KR100983096B1 - Underfill Hybrid Epoxy Compositions Having Improved Moisture Resistance and Fluidity - Google Patents

Abstract

The present invention (a) an epoxy resin having two or more glycidyl groups; (b) a hybrid epoxy resin having a siloxane bonded thereto; (c) acid anhydride, siloxane anhydride, silyl anhydride or mixtures thereof as curing agent; And (d) relates to a hybrid epoxy composition for semiconductor underfill with improved moisture resistance and flow resistance comprising a curing accelerator. The underfill composition of the present invention exhibits excellent flowability and can be filled quickly, and also has excellent moisture resistance, thereby improving the reliability of the package.

Epoxy, hybrid, underfill, siloxane

Description

Underfill Hybrid Epoxy Compositions Having Improved Moisture Resistance and Fluidity}

The present invention relates to a hybrid epoxy composition for semiconductor underfill excellent in moisture resistance and flowability.

As electronic products become smaller, thinner, and more versatile, encapsulation and mounting methods for semiconductor devices are also diversifying. An electronic component package for semiconductor devices, such as a cavity down type ball grid array package, a flip chip (FLIP CHIP), which is a type of CSP (chip scale package), and an integrated circuit IC such as a driving integrated circuit IC. A chip on board (COB) process and a potting process of a liquid chip on film (COF) used as an encapsulant are performed.

Flip chip technology is a technology in which the surface of the chip on which the integrated circuit is formed is attached to face the substrate. Flip chip technology may be used in a package or directly on a printed circuit board. When flip chip technology is used in a package, the chips are connected through solder joints, which are called flip chip in packages (FCIP). On the other hand, the case in which the chip is directly connected to the printed circuit board is called a flip chip on board (FCOB) or direct chip attach (DCA). However, when thermal shock test is performed on the flip chip package mounted in this manner, there is room for reliability of the connection between the circuit board and the solder bumps. This is because the different coefficients of thermal expansion of the chip, the wiring board and the solder ball cause thermal stress. In order to alleviate the stress caused by heat, the process of filling the space between the device and the substrate with a resin after mounting the chip on the substrate is an underfill process, and the material used therein is mainly an underfill material having a liquid phase.

Various epoxy resin compositions have been developed as underfill materials, but no epoxy resin compositions have yet been developed that have sufficient moisture resistance and flowability.

The present inventors can quickly fill an underfill space in a semiconductor device such as a flip chip assembly including a semiconductor chip mounted on a carrier substrate, and improve the reliability of the package in consideration of moisture resistance and thermal shock characteristics against moisture absorption. Epoxy resin compositions for underfill excellent in wettability and flowability have been developed and endeavored. As a result, the present invention was completed by confirming that siloxane anhydride or silyl anhydride was used as the hybrid epoxy resin and / or curing agent to which siloxane was bonded, and exhibited the above excellent characteristics.

Accordingly, an object of the present invention is to provide a hybrid epoxy composition for semiconductor underfill with improved moisture resistance and flowability.

Other objects and advantages of the present invention will become apparent from the following detailed description and claims.

According to an aspect of the present invention, the present invention is (a) an epoxy resin having two or more glycidyl groups; (b) hybrid epoxy resins having siloxanes bound thereto; (c) acid anhydride, siloxane anhydride, silyl anhydride or mixtures thereof as curing agent; And (d) provides a hybrid epoxy composition for semiconductor underfill improved moisture resistance and flowability comprising a curing accelerator.

The present inventors can quickly fill an underfill space in a semiconductor device such as a flip chip assembly including a semiconductor chip mounted on a carrier substrate, and improve the reliability of the package in consideration of moisture resistance and thermal shock characteristics against moisture absorption. Epoxy resin compositions for underfill excellent in wettability and flowability have been developed and endeavored. As a result, when siloxane anhydride or silyl anhydride was used as a hybrid epoxy resin and / or a hardening | curing agent to which siloxane was bonded, it confirmed that the said outstanding characteristic was shown.

The underfill epoxy composition of the present invention basically contains an epoxy resin, a curing agent and a curing accelerator.

The epoxy resin used in the present invention is (a) an epoxy resin having two or more glycidyl groups; And (b) two kinds of siloxane-bonded hybrid epoxy resins, or when siloxane anhydride or silyl anhydride is used as the curing agent, (a) an epoxy resin having two or more glycidyl groups; And (b) one type of hybrid epoxy resin to which siloxane is bound or both.

