TW202136355A - Underfill material, semiconductor package and method of manufacturing semiconductor package - Google Patents

Abstract

An underfill material includes: an epoxy resin; an aromatic amine curing agent; an inorganic filler; and a compound having a triazine ring and an alkoxysilyl group, or a compound having a triazine ring, a primary amino group and a melting point of 200 DEG C or less.

Description

Underfill material, semiconductor package, and manufacturing method of semiconductor package

The present disclosure relates to an underfill material, a semiconductor package, and a manufacturing method of the semiconductor package.

In the field of sealing various semiconductor elements used in semiconductor devices such as transistors and integrated circuits (IC), sealing with resin has become the mainstream in terms of productivity and manufacturing cost. As the resin for sealing, epoxy resin is widely used. The reason is that the epoxy resin has an excellent balance of various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion with embedded products.

In recent years, in the field of semiconductor devices, in order to cope with the miniaturization and thinning of packages, semiconductor devices based on so-called bare chip packaging in which bare chips are directly packaged on wiring substrates have become mainstream. Examples of semiconductor devices obtained by bare chip packaging include, for example, chip on board (COB), chip on glass (COG), tape carrier package (TCP), and the like.

In a flip-chip type semiconductor device formed by bump-connecting a semiconductor element to a wiring board, a liquid resin composition is used as an underfill material filled in the gap between the bump-connected semiconductor element and the substrate . For example, Patent Document 1 describes an underfill material using a polyfunctional epoxy resin and a hardener containing a phenolic compound and an acid anhydride. The underfill material protects electronic parts from temperature, humidity and mechanical external forces.

In flip-chip type semiconductor devices, previously, solder balls were mainly used in the connection between the semiconductor element and the substrate. On the other hand, with the increase in the number of terminals caused by the miniaturization and high integration of semiconductor devices, the use of copper pillars with solder sealed at the tip instead of the previous solder balls has gradually increased. Therefore, when a reflow furnace is used to connect the semiconductor device at a high temperature (for example, 260° C.) in order to mount the semiconductor device on a motherboard or the like, there may be a problem that the underfill material is peeled from the copper pillar.

As a method of improving the adhesion between the epoxy resin composition and copper, for example, Patent Document 2 to Patent Document 6 describe an epoxy resin composition containing a compound having excellent adhesion to copper. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-256646 [Patent Document 2] Japanese Patent Laid-Open No. 2007-2170 [Patent Document 3] Japanese Patent Laid-Open No. 2012-188629 [Patent Document 4] Japanese Patent Laid-Open No. 2016-169300 [Patent Document 5] Japanese Patent Laid-Open No. 2016-34906 [Patent Document 6] Japanese Patent Laid-Open No. 2017-2289

[The problem to be solved by the invention] However, when a compound with excellent adhesion to copper is generally applied to an underfill material, it often reacts with resin components such as epoxy resin and hardener to stabilize storage during the pot life, that is, at room temperature. Sexual deterioration. Furthermore, until now, the adhesion of the underfill material to copper at high temperatures (for example, 260°C) has not been verified.

In view of the foregoing circumstances, the subject of the present disclosure is to provide an underfill material with excellent pot life and excellent high-temperature adhesion to copper when made into a cured product, and a semiconductor package including the cured product of the underfill material and its manufacture method. [Means to solve the problem]

The means to solve the problem include the following implementation aspects. <1> An underfill material containing: epoxy resin, aromatic amine hardener, inorganic filler, and a compound having a triazine ring and an alkoxysilyl group. <2> The underfill material according to <1>, wherein the melting point of the compound having a triazine ring and an alkoxysilyl group is 200° C. or less. <3> The underfill material according to <1> or <2>, wherein the compound having a triazine ring and an alkoxysilyl group further has a primary amino group. <4> An underfill material containing: an epoxy resin, an aromatic amine hardener, an inorganic filler, and a compound having a triazine ring and a primary amine group and having a melting point of 200°C or less. <5> A semiconductor package including: a substrate, a semiconductor element arranged on the substrate, and a cured product of the underfill material according to any one of <1> to <4> that seals the semiconductor element. <6> A method for manufacturing a semiconductor package, including the step of filling a gap between a substrate and a semiconductor element arranged on the substrate with the underfill material described in any one of <1> to <5>; And the step of hardening the underfill material. [Effects of the invention]

According to the present disclosure, it is possible to provide an underfill material having excellent pot life and excellent high-temperature adhesion to copper when made into a cured product, and a semiconductor package including a cured product of the underfill material, and a manufacturing method thereof.

Hereinafter, an embodiment of the present disclosure will be described in detail. However, the embodiment of this disclosure is not limited to the following embodiment. In the following embodiments, its constituent elements (including element steps, etc.) are not essential unless otherwise specified. The same is true for the numerical value and its range, and does not limit the embodiment of the present disclosure.

In the present disclosure, in the term "step", in addition to a step independent of other steps, even if it cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved, the step is also included. In the present disclosure, the numerical values described before and after "～" are included in the numerical range indicated by "～" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical range described in the present disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples. In the present disclosure, each component may also include multiple equivalent substances. When there are multiple types of substances corresponding to each component in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the multiple types of substances present in the composition. In the present disclosure, a plurality of particles corresponding to each component may also be included. When there are multiple types of particles corresponding to each component in the composition, unless otherwise specified, the particle diameter of each component refers to a value related to a mixture of the multiple types of particles present in the composition.

＜＜Underfill material＞＞ The underfill material of the first embodiment of the present disclosure contains an epoxy resin, an aromatic amine hardener, an inorganic filler, and a compound having a triazine ring and an alkoxysilyl group (hereinafter, also referred to as "the first triazine-containing Ring compound"). The underfill material of the second embodiment of the present disclosure contains an epoxy resin, an aromatic amine hardener, an inorganic filler, and a compound having a triazine ring and a primary amine group and having a melting point of 200°C or less (hereinafter, also referred to as " The second compound containing a triazine ring"). Hereinafter, the underfill material of the first embodiment and the underfill material of the second embodiment may be collectively referred to as "underfill material of the present disclosure" or simply referred to as "underfill material" in some cases.

