TW201910422A - Epoxy resin composition - Google Patents

Epoxy resin composition Download PDF

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TW201910422A
TW201910422A TW107125662A TW107125662A TW201910422A TW 201910422 A TW201910422 A TW 201910422A TW 107125662 A TW107125662 A TW 107125662A TW 107125662 A TW107125662 A TW 107125662A TW 201910422 A TW201910422 A TW 201910422A
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epoxy resin
resin composition
viscosity
composition according
item
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TWI669341B (en
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徐浩然
李恩貞
李歡希
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南韓商Kcc公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32Epoxy compounds containing three or more epoxy groups
    • C08G59/38Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • C08G59/28Di-epoxy compounds containing acyclic nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014Nitrogen containing compounds
    • C08G59/4042Imines; Imides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention relates to an epoxy resin composition comprising an epoxy resin, an inorganic filler and a curing agent, wherein the epoxy resin is an epoxy mixture resin of a low-viscosity epoxy resin having a viscosity of 500 to 4,000 cps at 25 DEG C and a multifunctional epoxy resin having tri- or more functionalities, and the inorganic filler has an average particle size of 0.1 [mu]m to 5 [mu]m.

Description

環氧樹脂組合物Epoxy resin composition

本發明是有關於一種環氧樹脂組合物。The present invention relates to an epoxy resin composition.

隨著電子產品的微型化、重量減輕及薄型化、多功能化,半導體裝置之密封與建造方法亦隨之多樣化。尤其,表面黏著技術(surface mount technology)成為傳統引腳插入型(pin insert type)中的主流,且表面黏著技術封裝中有一種用於覆晶(flip chip)的黏著類型。此類型係為一種並非如往常透過打線接合(wire bonding)接觸而藉由晶片表面透過焊錫球(solder ball)或凸塊與基板之連結使微型化與薄型化成為可能的技術。With the miniaturization, weight reduction, thinness, and multifunctionality of electronic products, the sealing and construction methods of semiconductor devices have also diversified. In particular, surface mount technology has become the mainstream in traditional pin insert types, and a surface mount technology package has an adhesive type for flip chips. This type is a technology that makes miniaturization and thinning possible through the connection of a wafer surface through a solder ball or a bump to a substrate, rather than through a wire bonding contact as usual.

然而,如果以這類方法黏著的覆晶封裝經歷熱衝擊(thermal shock)測試,恐怕可能使關於電路板(circuit board)與焊錫凸塊(solder bump)之間連結狀態的可靠度缺陷增加,因為晶片、接線板(wire board)與焊錫球(solder ball)之熱膨脹係數(thermal expansion coefficient)相異會誘發熱應力(thermal stress)。為了緩和熱引起的應力,進行使晶片黏著於基板上且使樹脂裝填入裝置與基板之間的空間的製程(所謂的底部填充製程(underfill process))。用於此製程的材料為底部填充材料,且此材料通常具有液相,也就是說,這類底部填充製程係藉由施加底部填充材料如環氧樹脂組合物於焊球(solder ball)與墊(pad)之間的空間加以達成。However, if a flip-chip package adhered in this way is subjected to a thermal shock test, it is possible that reliability defects regarding the connection state between the circuit board and solder bumps may increase because Different thermal expansion coefficients of a chip, a wire board, and a solder ball can induce thermal stress. In order to alleviate the stress caused by heat, a process is performed in which a wafer is adhered to a substrate and a resin is filled into a space between the device and the substrate (a so-called underfill process). The material used for this process is an underfill material, and this material usually has a liquid phase, that is, this type of underfill process is performed by applying an underfill material such as an epoxy resin composition to a solder ball and a pad. (pad).

考慮到加工性(workability),這類底部填充材料必須具有裝填能力(packing ability)以滲入晶片與基板之間的孔隙,這類底部填充材料必須具有一定程度上不會與焊錫球(solder ball)的熱膨脹係數相差太多的小的熱膨脹係數,考慮到可靠度,這類底部填充材料必須具有良好的黏著力(adhesion),即於晶片與基板之接觸面的黏著性(adhesiveness),且這類底部填膠材料必須緩和前述之熱應力。然而,雖然其裝填能力是優異的且加工性被提升,裝填後可能造成環氧樹脂之缺陷,如滲出(bleeding)與溢流(overflow)。若反應熱小且未完成充足的揮發(volatilization)及氣泡移除,可能造成空洞(voids)與加工性之缺陷。In view of workability, such underfill materials must have a packing ability to penetrate the pores between the wafer and the substrate. Such underfill materials must have a degree of resistance to solder balls. The coefficient of thermal expansion is too small for a small coefficient of thermal expansion. Considering reliability, such underfill materials must have good adhesion, that is, the adhesiveness at the interface between the wafer and the substrate. The underfill material must alleviate the aforementioned thermal stress. However, although its filling ability is excellent and processability is improved, defects such as bleeding and overflow may be caused after the filling by epoxy resin. If the reaction heat is small and sufficient volatilization and bubble removal are not completed, voids and processability defects may be caused.

因此,開發一種可緩和黏著性、裝填能力與熱應力、使缺陷生成最小化、且具有優異的加工性及可靠度的用於底部填充之環氧樹脂組合物係為必要的。Therefore, it is necessary to develop an epoxy resin composition system for underfill that can alleviate adhesion, filling ability and thermal stress, minimize defect generation, and has excellent processability and reliability.

[先前技術文件][Prior Technical Document]

[專利文獻][Patent Literature]

(專利文獻1) 韓國專利號10-0529256(Patent Document 1) Korean Patent No. 10-0529256

本發明之一方面係提供一種環氧樹脂組合物。One aspect of the present invention is to provide an epoxy resin composition.

本發明提供一種環氧樹脂組合物,其包含一環氧樹脂(epoxy resin)、一無機填充劑(inorganic filler)及一固化劑(curing agent),其中環氧樹脂為一低黏度(viscosity)環氧樹脂與一多官能基環氧樹脂(multifunctional epoxy resin)之環氧樹脂混合物,此低黏度環氧樹脂於25 °C下具有一500 cps至4,000 cps的黏度,此多官能基環氧樹脂具有三或更多個官能基,且無機填充劑具有一0.1微米(μm)至5微米(μm)的平均粒徑。The invention provides an epoxy resin composition comprising an epoxy resin, an inorganic filler and a curing agent, wherein the epoxy resin is a low-viscosity ring An epoxy resin mixture of an epoxy resin and a multifunctional epoxy resin. This low viscosity epoxy resin has a viscosity of 500 cps to 4,000 cps at 25 ° C. This multifunctional epoxy resin has Three or more functional groups, and the inorganic filler has an average particle diameter of 0.1 micrometer (μm) to 5 micrometers (μm).