As the epoxy resin used in the present invention, any epoxy resin containing two or more glycidyl groups may be used in the present invention.

According to a preferred embodiment of the present invention, the epoxy resin having two or more glycidyl groups used in the present invention is a bisphenol A type epoxy resin of Formula 1, a bisphenol F type epoxy resin of Formula 2, a trifunctional epoxy resin of Formula 3 , Tetrafunctional epoxy of formula 4, bisphenol S type epoxy resin of formula 5, naphthalene type epoxy resin of formula 6, tert-butyl-catechol epoxy resin of formula 7, phenol novolac type epoxy resin of formula 8, cresol furnace A volac epoxy resin, a brominated bisphenol A (BPA) novolac epoxy resin, a hydrogenated BPA type epoxy resin of formula 9 or a mixture of the above epoxy resins:

Formula 1

delete

Formula 2

delete

Formula 3

이고,In Formula 3, R is

ego,

Formula 4

이고,In Formula 4, R is

ego,

Formula 5

In Formula 5, R ₁ and R ₂ are each independently hydrogen or an alkyl group,

6

Formula 7

In Formula 7, R is each independently hydrogen or an alkyl group,

Formula 8

In Formula 8, n is an integer of 1-10,000,

Formula 9

In Formula 9, each R is independently hydrogen or an alkyl group

In the above formula, the alkyl group means a straight-chain or pulverized saturated hydrocarbon group, preferably a C ₁ -C ₁₀ alkyl group, more preferably a C ₁ -C ₄ alkyl group, and most preferably a methyl group.

More preferably, the epoxy resin having two or more glycidyl groups used in the present invention is a bisphenol A type epoxy resin of Formula 1, a bisphenol F type epoxy resin of Formula 2, a trifunctional epoxy resin of Formula 3, Tetrafunctional resin, bisphenol S type epoxy resin of formula (5), tert-butyl-catechol epoxy resin of formula (7), or hydrogenate BPA type epoxy resin of formula (9), most preferably bisphenol F type epoxy resin.

One of the greatest features of the present invention is the use of hybrid epoxy resins in which siloxanes are bonded to improve moisture resistance and flowability.

According to a preferred embodiment of the invention, the siloxane-bonded hybrid epoxy resin is represented by the following general formula (1):

Formula 1

-(E) _m- (S) _n-

In the general formula, E represents an epoxy group, S represents a siloxane, and m and n are integers of 1-100.

The hybrid epoxy resin of the general formula (1) is a copolymer composed of an epoxy group and a siloxane. In Formula 1, the epoxy group and the siloxane may be regularly alternatingly arranged (alternating copolymer) and randomly arranged (random copolymer). In addition, in Formula 1, the epoxy group and the siloxane may be arranged in the form of a block copolymer. In this case, the polysiloxane formed by the polyoxide formed by the two or more continuous epoxy groups and the two or more continuous siloxanes may be arranged alternatively.

More preferably, the hybrid epoxy resin represented by the general formula (1) is a linear block copolymer in which an polyepoxide and a polysiloxane are bonded to each other.

또는

이 하이브리드 에폭시 수지의 적어도 하나의 말단에 결합된다.More preferably, an epoxy group or a cycloaliphatic epoxy group is bonded to at least one terminal and even more preferably both terminals of the hybrid epoxy resin bonded to the siloxane represented by the general formula (1). E.g,

or

It is bonded to at least one terminal of this hybrid epoxy resin.

According to a preferred embodiment of the present invention, the siloxane-bonded hybrid epoxy resin has a silicon content of 20-80 wt%.

According to a preferred embodiment of the present invention, the siloxane-bonded hybrid epoxy resin has an epoxy equivalent weight (EEW) of 600-3000 g / equiv.

According to a preferred embodiment of the present invention, the siloxane-bonded hybrid epoxy resin has a viscosity at room temperature of 20,000-100,000 cps.

The curing agent used in the present invention is an acid anhydride, siloxane anhydride, silyl anhydride or mixtures thereof. The siloxane anhydride and silyl anhydride may not be used when a hybrid epoxy resin having a siloxane bonded thereto is used as the epoxy resin.

Acid anhydrides as the curing agent used in the present invention include any acid anhydride known in the art.