The underfill material of the present disclosure has excellent pot life and excellent high-temperature adhesion to copper when it is made into a hardened product. In this disclosure, the high-temperature adhesiveness refers to adhesiveness at 260°C. The detailed reason why the pot life of the underfill material of the present disclosure and the high-temperature adhesiveness with respect to copper when used as a hardened product are not necessarily clear, but it is estimated as follows. The underfill material of the first embodiment contains a compound having a triazine ring and an alkoxysilyl group (the first triazine ring-containing compound). It is considered that the nitrogen atom in the triazine ring contributes to the high-temperature adhesion to copper. In addition, due to the presence of the alkoxysilyl group, the first triazine ring-containing compound has excellent compatibility with epoxy resin and is well dispersed in the underfill material. Therefore, it is considered that it has high temperature adhesion throughout the entire underfill material. good. Furthermore, when the first triazine ring-containing compound is used and the aromatic amine compound is used as the hardener, the reactivity of the first triazine ring-containing compound and the aromatic amine compound with respect to the epoxy group is not too high. Therefore, it is believed that the progress of gelation is relatively slow, and an excellent pot life can be obtained. The underfill material of the second embodiment contains a compound having a triazine ring and a primary amine group and having a melting point of 200° C. or lower (a second triazine ring-containing compound). It is considered that the nitrogen atom and the primary amine group in the triazine ring contribute to the high-temperature adhesion to copper. In addition, since the melting point of this compound is 200°C or less, it is considered that it will harden the underfill material during kneading (for example, about 25°C to 80°C), when filling the gap between the device and the substrate (for example, about 100°C to 120°C), and When (for example, about 80°C to 200°C), the dispersibility in the epoxy resin is excellent, and the high-temperature adhesiveness is good throughout the entire underfill material. Furthermore, when the second triazine ring-containing compound is used and the aromatic amine compound is used as the hardener, the reactivity of the second triazine ring-containing compound and the aromatic amine compound with respect to the epoxy resin is not too high. Therefore, it is believed that the progress of gelation is relatively slow, and an excellent pot life can be obtained.

The underfill material is preferably liquid at 25°C. In the present disclosure, the so-called "liquid" refers to a substance that exhibits fluidity and viscosity and exhibits viscosity, that is, a viscosity of 0.0001 Pa·s to 100 Pa·s. In addition, the term "liquid" refers to the state of liquid.

In the present disclosure, the viscosity is such that an EHD type rotary viscometer (for example, manufactured by Tokyo Keiki Co., Ltd., VISCONIC EHD type (trade name)) at 25°C for 1 minute, 10 revolutions per minute (10 rpm) ) Measured value during rotation. The measured value is obtained by using an EHD type rotary viscometer equipped with a cone rotor with a cone angle of 3° and a cone radius of 14 mm for a liquid kept at 25±1°C.

The viscosity of the underfill material is not particularly limited. Among them, from the viewpoint of high fluidity, the viscosity of the underfill material at 25°C is preferably 0.1 Pa·s to 100.0 Pa·s, more preferably 0.1 Pa·s to 50.0 Pa·s, and still more preferably 0.1 Pa·s～30.0 Pa·s.

In addition, as an index of the ease of filling when filling an underfill material in a narrow gap of tens to hundreds of μm at around 100°C to 120°C, the viscosity of the underfill material at 110°C is preferably 0.20 Pa·s Below, it is more preferably 0.15 Pa·s or less. Furthermore, the viscosity of the underfill material at 110°C can be measured by a rheometer (such as TA Instrument, AR2000, cone radius 20 mm, shear rate 32.5/sec).

The pot life of the underfill material measured by the following method after being placed at 25°C for 24 hours is preferably 100% or less, more preferably 90% or less, still more preferably 80% or less, particularly preferably 60% or less. The lower limit of the pot life is not particularly limited, and the lower the value, the better. Place the underfill material at 25°C for 24 hours, and then use an E-type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd., VISCONIC EHD type (trade name)) (cone angle 3°, rotation speed 10 revolutions per minute) (Rpm)) to determine the viscosity at 25°C (viscosity after storage). Among them, for a sample that cannot be measured at 10 revolutions per minute (rpm) due to high viscosity, the measurement is performed at 2.5 revolutions per minute (rpm). The pot life (%) is calculated according to the following formula as the viscosity increase rate after being left for 24 hours. Pot life (%)={(Viscosity after placement-initial viscosity)/initial viscosity}×100

The high-temperature adhesive strength of the underfill material to copper (Cu) measured by the following method is preferably 0.70 kgf or more, more preferably 0.80 kgf or more, and still more preferably 0.90 kgf or more. The higher the high temperature adhesive force, the better.

The adhesive force with respect to copper can be measured as follows, for example. Prepare a test piece formed by forming an underfill material with a diameter of 3 mm and a height of 3 mm on the surface of a copper plate. Use a bond tester (such as DS100 manufactured by DAGE) at a head speed of 50 μm/sec. Shear stress is applied downward, and the strength of the molded product peeling from the copper plate is measured. Specifically, it can be measured by the method described in the examples.

＜Epoxy resin＞ The type of epoxy resin is not particularly limited. The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule.

The epoxy resin may be solid or liquid at room temperature, and a solid epoxy resin and a liquid epoxy resin may be used in combination. From the viewpoint of lowering the viscosity of the underfill material, it is preferable to use an epoxy resin that is liquid at room temperature. From the viewpoint of fluidity during molding, the content of the solid epoxy resin is preferably 20% by mass or less with respect to the total epoxy resin.

The type of epoxy resin is not particularly limited. Specific examples of epoxy resins include novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; bisphenol A type epoxy resins and bisphenol F type epoxy resins. Bisphenol-type epoxy resin; N,N-diglycidyl aniline, N,N-diglycidyl toluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine and other glycidylamines Type epoxy resin; a phenol aralkyl type epoxy resin having at least one selected from the group consisting of a phenylene skeleton and a biphenylene skeleton; having a phenylene skeleton and a biphenylene skeleton Aralkyl type epoxy resins such as naphthol aralkyl type epoxy resins of at least one of the group consisting of skeletons; hydroquinone type epoxy resins; biphenyl type epoxy resins; stilbene type epoxy resins Epoxy resin; triphenol methane type epoxy resin; triphenol propane type epoxy resin; alkyl modified triphenol methane type epoxy resin; epoxy resin containing triazine nucleus; dicyclopentadiene modified phenol type Epoxy resin; naphthol type epoxy resin; naphthalene type epoxy resin; vinyl cyclohexene dioxide, dicyclopentadiene oxide, alicyclic diepoxy-adipate (alicyclic diepoxy-adipate) ) And other alicyclic epoxy resins; alkanediol diglycidyl ether, poly(alkylene glycol) diglycidyl ether, alkene glycol diglycidyl ether and other difunctional aliphatic rings with two epoxy groups in the molecule Oxygen compounds, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

In the case of using two or more epoxy resins, the two or more epoxy resins may be mixed in advance and then mixed with other components, or may be mixed with other components without mixing in advance.