有益效果Beneficial effect

根據本發明之實施例的環氧樹脂組合物,由於容易控制其黏度可實現優異的流度(fluidity)與流動性(flowability),且尤其由於優異的黏著性、裝填能力與熱應力可獲得穩定的加工性與優異的附接可靠度(attachment reliability)。According to the epoxy resin composition of the embodiment of the present invention, excellent fluidity and flowability can be achieved due to easy control of its viscosity, and stability can be achieved especially due to excellent adhesion, filling ability, and thermal stress Processability and excellent attachment reliability.

以下,將更詳細描述本發明以協助理解本發明。Hereinafter, the present invention will be described in more detail to assist in understanding the present invention.

應理解的是,本發明之說明書與申請專利範圍之用字或用詞不應以一般使用的字典定義之含意加以解讀。應進一步理解的是,基於發明人可適當定義用字或用詞之含意以最佳地描述本發明的原則,用字或用詞應解讀為具備與本發明技術概念之含意一致的含意。It should be understood that the words or terms used in the description of the present invention and the scope of patent application should not be interpreted with the meaning of a dictionary definition generally used. It should be further understood that, based on the inventor's ability to appropriately define the meaning of words or terms to best describe the principles of the present invention, the words or words should be interpreted as having meanings consistent with the meaning of the technical concept of the present invention.

根據本發明之實施例的環氧樹脂組合物包含一環氧樹脂、一無機填充劑及一固化劑,且環氧樹脂係為一低黏度環氧樹脂與一多官能基環氧樹脂之環氧樹脂混合物,此低黏度環氧樹脂於25 °C下具有一500 cps至4,000 cps的黏度,此多官能基環氧樹脂具有三或更多個官能基,且無機填充劑具有一0.1微米至5微米的平均粒徑。The epoxy resin composition according to the embodiment of the present invention includes an epoxy resin, an inorganic filler and a curing agent, and the epoxy resin is an epoxy resin of a low viscosity epoxy resin and a multifunctional epoxy resin. Resin mixture, this low viscosity epoxy resin has a viscosity of 500 cps to 4,000 cps at 25 ° C, this multifunctional epoxy resin has three or more functional groups, and the inorganic filler has a thickness of 0.1 microns to 5 The average particle size in microns.

根據本發明之實施例的環氧樹脂組合物,可輕易控制其黏度,裝填能力與流動性可為優異的,可提升其加工性,且可使組合物裝填後可能造成的滲出或空洞缺陷最小化,且從而可達成優異的可靠度。According to the epoxy resin composition of the embodiment of the present invention, its viscosity can be easily controlled, its filling ability and fluidity can be excellent, its processability can be improved, and it is possible to minimize oozing or void defects that may be caused after the composition is filled. And thus can achieve excellent reliability.

以下,將更詳細描述本發明。Hereinafter, the present invention will be described in more detail.

根據本發明之實施例的環氧樹脂組合物包含一環氧樹脂、一無機填充劑及一固化劑。An epoxy resin composition according to an embodiment of the present invention includes an epoxy resin, an inorganic filler, and a curing agent.

<環氧樹脂>< Epoxy resin >

根據本發明之實施例的環氧樹脂包含二或更多不同種類的環氧樹脂混合物,且可包含於25 °C下具有500 cps至4,000 cps的黏度的低黏度環氧樹脂及具有三或更多個官能基的多官能基環氧樹脂。The epoxy resin according to the embodiment of the present invention includes two or more different kinds of epoxy resin mixtures, and may include a low-viscosity epoxy resin having a viscosity of 500 cps to 4,000 cps at 25 ° C and three or more Multifunctional epoxy resin with multiple functional groups.

根據本發明之實施例的環氧樹脂組合物可包含含量為10重量份至60重量份的環氧樹脂,特別是15重量份至50重量份。若環氧樹脂包含於此含量範圍內,可輕易控制黏度,加工性可為優異的,且裝填能力與流動性可被提升。The epoxy resin composition according to an embodiment of the present invention may include the epoxy resin in an amount of 10 to 60 parts by weight, particularly 15 to 50 parts by weight. If the epoxy resin is included in this content range, the viscosity can be easily controlled, the processability can be excellent, and the filling ability and flowability can be improved.

(低黏度環氧樹脂於25 °C下具有一500 cps至4,000 cps的黏度)(Low viscosity epoxy resin with a viscosity of 500 cps to 4,000 cps at 25 ° C)

根據本發明之實施例的環氧樹脂組合物包含一於25 °C下具有一500 cps至4,000 cps的黏度的低黏度環氧樹脂,且可提升裝填能力與流動性(由於優異的流度使其得以快速滲進晶片與基板之間的孔隙)。在此情況中,黏度可藉由使用如布氏黏度計(Brookfield viscometer)加以測量。The epoxy resin composition according to the embodiment of the present invention includes a low viscosity epoxy resin having a viscosity of 500 cps to 4,000 cps at 25 ° C, and can improve the filling ability and fluidity (due to the excellent fluidity) (It can quickly penetrate into the gap between the wafer and the substrate). In this case, the viscosity can be measured by using, for example, a Brookfield viscometer.

具有一500 cps至4,000 cps的黏度的低黏度環氧樹脂,可以具有1,000 cps至3,500 cps的黏度,更尤其是1,500 cps至3,500 cps的黏度。若包含此黏度範圍內的環氧樹脂,可輕易控制黏度,可提升裝填能力與流動性,且可有利於加工性。若環氧樹脂包含一具有高於4,000 cps的黏度的高黏度環氧樹脂,把使用組合物的底部填充劑裝填於基板上之後,底部填充劑可溢流出基板外,且發生滲出之面積可能增加。Low viscosity epoxy resins with a viscosity of 500 cps to 4,000 cps can have a viscosity of 1,000 cps to 3,500 cps, and more particularly a viscosity of 1,500 cps to 3,500 cps. If the epoxy resin in this viscosity range is included, the viscosity can be easily controlled, the filling ability and fluidity can be improved, and the processability can be facilitated. If the epoxy resin contains a high-viscosity epoxy resin having a viscosity higher than 4,000 cps, after the underfill agent using the composition is filled on the substrate, the underfill agent may overflow out of the substrate, and the area where bleeding occurs may increase .