Preferably, the acid anhydride as the curing agent is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric Anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride or 5- (2,5-dioxotetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride. Most preferably, the acid anhydrides suitable for the present invention are methylhexahydrophthalic anhydride.

The siloxane anhydride used as the curing agent in the present invention includes any anhydride including siloxanes.

According to a preferred embodiment of the present invention, the siloxane anhydride as a curing agent is a siloxane anhydride in which both succinic anhydrides represented by the following formula (10) are located at both ends:

Formula 10

And in the formula, R ₁ -R ₆ are independently C _{1 -10} alkyl, C _{1 -10} alkoxy, C _{2 -10} alkenyl or C _{6 -14} aryl group, m is an integer of 1-10 to each other, n Is an integer of 1-100, p is an integer of 1-10.

In Chemical Formula 10, the term “C ₁ -C ₁₀ alkyl” refers to a straight or pulverized saturated hydrocarbon group having 1 to ₁₀ carbon atoms, preferably “C ₁ -C ₄ straight or branched alkyl”, which is a low-cost alkyl. Methyl, ethyl, n -propyl, isopropyl, isobutyl, n -butyl and t -butyl. The term “alkoxy” means an —Oalkyl group. Preferably, the alkoxy group includes methoxy and ethoxy.

The term “alkenyl group” refers to a straight or pulverized unsaturated hydrocarbon group having a specified carbon number, preferably C ₂ -C ₆ straight or branched chain alkenyl, which is a hydrocarbon group having 2 to 6 carbon atoms having at least one double bond. Examples include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, t -butenyl, n -pentenyl and n -hexenyl.

The term "aryl" refers to a substituted or unsubstituted monocyclic or polycyclic carbon ring which is wholly or partially unsaturated, preferably monoaryl or biaryl. Most preferably said aryl is substituted or unsubstituted phenyl.

According to a preferred embodiment of the invention, the silyl anhydride as a curing agent is a silyl anhydride with one succinic anhydride represented by the following formula (11) at one end:

Formula 11

In the formula, R ₁ -R ₃ are independently C _{1 -10} alkyl, C _{1 -10} alkoxy, C _{2 -10} alkenyl or C _{6 -14} aryl group to each other, m is an integer of 1-10.

And in the formula, R ₁ -R ₆ are independently C _{1 -10} alkyl, C _{1 -10} alkoxy, C _{2 -10} alkenyl or C _{6 -14} aryl group, m is an integer of 1-10 to each other, n Is an integer of 1-100, p is an integer of 1-10.

In Formula 11, the term “C ₁ -C ₁₀ alkyl” refers to a straight or pulverized saturated hydrocarbon group having 1 to ₁₀ carbon atoms, preferably “C ₁ -C ₄ straight or branched alkyl”, which is a low-cost alkyl. Methyl, ethyl, n -propyl, isopropyl, isobutyl, n -butyl and t -butyl. The term “alkoxy” means an —Oalkyl group. Preferably, the alkoxy group includes methoxy and ethoxy.

The term “alkenyl group” refers to a straight or pulverized unsaturated hydrocarbon group having a specified carbon number, preferably C ₂ -C ₆ straight or branched chain alkenyl, which is a hydrocarbon group having 2 to 6 carbon atoms having at least one double bond. Examples include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, t -butenyl, n -pentenyl and n -hexenyl.

The term "aryl" refers to a substituted or unsubstituted monocyclic or polycyclic carbon ring which is wholly or partially unsaturated, preferably monoaryl or biaryl. Most preferably said aryl is substituted or unsubstituted phenyl.

Most preferably, the siloxane anhydride and silyl anhydride as hardeners are represented by the following formulas (12) and (13), respectively:

Formula 12

Formula 13

Curing accelerators included in the hybrid epoxy composition of the present invention include any curing accelerator used in the epoxy composition in the art.

According to a preferred embodiment of the present invention, the curing accelerator included in the hybrid epoxy composition of the present invention is -OH, -COOH, SO ₃ H, -CONH ₂ , -CONHR (R represents an alkyl group), -SO ₃ NH ₂ , —SO ₃ NHR (R represents an alkyl group) or a curing accelerator having -SH or an imidazole series curing accelerator. R is preferably C ₁ -C ₁₀ alkyl, which means a straight or pulverized saturated hydrocarbon group having 1-10 carbon atoms, more preferably “C ₁ -C ₄ straight or branched alkyl”, which is a low-cost alkyl. Methyl, ethyl, n -propyl, isopropyl, isobutyl, n -butyl and t -butyl.