The epoxy equivalent of the epoxy resin is not particularly limited. The epoxy equivalent of the epoxy resin may be 60 g/eq or more, 70 g/eq or more, or 90 g/eq or more. The epoxy equivalent of the epoxy resin may be 500 g/eq or less, 300 g/eq or less, or 200 g/eq or less. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, it is preferably 60 g/eq to 500 g/eq, more preferably 70 g/eq to 300 g/eq, and still more preferably 90 g/eq～200 g/eq. The epoxy equivalent of an epoxy resin shall be the value measured by the method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7236:2009.

The content rate of the epoxy resin with respect to the total mass of the underfill material is not particularly limited. The content rate of the epoxy resin with respect to the total mass of the underfill material may be 0.5% by mass or more, or 2% by mass or more. The content rate of the epoxy resin with respect to the total mass of the underfill material may be 50% by mass or less, 40% by mass or less, or 30% by mass or less. From the viewpoints of viscosity, glass transition temperature, heat resistance, etc., relative to the total mass of the underfill material, the epoxy resin content is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 40% by mass , More preferably, it is 5 mass%-30 mass %.

In one aspect, from the viewpoints of injectability and reduction of the thermal expansion coefficient when the cured product is made, the underfill material preferably contains selected from the group consisting of bisphenol-type epoxy resin, glycidylamine-type epoxy resin and naphthalene. At least one of the group consisting of type epoxy resin. In addition, the underfill material more preferably contains any one of a bisphenol type epoxy resin, a glycidylamine type epoxy resin, and a naphthalene type epoxy resin.

The type of bisphenol epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol AD epoxy resin. Bisphenol-type epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. From the viewpoint of using the underfill material in a liquid form, the bisphenol-type epoxy resin is preferably liquid at normal temperature (25° C.). From the viewpoint of reducing the viscosity, the bisphenol-type epoxy resin is preferably a bisphenol-F-type epoxy resin.

When the underfill material contains a bisphenol type epoxy resin, the content of the bisphenol type epoxy resin is not particularly limited, and can be selected according to the desired characteristics of the underfill material. For example, relative to the total mass of the epoxy resin, the content of the bisphenol F type epoxy resin may be 20% by mass or more, 30% by mass or more, or 40% by mass or more. With respect to the total mass of the epoxy resin, the content of the bisphenol F type epoxy resin may be less than 90% by mass, 80% by mass or less, or 70% by mass or less. Relative to the total mass of the epoxy resin, the content of the bisphenol F epoxy resin may be 20% by mass or more and less than 90% by mass, or 30% to 80% by mass, or 40% to 40% by mass. 70% by mass.

The type of glycidylamine type epoxy resin is not particularly limited. The glycidylamine type epoxy resin is preferably bifunctional or higher, and from the viewpoint of improving the heat resistance after curing, it is preferably trifunctional or higher (that is, having three or more epoxy groups in a molecule) glycidylamine Type epoxy resin. Examples of the bifunctional glycidylamine epoxy resin include N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, and the like. Examples of trifunctional or higher glycidylamine epoxy resins include triglycidyl-p-aminophenol, 4,4'-methylenebis[N,N-bis(oxocyclopropylmethyl)aniline ]Wait. The glycidylamine type epoxy resin may be used alone or in combination of two or more. Among them, from the viewpoint of the viscosity at normal temperature (25° C.), triglycidyl-p-aminophenol is preferred.

From the viewpoint of reducing the viscosity of the underfill material, the molecular weight of the glycidylamine epoxy resin is preferably 300 or less.

In the case where the underfill material contains a glycidylamine-type epoxy resin, the content of the glycidylamine-type epoxy resin is not particularly limited. For example, with respect to the total mass of the epoxy resin, the content rate of the glycidylamine type epoxy resin may be 10% by mass or more, 20% by mass or more, or 25% by mass or more. Relative to the total mass of the epoxy resin, the content of the glycidylamine-type epoxy resin may be 60% by mass or less, 50% by mass or less, or 40% by mass or less. Relative to the total mass of the epoxy resin, the content of the glycidylamine epoxy resin may be 10% by mass to 60% by mass, or 20% by mass to 50% by mass, or 25% by mass to 40% by mass. .

The type of naphthalene type epoxy resin is not particularly limited. From the viewpoint of reducing the coefficient of thermal expansion, 1,6-bis(glycidyloxy)naphthalene is preferred.

In the case where the underfill material contains a naphthalene-type epoxy resin, the content of the naphthalene-type epoxy resin is not particularly limited. For example, with respect to the total mass of the epoxy resin, the content rate of the naphthalene-type epoxy resin may be 10% by mass or more, or 15% by mass or more. The content rate of the naphthalene type epoxy resin may be 30% by mass or less, or 25% by mass or less with respect to the total mass of the epoxy resin. The content rate of the naphthalene type epoxy resin may be 10% by mass to 30% by mass, or 15% by mass to 25% by mass relative to the total mass of the epoxy resin.

＜Aromatic amine hardener＞ The type of the aromatic amine hardener is not particularly limited, but it is preferably an aromatic amine compound having two or more of at least one selected from the group consisting of a primary amino group and a secondary amino group in one molecule, and more preferably It is an aromatic amine compound having two to four at least one selected from the group consisting of primary amine groups and secondary amine groups in one molecule, and more preferably two to four selected from primary amine groups and At least one aromatic amine compound in the group consisting of secondary amine groups. The aromatic amine hardener is preferably liquid at 25°C.

Examples of aromatic amine hardeners include diethyltoluene diamine such as 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine; 1 ,3,5-Triethyl-2,6-diaminobenzene and other triethyldiaminobenzene; 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3, Diaminodiphenylmethane such as 5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane, etc. The aromatic amine hardener may be used alone or in combination of two or more.

Among them, from the viewpoint of storage stability, it is preferably at least one selected from the group consisting of diaminodiphenylmethane and diethyltoluenediamine, and it is more preferable to use these in combination.