根據本發明之實施例,具有500 cps至4,000 cps的黏度的低黏度環氧樹脂可包含下列[化學式1]之化合物:According to an embodiment of the present invention, the low viscosity epoxy resin having a viscosity of 500 cps to 4,000 cps may include the following compound of [Chemical Formula 1]:

[化學式1][Chemical Formula 1]

在[化學式1]中,In [Chemical Formula 1],

R為5至15個碳原子的烴基(hydrocarbon)。R is a hydrocarbon of 5 to 15 carbon atoms.

尤其,[化學式1]的化合物係為一低黏度、低氯含量的環氧樹脂,且可為雙酚A型(bisphenol A-type)、雙酚F型(bisphenol F-type)或其樹脂混合物,且尤其可包含一下列[化學式2]之化合物:In particular, the compound of [Chemical Formula 1] is a low viscosity, low chlorine content epoxy resin, and may be bisphenol A-type, bisphenol F-type, or a resin mixture thereof. , And may especially include one of the following [Chemical Formula 2] compounds:

[化學式2][Chemical Formula 2]

根據本發明之實施例,具有一500 cps至4,000 cps的黏度的低黏度環氧樹脂之含量可為10重量份至60重量份,特別是15重量份至50重量份。若低黏度環氧樹脂的含量高於此範圍,黏度可能增加使流動性與裝填能力下降且使加工性下降。反之,若低黏度環氧樹脂的含量低於此範圍,裝填能力與流動性可能下降。According to an embodiment of the present invention, the content of the low viscosity epoxy resin having a viscosity of 500 cps to 4,000 cps may be 10 parts by weight to 60 parts by weight, particularly 15 parts by weight to 50 parts by weight. If the content of the low-viscosity epoxy resin is higher than this range, the viscosity may increase to decrease the flowability and filling ability and reduce the processability. Conversely, if the content of the low-viscosity epoxy resin is lower than this range, the filling ability and fluidity may decrease.

(具有三或更多個官能基的多官能基環氧樹脂)(Polyfunctional epoxy resin with three or more functional groups)

根據本發明之實施例的環氧樹脂組合物包含一具有三或更多個官能基的多官能基環氧樹脂,且可達成高的玻璃轉移溫度(Tg)及增加交聯密度(cross-link density)。The epoxy resin composition according to the embodiment of the present invention includes a polyfunctional epoxy resin having three or more functional groups, and can achieve high glass transition temperature (Tg) and increase cross-link density (cross-link). density).

具有三或更多個官能基的多官能基環氧樹脂可包含一或更多個化合物選自雙酚A型環氧樹脂(bisphenol A-type epoxy resin)、雙酚F型環氧樹脂(bisphenol F-type epoxy resin)、雙酚S型環氧樹脂(bisphenol S-type epoxy resin)、苯酚酚醛型環氧樹脂(phenol novolac-type epoxy resin)、甲酚酚醛型環氧樹脂(cresol novolac-type epoxy resin)、烷基酚酚醛型環氧樹脂(alkylphenol novolac-type epoxy resin) 、雙酚型環氧樹脂(bisphenol-type epoxy resin)、萘型環氧樹脂(naphthalene-type epoxy resin)、二環戊二烯型環氧樹脂(dicyclopentadiene-type epoxy resin)、三縮水甘油基異氰酸酯(triglycidyl isocyanate)、非環狀環氧樹脂(acyclic epoxy resin)及對氨基酚型環氧樹脂(p-amino phenol-type epoxy resin)。例如,多官能基環氧樹脂可包含日本環氧樹脂公司(Japan Epoxy Resins Co., Ltd.)之Epikote 152、Epikote 154、Epikote 828與YX-4000、大日本油墨公司(Dainippon Ink and Chemicals Co., DIC)之Epicron N-660、N-673與N-695、國都化學公司(Kukdo Chemistry Co., Ltd.)之YDCN-500-4P、YDCN-638、YH-300與YH-325、日本環氧樹脂公司(Japan Epoxy Resins Co., Ltd.)之JER 630與JER 604以及荒川化學(Arakawa Chemical Industries, Ltd.)之Compoceran E201與E202,但不限於此。A polyfunctional epoxy resin having three or more functional groups may include one or more compounds selected from the group consisting of bisphenol A-type epoxy resin, bisphenol F-type epoxy resin F-type epoxy resin), bisphenol S-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin epoxy resin), alkylphenol novolac-type epoxy resin, bisphenol-type epoxy resin, naphthalene-type epoxy resin, bicyclic Dicyclopentadiene-type epoxy resin, triglycidyl isocyanate, acyclic epoxy resin, and p-amino phenol- type epoxy resin). For example, the polyfunctional epoxy resin may include Epikote 152, Epikote 154, Epikote 828 and YX-4000 of Japan Epoxy Resins Co., Ltd., Dainippon Ink and Chemicals Co. , DIC) Epicron N-660, N-673 and N-695, Kukdo Chemistry Co., Ltd. YDCN-500-4P, YDCN-638, YH-300 and YH-325, Japan JER 630 and JER 604 of Japan Epoxy Resins Co., Ltd. and Compoceran E201 and E202 of Arakawa Chemical Industries, Ltd., but are not limited thereto.