More preferably, the curing accelerator used in the present invention is an imidazole series curing accelerator.

Suitable imidazole series curing accelerators for the present invention are imidazole, isimidazole, 2-methyl imidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, butylimidazole, 2- Heptadecenyl-4-methylimidazole, 2-methylimidazole, 2-undecenylimidazole, 1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2-unde Silimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 Guanaminoethyl-2-methylimidazole, adduct of imidazole and methylimidazole, adduct of imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidazole, phenyl Midiazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1- (dodecyl Vaginal) -2-methylimidazole, 2- (2-hydroxy-4-t-butylphenyl) -4,5-diphenylimidazole, 2- (2-methoxyphenyl) -4,5- Diphenylimidazole, 2- (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl-aminophenyl) -4,5-diphenylimidazole, 2- ( 2-hydroxyphenyl) -4,5-diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4, 2-naphthyl-4,5-diphenyl Midisol, 1-benzyl-2-methylimidazole, 2-p-methoxystyrylimidazole and the like.

According to a preferred embodiment of the present invention, the hybrid epoxy composition for semiconductor underfill of the present invention further comprises an epoxy silane coupling agent. Even more preferably, the epoxy silane coupling agent is N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltris (2-ethylethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyl trimethoxysilane, 3-chloropropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, bis [3- (trisethoxysilyl) propyl] tetrasulfide, 3-mercaptopropylmethyldimethoxysilane or 3-mercaptopropyltrimethoxysilane.

According to a preferred embodiment of the present invention, the underfill epoxy composition of the present invention further comprises an amine curing agent, an inorganic filler, a pigment (eg carbon black) or a mixture thereof. Optionally, the underfill epoxy composition of the present invention may include various additives such as air release agents, flow additives, adhesion promoters, and modifiers.

Suitable amine curing agents for the underfill compositions of the present invention include aliphatic amines, modified aliphatic amines, aromatic amines, secondary amines and tertiary amines, and the like, for example benzyldimethylamine, triethanolamine, triethylene Tetramin, diethylenetriamine, triethyleneamine, dimethylaminoethanol, tri (dimethylaminomethyl) phenol and the like.

Available as inorganic fillers include any filler known in the art and are preferably spherical or crushed inorganic ceramics (eg silica, alumina, etc.) having a particle size of 0.01-100 micrometers.

When the underfill composition of the present invention contains an epoxy resin having two or more glycidyl groups, a hybrid epoxy resin having a siloxane bond, an acid anhydride and a curing accelerator as a curing agent, two resin mixtures (two glycidyl groups) The content of the epoxy resin having two or more glycidyl groups is preferably 0.01-99 wt%, more preferably 5, based on the entire mixture of the epoxy resin and the hybrid epoxy resin in which the siloxane is bonded. -95 wt%. The content of the hybrid epoxy resin in which the siloxane is bonded is preferably 0.01-99 wt%, more preferably 5-95 wt%, based on the entire resin mixture. The content of the acid anhydride as the curing agent is preferably 0.01 to 200 parts by weight, more preferably 10 to 120 parts by weight based on 100 parts by weight of the resin. The content of the curing accelerator is preferably 0.01-10 parts by weight, more preferably 0.01-3 parts by weight based on 100 parts by weight of the resin.

When the underfill composition of the present invention contains an epoxy resin having two or more glycidyl groups, a siloxane anhydride or silyl anhydride as a curing agent, and a curing accelerator, an epoxy resin having two or more glycidyl groups is used. The content is preferably 0.01-99 wt%, more preferably 5-95 wt%, based on the total composition. The siloxane anhydride or silyl anhydride as the curing agent is preferably 0.01 to 200 parts by weight, more preferably 0.01 to 120 parts by weight based on 100 parts by weight of the resin. The content of the acid anhydride as the curing agent is preferably 0.01 to 200 parts by weight, more preferably 0.01 to 120 parts by weight based on 100 parts by weight of the resin. The content of the curing accelerator is preferably 0.01-10 parts by weight, more preferably 0.01-3 parts by weight based on 100 parts by weight of the resin.