The active hydrogen equivalent of the aromatic amine hardener is not particularly limited. The active hydrogen equivalent of the aromatic amine hardener may be 20 g/eq or more, 30 g/eq or more, or 40 g/eq or more. The active hydrogen equivalent of the aromatic amine hardener may be 200 g/eq or less, 100 g/eq or less, or 80 g/eq or less. From the viewpoint of taking into account the reduction in thermal stress of the cured product and the high glass transition temperature (Tg), it is preferably 20 g/eq to 200 g/eq, more preferably 30 g/eq to 100 g/eq, and still more preferably 40 g/eq～80 g/eq.

In addition to the aromatic amine hardener, the underfill material may also contain other hardeners. Examples of hardeners other than aromatic amine hardeners include: aliphatic amine hardeners, phenol hardeners, acid anhydride hardeners, imidazole compounds, imidazoline compounds, polythiol hardeners, polyaminoamide hardeners, isocyanates Hardener, blocked isocyanate hardener, etc.

The content of the aromatic amine hardener with respect to the total mass of the hardener is not particularly limited, but from the viewpoint of making the pot life and the high-temperature adhesion to copper particularly good when the hardened product is made, it is preferably 50 mass % Or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. Among them, the total content of at least one selected from the group consisting of diaminodiphenylmethane and diethyltoluenediamine relative to the total mass of the hardener is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more.

The equivalent ratio of epoxy resin to hardener (including aromatic amine hardener), that is, the ratio of the number of functional groups (active hydrogen in the case of an amine hardener) in the hardener to the number of epoxy groups in the epoxy resin (The number of functional groups in the hardener/the number of epoxy groups in the epoxy resin) is not particularly limited. From the viewpoint of minimizing the respective unreacted components, it is preferably set to be in the range of 0.5 to 2.0, and more preferably set to be in the range of 0.6 to 1.3. From the viewpoint of formability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

From the viewpoint of making the underfill material liquid at normal temperature (25° C.), it is preferable to select the hardener so that the entire hardener becomes liquid at normal temperature. That is, in the case of using only one kind of hardening agent, it is preferable that the hardening agent is liquid at normal temperature. In the case of using a combination of two or more hardeners, the two or more hardeners can be liquid at room temperature, or a part of the hardener that is solid at room temperature can also be used, and the two or more hardeners can be hardened When the agent is mixed, it becomes a liquid combination at room temperature. In the case of using a hardening agent that is solid at room temperature as the hardening agent, from the viewpoint of fluidity, the content of the hardening agent that is solid at room temperature is preferably 20 mass relative to the total mass of the hardening agent %the following.

＜Inorganic fillers＞ The type of inorganic filler is not particularly limited, for example, silicon dioxide, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, oxide Zirconium, zircon, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. Examples of inorganic fillers having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, composite hydroxides of magnesium and zinc, and zinc borate. One kind of inorganic filler may be used alone, or two or more kinds may be used in combination. Among them, from the viewpoint of reducing the thermal expansion coefficient, silica is preferred, and from the viewpoint of improving thermal conductivity, alumina is preferred.

The content of the inorganic filler is not particularly limited. Relative to the total mass of the underfill material, the content of the inorganic filler may be 30% by mass or more, 40% by mass or more, or 50% by mass or more. Relative to the total mass of the underfill material, the content of the inorganic filler may be 90% by mass or less, 80% by mass or less, or 75% by mass or less. From the viewpoint of both good fluidity and the desired effect brought by the inorganic filler, the content of the inorganic filler is preferably 30% to 90% by mass relative to the total mass of the underfill material. It is preferably 40% by mass to 80% by mass, and more preferably 50% by mass to 75% by mass.

When the inorganic filler is particulate, the average particle diameter is not particularly limited. For example, the volume average particle diameter of the inorganic filler may be 0.2 μm or more, or 0.5 μm or more. The volume average particle diameter of the inorganic filler may be 20 μm or less, or 15 μm or less. The volume average particle diameter of the inorganic filler is preferably 0.2 μm to 20 μm, more preferably 0.5 μm to 15 μm. If the volume average particle diameter is 0.2 μm or more, there is a tendency to further suppress the increase in the viscosity of the underfill material. If the volume average particle diameter is 20 μm or less, there is a tendency to further improve the filling properties for narrow gaps. The volume average particle diameter of the inorganic filler can be used as the particle diameter (D50 ) To determine.

＜Compounds containing triazine ring＞ -The first compound containing a triazine ring- The first triazine ring-containing compound has a triazine ring and an alkoxysilyl group. The position of the nitrogen in the triazine ring is not particularly limited. That is, the triazine as a skeleton may be any of 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine.

The first triazine ring-containing compound has the following structure: at least one of the hydrogen atoms bonded to the three carbon atoms on the _{triazine (C 3} H ₃ N _{3) is substituted with a monovalent group having an alkoxysilyl group} Structure. The substitution position of the monovalent group may be any of three carbon atoms. The number of substitutions of the monovalent group may be any one to three, preferably one or two, and more preferably one.

When the number of substitutions of the monovalent group having an alkoxysilyl group in the first triazine ring-containing compound is 1 or 2, the monovalent group having an alkoxysilyl group on the triazine ring A substituent other than the monovalent group having an alkoxysilyl group may be bonded to the carbon atom to which the group is not bonded, or the substituent may not be bonded.

The monovalent group having an alkoxysilyl group may be the alkoxysilyl group itself, or a monovalent group formed by bonding a linking group and a silicon atom of the alkoxysilyl group. In the case where the monovalent group having an alkoxysilyl group is a monovalent group formed by bonding a linking group to a silicon atom of the alkoxysilyl group, the linking group may be, for example, a hydrocarbon group, or may have a nitrogen atom, oxygen Hydrocarbyl of heteroatoms such as atoms. The length of the linking group, that is, the number of atoms in the chain of atoms (without hydrogen atoms, branched chains or substituents) existing between the silicon atoms of the alkoxysilyl group and the carbon atoms on the triazine ring can be, for example, 2. ～13, can also be 3～11.

The alkoxysilyl group has a structure represented by _{-Si(OR) 3.} Here, R each independently represents a hydrogen atom or an alkyl group, and at least one of the three Rs is an alkyl group. Among the three Rs, preferably two or more are alkyl groups, and more preferably three are all alkyl groups. As the alkyl group represented by R, each independently is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably an ethyl group.