更尤其,根據本發明之實施例的多官能基環氧樹脂可包含一環氧樹脂、一對氨基酚型環氧樹脂(p-amino phenol-type epoxy resin)及其混合物,在此環氧樹脂中,一液相雙酚A型環氧樹脂(bisphenol A-type epoxy resin)溶解於三官能基反應性稀釋劑(reactive diluent);且尤其更包含一環氧樹脂及一對氨基酚型環氧樹脂(p-amino phenol-type epoxy resin)的混合物,用以提升流度與裝填能力,此環氧樹脂中,一液相雙酚A型環氧樹脂(bisphenol A-type epoxy resin)溶解於三官能基反應性稀釋劑(reactive diluent)。More specifically, the polyfunctional epoxy resin according to the embodiment of the present invention may include an epoxy resin, a pair of p-amino phenol-type epoxy resins, and a mixture thereof. Here, the epoxy resin In the process, a liquid phase bisphenol A-type epoxy resin is dissolved in a trifunctional reactive diluent; in particular, it further comprises an epoxy resin and a pair of aminophenol-type epoxy resins. A mixture of p-amino phenol-type epoxy resin to improve fluidity and filling capacity. In this epoxy resin, a liquid phase bisphenol A-type epoxy resin is dissolved in three Functional group reactive diluent.

具有液相雙酚A型環氧樹脂(bisphenol A-type epoxy resin)溶解於三官能基反應性稀釋劑的環氧樹脂可有利於提供低黏度、於低溫下固化及非結晶度(noncrystallinity)。An epoxy resin having a liquid phase bisphenol A-type epoxy resin dissolved in a trifunctional reactive diluent can be advantageous in providing low viscosity, curing at low temperature, and noncrystallinity.

根據本發明之實施例,三官能基反應性稀釋劑可包含三個官能基選自由羥基(hydroxyl group)、甲醯基(formyl group)、羰基(carbonyl group)、羧基(carboxyl group)、胺基(amino group)、硝基(nitro group)、環氧基(epoxy group)、丙烯酸基(acrylic group)及不飽和鍵(unsaturated bond)組成的群組。According to an embodiment of the present invention, the trifunctional reactive diluent may include three functional groups selected from the group consisting of a hydroxyl group, a formyl group, a carbonyl group, a carboxyl group, and an amine group. (amino group), a nitro group, an epoxy group, an acrylic group, and an unsaturated bond.

尤其,三官能基反應性稀釋劑可包含三個環氧基(epoxy group)作為官能基。In particular, the trifunctional reactive diluent may include three epoxy groups as functional groups.

尤其,多官能基環氧樹脂可具有一4,000 cps至6,000 cps的黏度,且可包含下列[化學式3]之三官能基反應性稀釋劑:In particular, the polyfunctional epoxy resin may have a viscosity of 4,000 cps to 6,000 cps, and may include the following trifunctional reactive diluent of [Chemical Formula 3]:

[化學式3][Chemical Formula 3]

此外,根據本發明之實施例的對氨基酚型環氧樹脂(p-amino phenol-type epoxy resin)可包含例如N,N-bis(2,3-環氧丙基)-4-(2,3-環氧丙氧基)苯胺樹脂 (N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline resin),且可表示為下列[化學式4]:In addition, the p-amino phenol-type epoxy resin according to an embodiment of the present invention may include, for example, N, N-bis (2,3-epoxypropyl) -4- (2, 3-Glycidoxy) aniline resin (N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline resin), and can be expressed as the following [Chemical Formula 4]:

[化學式4][Chemical Formula 4]

根據本發明之實施例,若使用環氧樹脂(此環氧樹脂中,一液相雙酚A型環氧樹脂(bisphenol A-type epoxy resin)溶解於三官能基反應性稀釋劑)與對氨基酚型環氧樹脂(p-amino phenol-type epoxy resin)的樹脂混合物,其重量混合比例可為:例如1:0.6至1:1.5,尤其是1:0.7至1:1。According to the embodiment of the present invention, if an epoxy resin (in this epoxy resin, a liquid phase bisphenol A-type epoxy resin is dissolved in a trifunctional reactive diluent) and p-amino group are used. The resin mixture of p-amino phenol-type epoxy resin may have a weight mixing ratio of, for example, 1: 0.6 to 1: 1.5, especially 1: 0.7 to 1: 1.

根據本發明之實施例,可包含含量為5重量份至20重量份的多官能基環氧樹脂,更尤其是5重量份至15重量份。若多官能基環氧樹脂的含量低於此範圍,熱阻(heat resistance)、化學抗性(chemical resistance)與電性(electrical properties)可能不足,且若多官能基環氧樹脂的含量高於此範圍,阻燃性(flame retardancy)與黏著性可能下降。According to an embodiment of the present invention, the polyfunctional epoxy resin may be contained in an amount of 5 to 20 parts by weight, and more particularly 5 to 15 parts by weight. If the content of the polyfunctional epoxy resin is below this range, heat resistance, chemical resistance, and electrical properties may be insufficient, and if the content of the polyfunctional epoxy resin is higher than Within this range, flame retardancy and adhesion may decrease.

根據本發明之實施例,在環氧樹脂中,低黏度環氧樹脂的含量可高於具有三或更多個官能基的多官能基環氧樹脂的含量。According to an embodiment of the present invention, in the epoxy resin, the content of the low viscosity epoxy resin may be higher than the content of the polyfunctional epoxy resin having three or more functional groups.

根據本發明之實施例,低黏度環氧樹脂(具有一500 cps至4,000 cps的黏度)與多官能基環氧樹脂(具有三或更多個官能基)的重量混合比例可為1:0.1至1:0.8,尤其是1:0.3至1:0.6。若滿足此重量混合比例範圍,可輕易控制環氧樹脂組合物之黏度,且可實現優異的流度,從而提升裝填能力與流動性,且實現高的玻璃轉移溫度(Tg)。According to an embodiment of the present invention, the weight mixing ratio of the low viscosity epoxy resin (having a viscosity of 500 to 4,000 cps) and the polyfunctional epoxy resin (having three or more functional groups) may be 1: 0.1 to 1: 0.8, especially 1: 0.3 to 1: 0.6. If the weight mixing ratio range is satisfied, the viscosity of the epoxy resin composition can be easily controlled, and excellent fluidity can be achieved, thereby improving the filling ability and fluidity, and achieving a high glass transition temperature (Tg).

<無機填充劑>< Inorganic fillers >

根據本發明之實施例的環氧樹脂組合物包含一無機填充劑,此無機填充劑具有一0.1微米至5微米的平均粒徑(D50 ),且可增加樹脂與無機填充劑之間的結合力(binding force),且降低特定表面積由於黏度增加而發生的滲出,還實現了機械性能之提升與應力降低。The epoxy resin composition according to the embodiment of the present invention includes an inorganic filler. The inorganic filler has an average particle diameter (D 50 ) of 0.1 μm to 5 μm, and can increase the bonding between the resin and the inorganic filler. Binding (binding force), and reducing the exudation of a specific surface area due to an increase in viscosity, but also to improve mechanical properties and reduce stress.

