention has an initial viscosity in the above range, the rheometer viscosity double-thickening time measured by the procedure described in the examples described later is 20 min or more. The stability in the middle temperature range of 60 ° C. to 120 ° C. is good, and the workability when used as a pre-feed type and post-feed type underfill material is good.

  Moreover, the one-pack type epoxy resin composition of the present invention has good storage stability at room temperature and is excellent in pot life. Specifically, the rate of increase in viscosity after being left for 24 hours in an environment of 25 ° C. and 50% humidity is 1.5 times or less.

The one-component epoxy resin composition of the present invention is excellent in rapid curability and can be cured by heating at a temperature of 150 to 200 ° C. for 3 seconds to 2 hours.
The one-pack type epoxy resin composition of the present invention preferably has a gel time of 5 minutes or less as measured by the procedure described in the examples described later.

The underfill material of the present invention is composed of the one-pack type epoxy resin composition of the present invention.
Next, a method for using the underfill material of the present invention will be described.
The underfill material of the present invention is used as a pre-feed type underfill material or a post-feed type underfill material when manufacturing a semiconductor device in which a semiconductor chip is mounted on a wiring board by a flip chip bonding method.

When used as a pre-feed type underfill material, a semiconductor device is manufactured according to the procedure of the compression flow.
In the compression flow, first, the wiring board is heated and held at 60 ° C. to 120 ° C. This is for heating the wiring board to a temperature suitable for application of the underfill material in order to apply the underfill material to the portion to be reinforced with the underfill material (specifically, the electrode portion on the substrate and its periphery). .
Next, an underfill material is applied on the wiring board. Specifically, the underfill material is applied (dispensed) to a portion (specifically, the electrode portion on the substrate and its periphery) that is reinforced with the underfill material on the substrate using a flip chip bonder device.
Next, the semiconductor chip is aligned and pressed against the portion where the underfill is applied. At the time of pressure welding of the semiconductor, the wiring board is heated to 200 ° C. to 300 ° C. Thereby, an underfill material will be in a semi-hardened state.
Next, in order to completely cure the underfill material, a post cure process is performed. Specifically, the wiring board is heated to 150 to 200 ° C. to cure the underfill.

When used as a post-feed type underfill material, a semiconductor device is manufactured according to a capillary flow procedure.
In capillary flow, first, a semiconductor chip is connected to a wiring board. Specifically, the electrode part provided on the wiring board and the bump electrode of the semiconductor chip are connected. For example, when soldering both, the flux electrode is applied to the electrode part provided on the wiring board, the bump electrode of the semiconductor chip, or both, and then the bump electrode is applied to the electrode part. The semiconductor element is temporarily placed on the substrate so as to be positioned, and then the substrate is heated to melt the solder, thereby connecting the electrode portion and the bump electrode.
Next, the wiring board is heated and held at 60 ° C. to 120 ° C.
In this state, an underfill material is applied (dispensed) along the outer periphery of the semiconductor chip, and the gap between the two is filled with a capillary phenomenon.
Next, the wiring substrate is heated to 150 to 200 ° C. to cure the underfill.

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

(Example 1-9, Comparative Examples 1 to 10)
The components shown in the table below were weighed out in the amounts (parts by mass) shown in the table, and the mixture obtained by mixing the components was kneaded with a three roll mill to obtain a uniform one-pack type epoxy resin composition.
In addition, the symbol in a table | surface represents the following, respectively.
Liquid epoxy resin (a1): Naphthalene type epoxy resin (epoxy equivalent 140 g / Eq)
Liquid epoxy resin (a2): Bisphenol F type epoxy resin (epoxy equivalent 160 g / Eq)
Curing agent (b1): acid anhydride curing agent (3,4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1,2-dicarboxylic acid anhydride)
Curing agent (b2): phenolic curing agent (allylphenol novolac resin) (hydroxyl equivalent: 135 g / Eq)
Latent cure accelerator (c1): Microcapsule type latent cure accelerator (Novacure HX3088, 2 parts by mass of bisphenol A type liquid epoxy resin, latent cure accelerator in which an imidazole derivative is coated with a reaction product such as epoxy resin) Mixture in which 1 part by mass is dispersed (epoxy equivalent 170 g / Eq) (manufactured by Asahi Kasei E-Materials Co., Ltd.))
Latent curing accelerator (c2): amine adduct type latent curing accelerator (Amicure PN-40J (Ajinomoto Fine Techno Co., Ltd.))
Latent curing accelerator (c3): amine adduct type latent curing accelerator (Fujicure FXR-1211 (manufactured by Fuji Kasei Kogyo Co., Ltd.))
(D1): HIPA
(D2): NIPA
(D3): BTCA
(D′ 1): HIPA-2MZ (inclusion compound of HIPA and imidazole) (manufactured by Nippon Soda Co., Ltd.)
(D′ 2): NIPA-2MZ (inclusion compound of NIPA and imidazole) (manufactured by Nippon Soda Co., Ltd.)
(D′ 3): 5-aminoisophthalic acid (d′ 4): dimethyl isophthalate (d′ 5): dimethyl 5-hydroxyisophthalate (d′ 6): p-toluic acid inorganic filler (e1): spherical Silica (average particle size 0.6μm)

  The curability and pouring properties of the one-pack type epoxy resin composition obtained by the above procedure, the appearance of the cured product of the liquid sealing material, and the thermal cycle resistance were evaluated by the following methods.