The substituents other than the monovalent group having an alkoxysilyl group that can be bonded to the triazine ring are not particularly limited, and examples thereof include a halogen atom, an amino group, a hydroxyl group, an arylamino group, and an alkylamino group. Among them, an amine group is preferred, a primary amine group or a secondary amine group is more preferred, and a primary amine group is still more preferred. The number of substituents other than the monovalent group having an alkoxysilyl group is not particularly limited, but preferably the number of the monovalent group having an alkoxysilyl group and the number of the monovalent group having an alkoxysilyl group other than the monovalent group The total number of substituents is three.

Preferred examples of the first triazine ring-containing compound include compounds represented by the following general formula (I).

[化1]

In the formula (I), X represents a monovalent group having an alkoxysilyl group. The details of the monovalent group having an alkoxysilyl group in X are the same as the above-mentioned aspect.

The molecular weight of the triazine ring-containing compound is not particularly limited, and may be, for example, 100-800, 200-700, or 300-600.

The melting point of the first triazine ring-containing compound is not particularly limited. From the viewpoint of high-temperature adhesion and pot life, it is preferably 200°C or lower, more preferably 175°C or lower, and still more preferably 150°C or lower. From the viewpoint of handleability and dispersibility, the melting point of the first triazine ring-containing compound is preferably 0°C or higher, more preferably 10°C or higher, and still more preferably 25°C or higher. From the above viewpoints, the melting point of the first triazine ring-containing compound is preferably 0°C to 200°C, more preferably 10°C to 175°C, and still more preferably 25°C to 150°C.

From the viewpoint of a good balance of high-temperature adhesion to copper and excellent pot life, the content of the first triazine ring-containing compound relative to the total mass of the underfill material is preferably 0.05% by mass or more, and more preferably It is 0.10% by mass or more, more preferably 0.20% by mass or more. In addition, from the viewpoint of suppressing the increase in the viscosity of the underfill material itself, the content of the first triazine ring-containing compound relative to the total mass of the underfill material is preferably 3.0% by mass or less, more preferably 2.0% by mass or less , And more preferably 1.5% by mass or less. From the above viewpoints, the content of the first triazine ring-containing compound relative to the total mass of the underfill material is preferably 0.05% by mass to 3.0% by mass, more preferably 0.10% by mass to 2.0% by mass, and more preferably It is 0.20% by mass to 1.5% by mass.

-Second compound containing triazine ring- The second triazine ring-containing compound has a triazine ring and a primary amino group and has a melting point of 200° C. or less.

From the viewpoint of high-temperature adhesion and pot life, the melting point of the second triazine ring-containing compound is preferably 175°C or lower, more preferably 150°C or lower. From the viewpoint of handleability and dispersibility, the melting point of the second triazine ring-containing compound is preferably 0°C or higher, more preferably 10°C or higher, and still more preferably 25°C or higher. From the above viewpoints, the melting point of the second triazine ring-containing compound is preferably 0°C to 200°C, more preferably 10°C to 175°C, and still more preferably 25°C to 150°C. The melting point of the triazine ring-containing compound can be measured by a melting point analyzer or the like.

The position of the nitrogen in the triazine ring is not particularly limited. That is, the triazine as a skeleton may be any of 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine.

The second triazine ring-containing compound has the following structure: a structure in which at least one of the hydrogen atoms bonded to three carbon atoms on the _{triazine (C 3} H ₃ N _{3) is substituted with a monovalent group having a primary amino group} . The substitution position of the monovalent group may be any of three carbon atoms. The number of substitutions of the monovalent group may be any one to three.

When the number of substitutions of the monovalent group having a primary amine group in the second triazine ring-containing compound is 1 or 2, the monovalent group having a primary amine group on the triazine ring is not bonded A substituent other than the monovalent group having the primary amino group may be bonded to the bonded carbon atom, or the substituent may not be bonded.

The monovalent group having a primary amine group may be the primary amine group itself, or may be a monovalent group formed by bonding a linking group to the nitrogen atom of the primary amine group. In the case where the monovalent group having a primary amine group is a monovalent group formed by bonding a linking group to the nitrogen atom of the primary amine group, the linking group may be, for example, a hydrocarbon group, or may have a heteroatom such as a nitrogen atom and an oxygen atom的hydrocarbyl. The length of the linking group, that is, the number of atoms in the chain of atoms (excluding hydrogen atoms, branch chains or substituents) existing between the nitrogen atom of the primary amino group and the carbon atom on the triazine ring can be, for example, 1-10 , Can also be 1～5. The monovalent group having a primary amine group is preferably the primary amine group itself.

The substituents other than the monovalent group having a primary amino group that can be bonded to the triazine ring are not particularly limited, and examples include halogen atoms, amino groups, hydroxyl groups, arylamino groups, alkylamino groups, and alkoxy groups. From the viewpoint of pot life, the monovalent group of the silyl group and the like are preferably a monovalent group having an alkoxysilyl group. The details of the monovalent group having an alkoxysilyl group are the same as the monovalent group having an alkoxysilyl group described in the first triazine ring-containing compound. The number of substituents other than the monovalent group having a primary amino group is not particularly limited, and it is preferable that the sum of the number of the monovalent group having a primary amino group and the number of substituents other than the monovalent group having a primary amino group is three.

As a preferable example of the second triazine ring-containing compound, the compound represented by the general formula (I) can be cited.

From the viewpoint of a good balance of high-temperature adhesion to copper and excellent pot life, the content of the second triazine ring-containing compound relative to the total mass of the underfill material is preferably 0.05% by mass or more, more preferably It is 0.10% by mass or more, more preferably 0.20% by mass or more. In addition, from the viewpoint of suppressing the increase in the viscosity of the underfill material itself, the content of the second triazine ring-containing compound relative to the total mass of the underfill material is preferably 3.0% by mass or less, more preferably 2.0% by mass or less , And more preferably 1.5% by mass or less. From the above point of view, the content of the second triazine ring-containing compound relative to the total mass of the underfill material is preferably 0.05% by mass to 3.0% by mass, more preferably 0.10% by mass to 2.0% by mass, and more preferably It is 0.20% by mass to 1.5% by mass.

＜Various additives＞ In addition to the above-mentioned components, the underfill material may also contain various additives such as a hardening accelerator, a stress reliever, a coupling agent, an ion scavenger, an exudation inhibitor, and a coloring agent. In addition to the additives exemplified below, the underfill material may also contain various additives known in the technical field as necessary.