無機填充劑可包含多種無機材料,該些無機材料可具備一低的熱膨脹係數(thermal expansion coefficient),但可使用如具有一0.2微米至3微米的平均粒徑(D50 )的二氧化矽(silica),更尤其是0.5微米至2微米。在此情況中,二氧化矽粒子的平均粒徑(D50 )可藉由使用如雷射繞射法(laser diffraction method)加以測量。根據雷射繞射法,通常可從亞微米(submicron)範圍測量至約幾毫米(millimeters)的粒徑,且可獲得高再現性(reproducibility)與高解析度(resolution)的測量結果。The inorganic filler may include a variety of inorganic materials. These inorganic materials may have a low thermal expansion coefficient. However, for example, silicon dioxide (D 50 ) having an average particle diameter (D 50 ) of 0.2 μm to 3 μm may be used. silica), and more particularly 0.5 to 2 microns. In this case, the average particle diameter (D 50 ) of the silicon dioxide particles can be measured by using, for example, a laser diffraction method. According to the laser diffraction method, a particle diameter of about several millimeters can usually be measured from a submicron range, and measurement results with high reproducibility and resolution can be obtained.

根據本發明之實施例,若具有平均粒徑的無機填充劑與環氧樹脂一起使用,可增加環氧樹脂與無機填充劑之間的結合力,可降低特定表面積由於黏度增加而發生的滲出,且可降低高溫下的熱膨脹係數以改善封裝之翹曲現象(warpage phenomenon)。According to the embodiment of the present invention, if an inorganic filler having an average particle diameter is used together with an epoxy resin, the bonding force between the epoxy resin and the inorganic filler can be increased, and the bleeding of a specific surface area due to an increase in viscosity can be reduced. In addition, the thermal expansion coefficient at a high temperature can be reduced to improve the warpage phenomenon of the package.

此外,具有一1微米或更小的小粒徑的微小二氧化矽可用以裝填一微小的凸塊間隙(bump gap),且例如可使用1微米或更小的粉碎型二氧化矽大粒子。在裝填液相樹脂時,粉碎型大粒子可降低黏度,且高密度裝填係為可能的。In addition, micro-silicon dioxide having a small particle diameter of 1 micron or less can be used to fill a tiny bump gap, and for example, pulverized silicon dioxide large particles of 1 micron or less can be used. When filling liquid-phase resin, pulverized large particles can reduce viscosity, and high-density filling systems are possible.

根據本發明之實施例,無機填充劑之含量可在增加與環氧樹脂的結合力及實現高溫下低熱膨脹係數上扮演決定性角色,且例如可為45重量份至70重量份,尤其是50重量份至65重量份。若無機填充劑包含於前述含量範圍內,可增加無機填充劑與樹脂的結合力、可避免晶片破裂,且可使滲出之發生降至最低。若無機填充劑的含量低於前述範圍,可能具有大的熱膨脹係數,且在熱衝擊測試(thermal shock test)期間可能產生破裂,且若無機填充劑的含量高於前述範圍,黏度增加過多且可能產生加工性之缺陷。若使用溶劑降低黏度,可能對固化後的物理性質產生不利影響,且當底部填充製程期間未充分達成揮發與氣泡控制,可能有空洞生成。According to the embodiment of the present invention, the content of the inorganic filler can play a decisive role in increasing the binding force with the epoxy resin and achieving a low thermal expansion coefficient at high temperatures, and may be, for example, 45 to 70 parts by weight, and especially 50 to 50 parts Parts to 65 parts by weight. If the inorganic filler is included in the foregoing content range, the binding force between the inorganic filler and the resin can be increased, wafer cracking can be avoided, and the occurrence of bleeding can be minimized. If the content of the inorganic filler is lower than the foregoing range, it may have a large thermal expansion coefficient, and cracks may occur during the thermal shock test, and if the content of the inorganic filler is higher than the foregoing range, the viscosity increases excessively and may increase Defective workability. If a solvent is used to reduce the viscosity, it may adversely affect the physical properties after curing, and when the volatilization and bubble control are not fully achieved during the underfill process, voids may be formed.

根據本發明之實施例,環氧樹脂混合物與無機填充劑的重量混合比例可為1:0.7至1:3。尤其,低黏度環氧樹脂與無機填充劑的重量混合比例可為1:1.1至1:2。隨著重量混合比例在此範圍中,可提升與樹脂的結合力,且可使滲出之發生降至最低。更具體地,當無機填充劑含量過低,由於流動性不平均可能發生空洞與溢流,且黏度過低以致無法引發滲出。此外,若無機填充劑的含量過高,可能有空洞生成。According to an embodiment of the present invention, a weight mixing ratio of the epoxy resin mixture and the inorganic filler may be 1: 0.7 to 1: 3. In particular, the weight mixing ratio of the low-viscosity epoxy resin and the inorganic filler may be 1: 1.1 to 1: 2. As the weight mixing ratio is in this range, the binding force with the resin can be improved, and the occurrence of bleeding can be minimized. More specifically, when the content of the inorganic filler is too low, voids and overflows may occur due to uneven fluidity, and the viscosity is too low to cause exudation. In addition, if the content of the inorganic filler is too high, voids may be generated.

<固化劑>< curing agent >

根據本發明之實施例的環氧樹脂組合物可包含一用以控制固化速率的固化劑。The epoxy resin composition according to the embodiment of the present invention may include a curing agent for controlling the curing rate.

固化劑可使用胺系(amine-based)固化劑,尤其是具有一低於300 cps的黏度的胺系(amine-based)固化劑。在此情況中,相較於使用其他種類固化劑(例如酸酐固化劑)的情況,此情況可能有利於反應性之控制。更尤其,固化劑可包含選自由聚丙烯醚二胺(polyoxypropylene diamine)、改質脂族胺(modified aliphatic amine)及改質脂環胺(modified alicyclic amine)所組成的群組中至少一材料。例如可使用市售胺系(amine-based)固化劑中Shin-A T&C公司的XHL-0245。The curing agent may be an amine-based curing agent, especially an amine-based curing agent having a viscosity of less than 300 cps. In this case, compared with the case of using other kinds of curing agents (for example, an acid anhydride curing agent), this case may be advantageous for controlling reactivity. More specifically, the curing agent may include at least one material selected from the group consisting of polyoxypropylene diamine, modified aliphatic amine, and modified alicyclic amine. For example, commercially available amine-based curing agent XHL-0245 from Shin-A T & C Company can be used.