(Pot life, thickening ratio)
The initial viscosity of 1 g of a one-pack type epoxy resin composition collected as an evaluation sample was measured at 25 ° C. using a HAAKE rheometer (model number: MARS2), and then the evaluation sample was put in a sealed container. The viscosity at the time of storage for 24 hours in an environment of 25 ° C. and 50% humidity was measured in the same procedure, and the ratio to the viscosity immediately after preparation was calculated.

(Rheometer viscosity double viscosity increase time)
After measuring the initial viscosity of the evaluation sample with a HAAKE rheometer (model number: MARS2), when the evaluation sample is held at 80 ° C., the viscosity of the evaluation sample is twice the initial viscosity. The time required until is measured. About Example 4, 11 and the comparative example 1, the same measurement was implemented also about the case where the sample for evaluation was hold | maintained at 90 degreeC and 100 degreeC.

(Geltime)
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.

In all of the one-component epoxy resin compositions of Examples 1 to 9 , the evaluation results of the initial viscosity, pot life, gel time, and rheometer viscosity doubled thickening time were all good.
As is clear from the comparison of Examples 1 to 5, by adjusting the content of HIPA as the component (d), the quick curability of the one-pack type epoxy resin composition, the stability in the intermediate temperature range, Can be adjusted.
Moreover, as shown in Examples 6 and 7, the intended effect can be exhibited even when the type of the latent curing accelerator is changed.
Moreover, as shown in Example 8, even when NIPA is used as the component (d), the intended effect can be exhibited.
Moreover, as shown in Example 9, even when a phenolic curing agent is used as the component (b), the intended effect can be exhibited .
(D) Comparative examples 1-3 which did not contain a component were all inferior in the evaluation result of the rheometer viscosity 2 time thickening time. Further, as is clear from the comparison between Example 4 and Comparative Example 1, by containing HIPA as the component (d), stability in the middle temperature range of 60 to 100 ° C., particularly 80 to 90 ° C. Improved stability in the middle temperature range.
Further, Comparative Examples 4 and 5 using an inclusion compound of HIPA or NIPA and imidazole instead of the components (c) and (d) had a medium temperature compared to Comparative Example 1 containing no component (d). Although the stability of the area has improved, the fast curability has decreased accordingly.
(D) In place of component, compounds having structures similar to HIPA and NIPA (Comparative Examples 7 to 10 using 5-aminoisophthalic acid, dimethyl isophthalate, dimethyl 5-hydroxyisophthalate, and p-toluic acid are all used. The evaluation result of the rheometer viscosity double thickening time was inferior.

Claims (7)

(A) a liquid epoxy resin, (b) an acid anhydride curing agent or a phenol type curing agent, (c) a latent curing accelerator, (d) 5-hydroxy isophthalic acid, 5-nitro-isophthalic acid or the thereof mixture only contains the (c) a latent curing accelerator, a microcapsule-type latent curing accelerator and core amine adduct compound, or a amine adduct type latent curing agent, one-pack type epoxy resin Composition.   The one-pack type epoxy resin composition of Claim 1 whose said (c) latent hardening accelerator is solid at normal temperature. The one-pack type epoxy resin composition of Claim 1 or 2 whose mass ratio ((d) / (c)) of said (c) and said (d) is 0.01-5 . Furthermore, the one-pack type epoxy resin composition in any one of Claims 1-3 containing an inorganic filler . The underfill material which consists of a one-pack type epoxy resin composition in any one of Claims 1-4 . A method of manufacturing a semiconductor device in which a semiconductor chip is mounted on a wiring board by a flip chip bonding method,
A step of heating the wiring board and maintaining it at 60 ° C. to 120 ° C .;
Applying the underfill material according to claim 5 on the wiring board;
A step of aligning and pressing a semiconductor chip on a portion of the wiring board to which the underfill has been applied; and
Curing the underfill material at 150 ° C. to 200 ° C .;
A method of manufacturing a semiconductor device including: A method of manufacturing a semiconductor device in which a semiconductor chip is mounted on a wiring board by a flip chip bonding method,
Connecting a semiconductor chip to a wiring board;
A step of heating the wiring substrate and maintaining the temperature at 60 ° C. to 120 ° C .;
A method for manufacturing a semiconductor device, comprising: filling the gap between the wiring substrate and the semiconductor chip with the underfill material according to claim 5; and curing the underfill material at 150 ° C. to 200 ° C.