(Hardening accelerator) The underfill material may also contain a hardening accelerator. The kind of hardening accelerator is not particularly limited, and it can be selected according to the kind of epoxy resin and hardening agent, the desired characteristics of the underfill material, and the like. Specific examples include: 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-dibutyl Amino-1,8-diaza-bicyclo[5.4.0]undecene-7 and other cyclic amidine compounds; addition of p-cyclic amidine compounds to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone , 1,4-Naphthoquinone, 2,3-Dimethylbenzoquinone, 2,6-Dimethylbenzoquinone, 2,3-Dimethoxy-5-methyl-1,4-benzoquinone, 2 ,3-Dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, diazophenylmethane, phenol resins and other compounds with π bonds that have intramolecular polarization Compounds; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of tertiary amine compounds; 2-methylimidazole , 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl -4,5-Dihydroxymethylimidazole and other imidazole compounds; derivatives of imidazole compounds; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, diphenyl Organic phosphine compounds such as phosphine and phenylphosphine; phosphorus with intramolecular polarization formed by adding maleic anhydride, the quinone compound, diazophenylmethane, phenol resin and other compounds with π bond to the organic phosphine compound Compound; Tetraphenylphosphonium tetraphenylborate, triphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, etc. Tetraphenylborate; derivatives of tetraphenylborate; tetraphenylborane complexes such as triphenylphosphine-triphenylborane complexes, morpholine-triphenylborane complexes, etc. . One type of hardening accelerator may be used alone, or two or more types may be used in combination.

In the case where the underfill material contains a hardening accelerator, the content of the hardening accelerator is not particularly limited. With respect to 100 parts by mass of the epoxy resin, it is preferably 0.1 parts by mass to 15 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass. Parts by mass, more preferably 0.8 parts by mass to 5 parts by mass.

(Stress reliever) The underfill material may also contain a stress reliever. The type of stress reliever is not particularly limited. Examples include: Thermoplastic elastomer, Natural Rubber (NR), Acrylonitrile Butadiene Rubber (NBR), Acrylic rubber, Urethane rubber , Silicone rubber and other particles. One kind of stress reliever may be used alone, or two or more kinds may be used in combination.

In the case where the underfill material contains a stress reliever, the content of the stress reliever is not particularly limited. It is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass relative to 100 parts by mass of the epoxy resin. Mass parts.

(Coupling agent) The underfill material may also contain a coupling agent. The type of coupling agent is not particularly limited, and examples include: epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane and other silane compounds; titanium compounds; aluminum chelate compounds; aluminum/ Zirconium compounds, etc. One type of coupling agent may be used alone, or two or more types may be used in combination.

In the case where the underfill material contains a coupling agent, the content of the coupling agent is not particularly limited. Relative to 100 parts by mass of the epoxy resin, it is preferably 0.01 parts by mass to 5 parts by mass, more preferably 0.02 parts by mass to 2.5 parts by mass .

(Ion trap) The underfill material may also contain an ion trap. The type of ion trapping agent is not particularly limited, and examples thereof include compounds represented by the following general formula (VI-1) or the following general formula (VI-2).

Mg _1-a Al _a (OH) ₂ (CO ₃ ) _a/2 ·uH ₂ O (VI-1) (In the general formula (VI-1), a is 0<a≦0.5, u is a positive number) BiO _b (OH) _c (NO ₃ ) _d (VI-2) (In the general formula (VI-2), b is 0.9≦b≦1.1, c is 0.6≦c≦0.8, and d is 0.2≦d≦0.4)

The ion scavenger can be obtained in the form of a commercially available product. As the compound represented by the general formula (VI-1), for example, "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd., trade name) can be obtained as a commercially available product. In addition, as the compound represented by the general formula (VI-2), for example, "IXE500" (manufactured by Toagosei Co., Ltd., trade name) can be obtained as a commercially available product.

In addition, examples of ion scavengers other than those described above include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like. One kind of ion scavenger may be used alone, or two or more kinds may be used in combination.

In the case where the underfill material contains an ion scavenger, the content of the ion scavenger is not particularly limited. From the viewpoint of achieving sufficient moisture resistance reliability, it is preferably 1 part by mass relative to 100 parts by mass of epoxy resin Above, more preferably 2 parts by mass or more. From the viewpoint of fully exerting the effects of other components, the content of the ion scavenger is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less relative to 100 parts by mass of the epoxy resin. From the above viewpoints, the content of the ion scavenger is preferably 1 part by mass to 15 parts by mass, more preferably 1 part by mass to 10 parts by mass, and still more preferably 2 parts by mass to 100 parts by mass of epoxy resin. 5 parts by mass.

In addition, the average particle diameter of the ion scavenger is preferably 0.1 μm to 3.0 μm, and the maximum particle diameter is preferably 10 μm or less. The average particle diameter of the ion scavenger can be measured in the same manner as in the case of the inorganic filler.

(Exudation inhibitor) The underfill material may also contain an exudation inhibitor. The type of bleed inhibitor is not particularly limited, and examples include nonionic surfactants, silicone-modified epoxy resins, and the like. One kind of exudation inhibitor may be used alone, or two or more kinds may be used in combination.

The content of the exudation inhibitor is not particularly limited. With respect to 100 parts by mass of the epoxy resin, it is preferably 0.1 parts by mass to 5 parts by mass, more preferably 0.2 parts by mass to 2 parts by mass, and still more preferably 0.3 parts by mass to 1 part by mass. share.

(Colorant) The underfill material may also contain colorants. The type of coloring agent is not particularly limited, and examples thereof include carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide (Bengala). A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more types.

When the underfill material contains a colorant, the content of the colorant is not particularly limited, and it is preferably 0.001 part by mass to 1 part by mass, and more preferably 0.02 part by mass to 0.5 part by mass relative to the total amount of the underfill material.

[Preparation method of underfill material] The underfill material can be obtained, for example, by performing stirring, melting, mixing, dispersing, etc., while applying heat treatment to each component collectively or separately as necessary. The device used for mixing, stirring, dispersing, etc. of these components is not particularly limited, and examples include a crushing machine, three-roll mill, ball mill, planetary mixer, bead mill, etc., including a stirring device, heating device, etc. . Using these devices, the components are mixed, kneaded, and defoamed as necessary, thereby obtaining an underfill material.