根據本發明之實施例,環氧樹脂組合物可包含含量為5重量份至15重量份的固化劑,且在前述範圍內,可輕易控制固化速率,且可獲得適當的固化性質,且從而可提升加工性。According to an embodiment of the present invention, the epoxy resin composition may include a curing agent in an amount of 5 parts by weight to 15 parts by weight, and within the foregoing range, the curing rate can be easily controlled, and appropriate curing properties can be obtained. Improve processability.

<添加劑>< Additives >

根據本發明之實施例的環氧樹脂組合物,在不損害本發明之目的的範圍內,必要時可更包含除了前述成分以外的多種添加劑。例如,可額外使用用以簡單移除氣泡的消泡劑(defoaming agent)、著色劑(coloring agent)、矽烷偶合劑(silane coupling agent)、用以提升滲透性質的表面張力控制劑(surface tension controlling agent)、搖變控制劑(thixotropy controlling agent)、應力消除劑(stress relieving agent)或用以提升無機填充劑凝聚性(agglomeration)的分散劑(dispersing agent);著色劑例如用以提升產品外觀的碳黑(carbon black)等;矽烷偶合劑例如用以提升機械性質與黏著性的環氧丙氧丙基三甲氧基矽烷(glycidoxypropyltrimethoxysilane)與2-(3,4-環氧環已烷基)乙基三甲氧基矽烷(2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane);搖變控制劑例如氣相式二氧化矽(fumed silica),用以提升搖變性與造模性(moldability);應力消除劑例如矽粉末(silicon powder)、橡膠粉末及表面改質矽粉末。The epoxy resin composition according to the embodiment of the present invention may further include various additives in addition to the foregoing components, as long as the object of the present invention is not impaired. For example, a defoaming agent, a coloring agent, a silane coupling agent, and a surface tension controlling agent to improve permeability can be additionally used agent), thixotropy controlling agent, stress relieving agent or dispersing agent used to improve agglomeration of inorganic fillers; colorants such as those used to improve the appearance of products Carbon black, etc .; Silane coupling agents, such as glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyl, are used to improve mechanical properties and adhesion. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Shake control agents such as fumed silica to improve shake and moldability; stress relief agents Examples include silicon powder, rubber powder, and surface-modified silicon powder.

根據本發明之實施例,可包含含量為0.1重量份至5重量份的添加劑,尤其是0.5重量份至3重量份。尤其,分散劑與消泡劑可提升空洞改良效應(void improving effect)與無機填充劑的凝聚性,且可各別包含0.1重量份至0.7重量份範圍內的分散劑與消泡劑。According to an embodiment of the present invention, an additive may be included in an amount of 0.1 to 5 parts by weight, especially 0.5 to 3 parts by weight. In particular, the dispersing agent and the defoaming agent can improve the cohesiveness of the void improving effect and the inorganic filler, and can each contain a dispersing agent and an antifoaming agent in a range of 0.1 parts by weight to 0.7 parts by weight.

同時,根據本發明之實施例的環氧樹脂組合物之製備可例如使一環氧樹脂、一無機填充劑、一固化劑與其他添加劑一次注入或材料逐一注入,且必要時一邊加熱一邊攪拌、混合及分散。用以混合、攪拌及分散混合物的儀器實施例沒有具體限制,但可使用配有攪拌與加熱儀器的混合物粉碎機(pulverizer)、三軸輥磨機(triaxial roll mill)、球磨機(ball mill)、真空臼研機(vacuum mortar)、行星式攪拌機(planetary-type mixer)等,或可使用這些儀器之適當組合。At the same time, the epoxy resin composition according to the embodiment of the present invention can be prepared by, for example, injecting an epoxy resin, an inorganic filler, a curing agent, and other additives at one time or injecting materials one by one, and heating and stirring when necessary, Mix and disperse. Examples of the apparatus for mixing, stirring, and dispersing the mixture are not specifically limited, but a mixture pulverizer, a triaxial roll mill, a ball mill, A vacuum mortar, a planetary-type mixer, or the like, or a suitable combination of these instruments may be used.

同時,封膠製程(molding process)可使用常見的點膠製程(dispensing process),且可於130°C的電爐(oven)中進行固化約30分鐘。根據情況,可改變固化溫度且可藉由控制固化促進劑(curing accelerator)以減少固化時間。Meanwhile, the molding process can use a common dispensing process, and can be cured in an oven at 130 ° C for about 30 minutes. Depending on the situation, the curing temperature can be changed and the curing accelerator can be controlled to reduce the curing time.

鑒於樹脂組合物孔隙裝填能力與製程加工性,若使用布氏黏度計(Brookfield viscometer)於25°C下以10 rpm測量根據本發明之實施例的環氧樹脂組合物之黏度,可能為例如5,000 cps至50,000 cps,尤其是10,000 cps至30,000 cps,更尤其是12,000 cps至25,000 cps。若實現黏度落在前述範圍內,可提升加工性與缺陷生成率以及裝填能力。若根據本發明之環氧樹脂組合物的黏度小於5,000 cps,可能發生樹脂溢流導致滲出,且若黏度大於50,000 cps,孔隙裝填時間過長且點膠製程期間的加工性可能變弱。In view of the pore filling ability and process processability of the resin composition, if a Brookfield viscometer is used to measure the viscosity of the epoxy resin composition according to the embodiment of the present invention at 10 rpm at 25 ° C, it may be, for example, 5,000 cps to 50,000 cps, especially 10,000 cps to 30,000 cps, and more particularly 12,000 cps to 25,000 cps. If the viscosity falls within the aforementioned range, processability, defect generation rate, and filling ability can be improved. If the viscosity of the epoxy resin composition according to the present invention is less than 5,000 cps, resin overflow may cause bleeding, and if the viscosity is more than 50,000 cps, the pore filling time is too long and the processability during the dispensing process may be weakened.