According to a preferred embodiment of the present invention, the hybrid epoxy composition for underfill of the present invention exhibits a moisture absorption of 0.20-1.3%. The moisture absorption rate was analyzed by measuring the change in weight after 24 hours of moisture absorption in a constant temperature and humidity chamber of 85 ℃ / 85 RH (relative humidity)% conditions as described in the following examples. As demonstrated in the following Experimental Example, the hybrid epoxy composition for underfill of the present invention shows very low moisture absorption of 1.1% or less, it can be seen that it has excellent moisture resistance.

In addition, as can be seen in the experimental example, the underfill hybrid epoxy composition of the present invention shows a penetration rate of less than 15 seconds, it can be seen that the flowability is very excellent.

As described above, the present invention provides a hybrid epoxy composition for underfill. The underfill composition of the present invention exhibits excellent flowability and can be filled quickly, and also has excellent moisture resistance, thereby improving the reliability of the package.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Example  One

Next, the composition of Table 1 was prepared, and a spherical silica (average particle size of 5 μm) was mixed in a weight ratio of 25:75 to finally prepare an epoxy resin composition for semiconductor underfill of the present invention.

Raw material Content (Phr) Bisphenol F type epoxy resin ¹⁾ 100 MHHPA ²⁾ 45 Succinic anhydride terminated polydimethoxysiloxane ³⁾ 45 Epoxy silane coupling agent ⁴⁾ 0.5 BDMA ⁵⁾ One EI-24C ⁶⁾ One

¹⁾ Kukdo Chemical Co., Ltd., viscosity 3500-4500 cps; ²⁾ methylhexahydrophthalic anhydride, Kukdo Chemical Co., Ltd .; ³⁾ succinic anhydride terminated polydimethylsiloxane, Gelest Co .; ⁴⁾ epoxy silane, UCT Co., Ltd .; ⁵⁾ benzyldimethylamine, sigma aldrich; ⁶⁾ imidazole curing accelerator, Shikoku Co., Ltd.

Example  2

Next, the composition of Table 2 was prepared, and a spherical silica (average particle size of 5 μm) was mixed in a weight ratio of 25:75 to finally prepare an epoxy resin composition for semiconductor underfill of the present invention.

Raw material Content (Phr) Bisphenol F type epoxy resin ¹⁾ 100 MHHPA ²⁾ 45 3- (triethoxysilyl) propylsuccinic anhydride ³⁾ 45 Epoxy silane coupling agent ⁴⁾ 0.5 BDMA ⁵⁾ One EI-24C ⁶⁾ One

¹⁾ Kukdo Chemical Co., Ltd., viscosity 3500-4500 cps; ²⁾ methylhexahydrophthalic anhydride, Kukdo Chemical Co., Ltd .; ³⁾ 3- (triethoxysilyl) propylsuccinic anhydride, Gelest Co .; ⁴⁾ Epoxysilane, UCT Co., Ltd .; ⁵⁾ benzyldimethylamine, sigma aldrich; ⁶⁾ imidazole curing accelerator, Shikoku Co., Ltd.

Example  3

Next, the composition of Table 3 was prepared, and a spherical silica (average particle size of 5 μm) was mixed in a weight ratio of 25:75 to finally prepare an epoxy resin composition for semiconductor underfill of the present invention.

Raw material Content (Phr) Bisphenol F type epoxy resin ¹⁾ 95 Hybrid Epoxy Resin Bonded with Siloxane ²⁾ 5 MHHPA ³⁾ 90 Epoxy silane coupling agent ⁴⁾ 0.5 BDMA ⁵⁾ One EI-24C ⁶⁾ One

이 결합된 하이브리드 에폭시 수지; ³⁾메틸헥사하이드로프탈산 무수물, (주)국도화학; ⁴⁾에폭시 실란, (주)UCT; ⁵⁾벤질디메틸아민, 시그마 알드리치; ⁶⁾이미다졸 경화 촉진제, (주)시코쿠 ¹⁾ Kukdo Chemical Co., Ltd., viscosity 3500-4500 cps; ²⁾ linear block copolymers in which polyepoxides and polysiloxanes are bonded alderatively at both ends;

This bonded hybrid epoxy resin; ³⁾ methylhexahydrophthalic anhydride, Kukdo Chemical Co., Ltd .; ⁴⁾ epoxy silane, UCT Co., Ltd .; ⁵⁾ benzyldimethylamine, sigma aldrich; ⁶⁾ imidazole curing accelerator, Shikoku Co., Ltd.