[Use of underfill material] Underfill materials can be used in various packaging technologies. In particular, the underfill material of the present disclosure can be preferably used as the underfill material used in flip-chip packaging technology, that is, it can be preferably used to fill the gap between the semiconductor element and the substrate that are bonded by bumps or the like. The purpose of the crevice. In addition, the underfill material of the present disclosure can be preferably used as the underfill material used in the flip-chip packaging technology using copper pillars.

The types of semiconductor elements and substrates are not particularly limited, and can be appropriately selected from among ordinary users in the field of semiconductor packaging. The method of using the underfill material to fill the gap between the semiconductor element and the substrate is not particularly limited.

＜＜Semiconductor Package＞＞ The semiconductor package of the present disclosure includes a substrate, a semiconductor element arranged on the substrate, and a cured product of the underfill material of the present disclosure that seals the semiconductor element.

In semiconductor packaging, the types of semiconductor elements and substrates are not particularly limited, and can be appropriately selected from general users in the field of semiconductor packaging. From the viewpoint that the underfill material of the present disclosure is particularly useful, the semiconductor package is preferably a flip-chip package type semiconductor package, and more preferably a flip-chip package type that uses copper pillars as bumps for connecting semiconductor elements and substrates. Semiconductor packaging.

＜＜Method of manufacturing semiconductor package＞＞ The manufacturing method of the semiconductor package of the present disclosure includes: using the underfill material of the present disclosure to fill the gap between the substrate and the semiconductor element disposed on the substrate; and the step of hardening the underfill material.

The details of the semiconductor package are as described above. There are no particular restrictions on the method of filling the gap between the semiconductor element and the substrate with the underfill material, and the method of hardening the underfill material after filling. For example, it can be enumerated: after the semiconductor element and the substrate are connected, an underfill material is applied to the gap between the semiconductor element and the substrate by capillary phenomenon, and then the underfill material is cured; and the semiconductor element and the substrate are first added. At least one of the surfaces is provided with an underfill material, and when the semiconductor element and the substrate are connected by thermocompression bonding, the connection of the semiconductor element and the substrate and the hardening reaction of the underfill material are applied together. As the method of applying the underfill material, an injection method, a dispensing method, a printing method, etc. can be cited.

The hardening conditions of the underfill material are not particularly limited. For example, heating at 80°C to 200°C for 1 minute to 150 minutes is preferred. [Example]

Hereinafter, the above-mentioned embodiments will be described in detail with examples, but the scope of the embodiments of the present disclosure is not limited to these examples.

[Preparation of underfill material] The components shown in Table 1 and Table 2 were mixed in the compounding amounts shown in the same table to prepare an underfill material. The details of each component are as follows. In Table 1 and Table 2, blank columns indicate unmixed ingredients.

Epoxy resin 1···Liquid bisphenol F epoxy resin, epoxy equivalent: 160 g/eq, trade name "EPOTOTO YDF-8170C", NIPPON STEEL Chemical& Material) Co., Ltd. Epoxy resin 2···Triglycidyl-p-aminophenol, epoxy equivalent: 95 g/eq, trade name "jER 630", Mitsubishi Chemical Corporation Epoxy resin 3···1,6-bis(glycidyloxy)naphthalene, epoxy equivalent: 143 g/eq, trade name "EPICLON HP-4032D", DIC Co., Ltd. company

Hardener 1···Diethyltoluenediamine, trade name "jER cure (jER cure) W", active hydrogen equivalent: 45 g/eq, Mitsubishi Chemical Corporation Hardener 2···3,3'-diethyl-4,4'-diaminodiphenylmethane, trade name "KAYAHARD AA", active hydrogen equivalent: 63 g/eq, Nippon Kayaku Co., Ltd. Hardener 3···3,4-Dimethyl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic anhydride, trade name "YH-306", Anhydride equivalent: 234 g/eq, Mitsubishi Chemical Corporation Hardener 4···2-allylphenol-formaldehyde polycondensate, trade name "MEH-8000H", active hydrogen equivalent: 140 g/eq, Minghe Chemical Co., Ltd.

Hardening accelerator 1···Triphenylphosphine Hardening accelerator 2···2-Phenyl-4-methyl-5-hydroxymethylimidazole Ion scavenger···Compound represented by general formula (VI-2), trade name: "IXE500", Toagosei Co., Ltd. Coloring agent···Carbon black, trade name "MA-100", Mitsubishi Chemical Corporation Inorganic fillers···Spherical silicon dioxide whose surface is treated with epoxy silane coupling agent, trade name "SE2200-SEJ", volume average particle diameter 0.6 μm, Admatechs Co., Ltd.

As the test compound, the following compounds, which are commercially available, were used.

Compound 1···Triazine derivative (trade name: VD-5, Shikoku Chemical Industry Co., Ltd., the following compound, R is a divalent linking group)

[化2]

Compound 2···Melamine (the following compounds)

[化3]

Compound 3···6-Phenyl-1,3,5-triazine-2,4-diamine (the following compound)

[化4]

Compound 4···3-Amino-1,2,4-triazole (the following compounds)

[化5]

Compound 5···5-Amino-1H-tetrazole (the following compound)

[化6]

Compound 6···1,2,3-benzotriazole (trade name: BT-120, Chengbei Chemical Industry Co., Ltd., the following compound)

[化7]

Compound 7···1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (trade name: BT-LX, Chengbei Chemical Industry Co., Ltd., the following compound)

[化8]

[Table 1] Element unit Example 1 2 3 4 5 6 Epoxy resin Epoxy 1 Mass parts 50 50 50 50 40 30 Epoxy 2 Mass parts 30 30 30 30 40 50 Epoxy 3 Mass parts 20 20 20 20 20 20 hardener Hardener 1 Mass ratio 25 25 25 25 25 25 Hardener 2 Mass ratio 75 75 75 75 75 75 Ion trap Mass parts 3.0 3.0 3.0 3.0 3.0 3.0 Colorant quality% 0.05 0.05 0.05 0.05 0.05 0.05 Test compound Compound 1 quality% 1.0 0.50 0.25 0.10 0.25 0.25 Inorganic filler quality% 60 60 60 60 60 60