根據本發明之實施例的環氧樹脂組合物,黏度控制係為容易的,可達成優異的流度與流動性,尤其是黏著性、裝填能力與熱應力可為優異的,且可獲得穩定的加工性及優異的黏著性可靠度。若使這類環氧樹脂組合物用作製造半導體裝置的底部填充材料,更尤其是覆晶底部填充,可獲得優異的可靠度。According to the epoxy resin composition according to the embodiment of the present invention, the viscosity control system is easy, and excellent fluidity and fluidity can be achieved. In particular, adhesiveness, filling ability, and thermal stress can be excellent, and stable Processability and excellent adhesion reliability. If such an epoxy resin composition is used as an underfill material for manufacturing a semiconductor device, and more particularly a flip-chip underfill, excellent reliability can be obtained.

以下將藉由實施例更詳細描述本發明。根據本發明之實施例可變更為其他多種類型,且本發明之範圍不應侷限於以下實施例。本發明之實施例提供以對該技術領域具有通常知識者完整描述本發明。Hereinafter, the present invention will be described in more detail through examples. The embodiments according to the present invention can be changed to other various types, and the scope of the present invention should not be limited to the following embodiments. Embodiments of the present invention are provided to provide a complete description of the present invention to those skilled in the art.

實施例Examples

實施例1Example 1

使用環氧樹脂、無機填充劑、固化劑與添加劑以下表1所示之組成分(重量份)製備一環氧樹脂組合物。An epoxy resin composition was prepared using an epoxy resin, an inorganic filler, a curing agent, and an additive (parts by weight) shown in Table 1 below.

尤其,在行星式攪拌機內混合胺系固化劑之環氧樹脂混合物、低黏度環氧樹脂及多官能基環氧樹脂。將平均粒徑約0.3微米的二氧化矽與碳黑放入該攪拌機且使其混合,接著將添加劑(例如矽烷化合物(silane compound))、分散劑與消泡劑加入攪拌機並攪拌以製備環氧樹脂組合物。In particular, an epoxy resin mixture of an amine curing agent, a low viscosity epoxy resin, and a polyfunctional epoxy resin are mixed in a planetary mixer. Put silicon dioxide and carbon black with an average particle size of about 0.3 microns into the mixer and mix them. Then add additives (such as silane compound), dispersant and defoamer to the mixer and stir to prepare epoxy. Resin composition.

實施例2Example 2

除了將環氧樹脂與無機填充劑改為如下表1所示之含量,進行如實施例1之方法以製備環氧樹脂組合物。Except that the epoxy resin and the inorganic filler were changed to the contents shown in Table 1 below, the method as in Example 1 was performed to prepare an epoxy resin composition.

實施例3Example 3

除了將環氧樹脂與無機填充劑改為如下表1所示之含量,進行如實施例1之方法以製備環氧樹脂組合物。Except that the epoxy resin and the inorganic filler were changed to the contents shown in Table 1 below, the method as in Example 1 was performed to prepare an epoxy resin composition.

實施例4Example 4

除了將低黏度環氧樹脂與多官能基環氧樹脂改為如下表1所示之含量,進行如實施例1之方法以製備環氧樹脂組合物。Except changing the low-viscosity epoxy resin and the polyfunctional epoxy resin to the contents shown in Table 1 below, the method as in Example 1 was performed to prepare the epoxy resin composition.

比較例1Comparative Example 1

除了不使用具有三或更多個官能基的多官能基環氧樹脂及如下表1所示增加低黏度環氧樹脂之含量,進行如實施例1之方法以製備環氧樹脂組合物。Except not using a polyfunctional epoxy resin having three or more functional groups and increasing the content of the low viscosity epoxy resin as shown in Table 1 below, the method as in Example 1 was performed to prepare an epoxy resin composition.

比較例2Comparative Example 2

除了使用如下表1所示之具有5,000 cps至6,000 cps的黏度的高黏度環氧樹脂(而非具有2,000 cps至3,000 cps的黏度的低黏度環氧樹脂),進行如實施例1之方法以製備環氧樹脂組合物。Except using a high viscosity epoxy resin having a viscosity of 5,000 cps to 6,000 cps as shown in Table 1 below (instead of a low viscosity epoxy resin having a viscosity of 2,000 cps to 3,000 cps), the method as in Example 1 was performed to prepare Epoxy resin composition.

比較例3Comparative Example 3

除了使用如下表1所示之具有約10微米的平均粒徑的二氧化矽(而非具有約0.3微米的平均粒徑的二氧化矽),進行如實施例1之方法以製備環氧樹脂組合物。Except using silicon dioxide having an average particle diameter of about 10 microns (instead of silicon dioxide having an average particle diameter of about 0.3 microns) shown in Table 1 below, the method as in Example 1 was performed to prepare an epoxy resin composition Thing.

比較例4Comparative Example 4

除了將環氧樹脂與無機填充劑改為如下表1所示之含量,進行如實施例1之方法以製備環氧樹脂組合物。Except that the epoxy resin and the inorganic filler were changed to the contents shown in Table 1 below, the method as in Example 1 was performed to prepare an epoxy resin composition.

比較例5Comparative Example 5

除了將環氧樹脂與無機填充劑改為如下表1所示之含量,進行如實施例1之方法以製備環氧樹脂組合物。Except that the epoxy resin and the inorganic filler were changed to the contents shown in Table 1 below, the method as in Example 1 was performed to prepare an epoxy resin composition.

[表1] [Table 1]

試驗實施例Test example

1) 黏度1) viscosity

使用錐板式(Cone & Plate-type)布氏黏度計於25°C下測量黏度。Cone & Plate-type Brookfield viscometer was used to measure the viscosity at 25 ° C.

2) 流率2) Flow rate

底部填充劑於基板100°C時裝填於玻璃基板上的封裝內(凸塊間隙18微米)The underfill is filled in the package on the glass substrate at 100 ° C (18 micron bump gap)

3) 空洞3) Hollow

在將底部填充劑裝填於溫度100°C的熱基板上的封裝內(凸塊間隙18微米)後,以肉眼及顯微鏡透過玻璃基板確認空洞。After filling the underfill in a package on a hot substrate at a temperature of 100 ° C (18 micron bump gap), the cavity was confirmed through the glass substrate with the naked eye and a microscope.