Example  4

Next, the composition of Table 4 was prepared, and spherical silica (average particle size of 5 μm) was mixed in a weight ratio of 25:75 to finally prepare an epoxy resin composition for semiconductor underfill of the present invention.

Raw material Content (Phr) Bisphenol F type epoxy resin ¹⁾ 10 Hybrid Epoxy Resin Bonded with Siloxane ²⁾ 90 MHHPA ³⁾ 90 Epoxy silane coupling agent ⁴⁾ 0.5 BDMA ⁵⁾ One EI-24C ⁶⁾ One

이 결합된 하이브리드 에폭시 수지; ³⁾메틸헥사하이드로프탈산 무수물, (주)국도화학; ⁴⁾에폭시 실란, (주)UCT; ⁵⁾벤질디메틸아민, 시그마 알드리치; ⁶⁾이미다졸 경화 촉진제, (주)시코쿠 ¹⁾ Kukdo Chemical Co., Ltd., viscosity 3500-4500 cps; ²⁾ linear block copolymers in which polyepoxides and polysiloxanes are bonded alderatively at both ends;

This bonded hybrid epoxy resin; ³⁾ methylhexahydrophthalic anhydride, Kukdo Chemical Co., Ltd .; ⁴⁾ epoxy silane, UCT Co., Ltd .; ⁵⁾ benzyldimethylamine, sigma aldrich; ⁶⁾ imidazole curing accelerator, Shikoku Co., Ltd.

Experimental Example  One: For underfill  Characterization of Epoxy Resin Compositions

Various properties were analyzed for the underfill epoxy resin compositions prepared in Comparative Examples and Examples, and the results are shown in Table 6.

Measurement item Example 1 Example 2 Example 3 Example 4 Viscosity 25
(cps) 300 ± 50 300 ± 50 400 ± 50 35,000 ± 1,000 Glass transition temperature 110 ± 10 ℃ 110 ± 10 ℃ 108 ± 10 ℃ 110 ± 10 ℃ Coefficient of thermal expansion Alpha 1 75 82 92 25 Alpha 2 175 180 190 113 Gel time at 150 ℃ 100 ± 5 seconds 100 ± 5 seconds 120 ± 5 seconds 100 ± 5 seconds Moisture absorption 1.1% 1.1% 1.05% 0.35% Penetration speed <15 seconds <15 seconds <15 seconds <30 seconds

The analysis was as follows:

1) Viscosity Cone amp: Measured at 25 ° C. using a plate Brookfield viscometer.

2) Glass transition temperature (Tg) and coefficient of thermal expansion: evaluated by TMA (Thermo Mechanical Analyser) (heating rate 10 ℃ / min)

3) Gelation time: Evaluated with a sample amount of 20-30 mg at 150 ° C. with a hot plate. Using the stopwatch, the time point at which the liquid composition cured and became a solid phase was measured.

4) Moisture Absorption: After 24 hours of moisture absorption in a constant temperature and humidity chamber at 85 ° C./85 RH%, the change in weight is measured (saturation state measurement).

5) Penetration rate measurement: Cover glass of 400 x 400 mil with L-shape on the cover glass edge with a gap of 24 μm (2 mil) on BT resin substrate, and the liquid epoxy composition reaches the opposite edge by capillary effect. Measure the time to do (80 ℃).

As can be seen from the above table, the epoxy composition of the present invention has a low moisture absorption rate. Typically, the epoxy composition exhibits a moisture absorption rate of 1.5% or more, but the epoxy composition of the present invention exhibits a moisture absorption rate of 1.1% or less, in particular, in Example 4, a moisture absorption rate of 0.35%. Therefore, it can be seen that the epoxy composition of the present invention is very excellent in moisture resistance required for the underfill composition.

In addition, the epoxy composition of the present invention has a very fast penetration rate. As can be seen from the table, the epoxy composition of the present invention exhibits a penetration rate of 15 seconds or less except for Example 4. Therefore, it can be seen that the epoxy composition of the present invention is very excellent in the flowability required in the underfill composition.

Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that the specific technology is merely a preferred embodiment, and the scope of the present invention is not limited thereto. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (13)

(a) epoxy resins having two or more glycidyl groups; (b) a hybrid epoxy resin having a siloxane bonded thereto; (c) 0.01-200 parts by weight of a curing agent based on 100 parts by weight of the resin as an acid anhydride, a mixture of acid anhydride and siloxane anhydride or a mixture of acid anhydride and silyl anhydride; (d) 0.01-10 parts by weight of a curing accelerator based on 100 parts by weight of the resin; Moisture and flow resistance properties include (e) a silane coupling agent and (f) a spherical or crushed inorganic ceramic having a particle size of 0.01-100 micrometers, which is three times by weight to the weight of (a)-(e). Improved hybrid epoxy composition for semiconductor underfill. The epoxy resin of claim 1, wherein the epoxy resin having two or more glycidyl groups is a bisphenol A type epoxy resin of Formula 1, a bisphenol F type epoxy resin of Formula 2, a trifunctional epoxy resin of Formula 3, or a tetrafunctional of Formula 4 Epoxy, bisphenol S type epoxy resin of formula 5, naphthalene type epoxy resin of formula 6, tert-butyl-catechol epoxy resin of formula 7, phenol novolac type epoxy resin of formula 8, cresol novolac epoxy resin, BPA (brominated) bisphenol A) a novolak epoxy resin, a hydrogenated BPA type epoxy resin of formula 9 or a hybrid epoxy composition for a semiconductor underfill, characterized in that a mixture of the epoxy resins: Formula 1

Formula 2

Formula 3

In Formula 3, R is

ego, Formula 4

In Formula 4, R is

ego, Formula 5

In Formula 5, R ₁ and R ₂ are each independently hydrogen or an alkyl group, 6

Formula 7

In Formula 7, R is each independently hydrogen or an alkyl group, Formula 8

In Formula 8, n is an integer of 1-10,000, Formula 9

In Formula 9, each R is independently hydrogen or an alkyl group The hybrid epoxy composition for semiconductor underfill according to claim 1, wherein the siloxane-bonded hybrid epoxy resin is represented by the following general formula (1): Formula 1 -(E) _m- (S) _n- In the general formula, E represents an epoxy group, S represents a siloxane, and m and n are integers of 1-100. The hybrid epoxy composition for semiconductor underfill according to claim 3, wherein an epoxy group or a cycloaliphatic epoxy group is bonded to at least one end of the hybrid epoxy resin having a siloxane bond represented by the general formula (1). The acid anhydride as the curing agent is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, Glutaric anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride or 5- (2,5-dioxotetrahydro) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid It is anhydride, The hybrid epoxy composition for semiconductor underfills characterized by the above-mentioned. The hybrid epoxy composition for semiconductor underfill according to claim 1, wherein the siloxane anhydride as the curing agent is represented by the following Chemical Formula 10: Formula 10

And in the formula, R ₁ -R ₆ are independently C _{1 -10} alkyl, C _{1 -10} alkoxy, C _{2 -10} alkenyl or C _{6 -14} aryl group, m is an integer of 1-10 to each other, n Is an integer of 1-100, p is an integer of 1-10. 2. The hybrid epoxy composition for semiconductor underfill according to claim 1, wherein the silyl anhydride as the curing agent is represented by the following general formula (11): Formula 11

In the formula, R ₁ -R ₃ are independently C _{1 -10} alkyl, C _{1 -10} alkoxy, C _{2 -10} alkenyl or C _{6 -14} aryl group to each other, m is an integer of 1-10. According to claim 1, wherein the curing accelerator is -OH, -COOH, SO ₃ H, -CONH ₂ , -CONHR (R represents an alkyl group), -SO ₃ NH ₂ , -SO ₃ NHR (R is An alkyl group) or a curing accelerator having -SH or an imidazole series curing accelerator. delete The method of claim 1, wherein the silane coupling agent is N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltris (2-ethylethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, bis [ 3- (trisethoxysilyl) propyl] tetrasulfide, 3-mercaptopropylmethyldimethoxysilane, or 3-mercaptopropyltrimethoxysilane. A hybrid epoxy composition for semiconductor underfill. The hybrid epoxy composition for semiconductor underfill according to claim 1, wherein the siloxane-bonded hybrid epoxy resin has a silicon content of 20-80 wt%. The hybrid epoxy composition of claim 1, wherein the siloxane-bonded hybrid epoxy resin has an epoxy equivalent weight (EEW) of 600-3000 g / equiv. The hybrid epoxy composition for semiconductor underfill according to claim 1, wherein the hybrid epoxy composition for underfill exhibits a moisture absorption of 0.20-1.3%.