[Table 2] Element unit Comparative example 1 2 3 4 5 6 7 8 9 Epoxy resin Epoxy 1 Mass parts 50 50 50 50 50 50 50 50 50 Epoxy 2 Mass parts 30 30 30 30 30 30 30 30 30 Epoxy 3 Mass parts 20 20 20 20 20 20 20 20 20 hardener Hardener 1 Mass ratio 25 25 25 25 25 25 25 Hardener 2 Mass ratio 75 75 75 75 75 75 75 Hardener 3 Mass ratio 100 Hardener 4 Mass ratio 100 Hardening accelerator Hardening accelerator 1 Mass parts 1.0 Hardening accelerator 2 Mass parts 1.0 Ion trap Mass parts 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Colorant quality% 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Test compound Compound 1 quality% 1.0 1.0 Compound 2 quality% 1.0 Compound 3 quality% 1.0 Compound 4 quality% 1.0 Compound 5 quality% 1.0 Compound 6 quality% 1.0 Compound 7 quality% 1.0 Inorganic filler quality% 60 60 60 60 60 60 60 60 60

In Tables 1 and 2, the blending amount of the curing agent is represented by the mass ratio when the total mass of the curing agent is 100. The blending amount of the colorant, the inorganic filler, and the test compound is expressed in terms of the content rate (mass %) relative to the total mass of the underfill material. The blending amounts of the hardening accelerator and the ion scavenger are expressed in parts by mass of each component with respect to 100 parts by mass of the epoxy resin in total. In the underfill material, the ratio of the number of active hydrogens in the curing agent to the number of epoxy groups in the epoxy resin (the number of active hydrogens in the curing agent/the number of epoxy groups in the epoxy resin) is 1.0.

[Evaluation of Viscosity] The viscosity (Pa·s) of the underfill material at 25°C is based on the E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., VISCONIC EHD type (trade name)) (cone angle 3°, rotation speed 10 rpm) Minutes (rpm)) to determine.

[Evaluation of the applicable period] Place the underfill material at 25°C for 24 hours, and then use an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., VISCONIC EHD type (trade name)) (cone angle 3°, rotation speed 10 revolutions per minute ( rpm)) to determine the viscosity at 25°C (viscosity after storage). Among them, for a sample that cannot be measured at 10 revolutions per minute (rpm) due to high viscosity, the measurement is performed at 2.5 revolutions per minute (rpm). The pot life (%) is calculated according to the following formula as the viscosity increase rate after being left for 24 hours. Pot life (%)={(Viscosity after placement-initial viscosity)/initial viscosity}×100

[Evaluation of Adhesion at 25°C or 260°C] ·Adhesion to copper (Cu) A test piece is produced by forming an underfill material with a diameter of 3 mm and a height of 3 mm on the surface of a copper plate. Use a bond tester DS100 model (manufactured by DAGE) at a head speed of 50 μm/sec, 25°C or Shear stress was applied at 260°C, and the strength of the molded product peeled from the copper plate was measured.

The evaluation results are shown in Table 3 and Table 4. In Table 3 and Table 4, "-" indicates non-compliance. The "unmeasurable" in the evaluation of the pot life means that the viscosity increase is large and cannot be measured.

[table 3] project unit Example 1 2 3 4 5 6 Type of test compound - Compound 1 Compound 1 Compound 1 Compound 1 Compound 1 Compound 1 Melting point of test compound °C 89～90 89～90 89～90 89～90 89～90 89～90 The amount of test compound quality% 1.0 0.50 0.25 0.10 0.25 0.25 Viscosity (25℃) Pa·s 27 twenty three twenty two twenty two twenty one 17 Pot life (25℃/24 hours) % 53 62 74 70 63 86 Copper Adhesive 25℃ kgf 7.4 7.1 7.2 6.9 8.2 8.3 260°C kgf 0.92 0.89 0.85 0.81 1.00 0.95

[Table 4] project unit Comparative example 1 2 3 4 5 6 7 8 9 Type of test compound - - Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Compound 7 Compound 1 Compound 1 Melting point of test compound °C - 345 228 150～159 207 95 -(Liquid at 25°C) 89～90 89～90 The amount of test compound quality% - 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Viscosity (25℃) Pa·s twenty three 29 twenty four 27 37 40 twenty three 8 32 Pot life (25℃/24 hours) % 70 68 88 229 Unable to determine Unable to determine 256 118 246 Copper Adhesive 25℃ kgf 10.3 9.0 5.6 7.2 7.7 6.9 6.4 5.7 18.5 260°C kgf 0.45 0.60 0.19 0.30 0.37 0.24 0.23 0.24 0.28

As shown in Tables 3 and 4, the underfill materials of Examples 1 to 6 containing the test compound 1 have excellent pot life and adhesion to copper at 260°C. On the other hand, the underfill material of Comparative Example 1 that did not contain the test compound 1 had a slightly higher adhesion to copper at 25°C, but poor adhesion to copper at 260°C. Among the underfill materials of Comparative Example 2 to Comparative Example 7 containing various test compounds, some have a significantly poor pot life or poor adhesion to copper at 260°C. In addition, although the test compound 1 was included, the underfill material of Comparative Example 8 or Comparative Example 9 in which the curing agent was replaced with the curing agent 3 or the curing agent 4 also had poor pot life and adhesion to copper at 260°C.

The entire content of the disclosure of Japanese Patent Application No. 2020-009238 is incorporated into this specification by reference. All documents, patent applications, and technical specifications described in this specification are cited and incorporated into this specification to the same extent as when specifically and separately described incorporation of each document, patent application, and technical specifications by reference.

without

without

Claims (6)

An underfill material containing: Epoxy resin, Aromatic amine hardener, Inorganic filler materials, and Compound with triazine ring and alkoxysilyl group. The underfill material according to claim 1, wherein the melting point of the compound having a triazine ring and an alkoxysilyl group is 200°C or less. The underfill material according to claim 1 or claim 2, wherein the compound having a triazine ring and an alkoxysilyl group further has a primary amine group. An underfill material containing: Epoxy resin, Aromatic amine hardener, Inorganic filler materials, and A compound with a triazine ring and a primary amine group and a melting point of 200°C or less. A semiconductor package includes: a substrate, a semiconductor element arranged on the substrate, and a cured product of the underfill material according to any one of claims 1 to 4 for sealing the semiconductor element. A method for manufacturing a semiconductor package, comprising: filling the gap between a substrate and a semiconductor element arranged on the substrate with the underfill material according to any one of claim 1 to claim 5; and The step of hardening the underfill material is described.