4) 滲出4) Exudation

在將底部填充劑裝填於溫度100°C的熱基板上的封裝內(凸塊間隙18微米)後,使用顯微鏡測量流出玻璃基板的底部填膠充劑的尺寸。After filling the underfill in a package on a hot substrate at a temperature of 100 ° C. (bump gap of 18 microns), the size of the underfill filler flowing out of the glass substrate was measured using a microscope.

[表2] [Table 2]

如上表2所示,當比較本發明之實施例1與比較例1和比較例2,本發明之實施例1具有介於12,000 cps至25,000 cps特定範圍內的黏度,且少量發生空洞與溢流。As shown in Table 2 above, when Example 1 of the present invention is compared with Comparative Example 1 and Comparative Example 2, Example 1 of the present invention has a viscosity in a specific range of 12,000 cps to 25,000 cps, and a small amount of voids and overflow occur. .

特別是黏度,實施例1的環氧樹脂組合物具有2,400 cps的適當黏度,且其流度、裝填能力與流動性良好,且從而,其加工性係為優異的。Especially the viscosity, the epoxy resin composition of Example 1 has an appropriate viscosity of 2,400 cps, and its fluidity, filling ability, and fluidity are good, and therefore, its processability is excellent.

同時,當比較裝填底部填充劑後從玻璃基板溢出的底部填充劑尺寸,實施例1的封膠弧角(fillet)尺寸為280微米,但不包含多官能基環氧樹脂的比較例1及使用高黏度環氧樹脂而非低黏度環氧樹脂的比較例2的封膠弧角(fillet)尺寸為370微米至460微米,為實施例1的1.2至1.6倍。At the same time, when comparing the size of the underfill that overflowed from the glass substrate after the underfill was filled, the fillet size of Example 1 was 280 microns, but Comparative Example 1 that did not include a polyfunctional epoxy resin and used The fillet size of Comparative Example 2 of the high viscosity epoxy resin rather than the low viscosity epoxy resin is 370 μm to 460 μm, which is 1.2 to 1.6 times that of Example 1.

此外,下表3顯示改變低黏度環氧樹脂與具有三或更多個官能基的多官能基環氧樹脂含量的試驗結果。In addition, Table 3 below shows the test results of changing the contents of the low viscosity epoxy resin and the polyfunctional epoxy resin having three or more functional groups.

[表3] [table 3]

如上表3所示,發現黏度、流率與空洞隨低黏度環氧樹脂與多官能基環氧樹脂的含量而明顯改變。As shown in Table 3 above, it was found that the viscosity, flow rate, and voids significantly changed with the contents of the low-viscosity epoxy resin and the polyfunctional epoxy resin.

尤其,實施例1的環氧樹脂組合物於10 rpm下具有一24,000 cps的黏度,但實施例4的環氧樹脂組合物(包含含量明顯多於低黏度環氧樹脂的多官能基環氧樹脂)中,發現組合物的黏度明顯增加為51,000 cps。因此,發現實施例1的流率比實施例4的流率快2倍或更多倍。In particular, the epoxy resin composition of Example 1 has a viscosity of 24,000 cps at 10 rpm, but the epoxy resin composition of Example 4 (contains a polyfunctional epoxy resin containing significantly more than a low viscosity epoxy resin) ), The viscosity of the composition was found to increase significantly to 51,000 cps. Therefore, the flow rate of Example 1 was found to be 2 or more times faster than that of Example 4.

此外,實施例1的環氧樹脂組合物中並未觀察到空洞,但實施例4的環氧樹脂組合物中有空洞產生。In addition, no void was observed in the epoxy resin composition of Example 1, but voids were generated in the epoxy resin composition of Example 4.

同時,表4顯示根據二氧化矽平均粒徑的試驗結果。Meanwhile, Table 4 shows the test results based on the average particle diameter of silicon dioxide.

[表4] [Table 4]

如上表4所示,當比較實施例1的環氧樹脂組合物(使用平均粒徑0.3微米的二氧化矽)與比較例3的組合物(使用平均粒徑約10微米的二氧化矽),發現其流率與空洞有所差異。As shown in Table 4 above, when comparing the epoxy resin composition of Example 1 (using an average particle diameter of 0.3 micron) and the composition of Comparative Example 3 (using an average particle diameter of about 10 micron), It is found that the flow rate is different from the void.

尤其,實施例1的環氧樹脂組合物的流率為21秒,而比較例3的環氧樹脂組合物的流率為31秒,且發現比較例3的流率降低為實施例1的1/1.5。In particular, the flow rate of the epoxy resin composition of Example 1 was 21 seconds, while the flow rate of the epoxy resin composition of Comparative Example 3 was 31 seconds, and it was found that the flow rate of Comparative Example 3 was reduced to 1 in Example 1 /1.5.

此外,當裝填底部填充劑後以肉眼或顯微鏡透過玻璃基板觀察空洞時,使用實施例1之環氧樹脂組合物(使用平均粒徑約0.3微米的二氧化矽)的情況下不會產生空洞。相反的,使用比較例3之環氧樹脂組合物(使用平均粒徑約10微米的二氧化矽)的情況下,發現空洞生成。In addition, when the cavity is observed through the glass substrate with the naked eye or a microscope after the underfill is filled, the cavity is not generated when the epoxy resin composition of Example 1 is used (silicon dioxide having an average particle diameter of about 0.3 μm). In contrast, when the epoxy resin composition of Comparative Example 3 was used (silicon dioxide having an average particle diameter of about 10 μm), voids were found to be formed.

此外,下表5顯示環氧樹脂混合物與無機填充劑重量混合比例的試驗結果。In addition, Table 5 below shows the test results of the weight mixing ratio of the epoxy resin mixture and the inorganic filler.

[表5] [table 5]

如上表5所示,發現黏度、流率、空洞、滲出與溢流隨環氧樹脂混合物與無機填充劑的重量混合比例而明顯改變。As shown in Table 5 above, it was found that the viscosity, flow rate, voids, exudation, and overflow significantly change with the weight mixing ratio of the epoxy resin mixture and the inorganic filler.

尤其,當比較實施例2與比較例4,發現無機填充劑的含量下降且黏度降低,因此流率增加。然而,當無機填充劑的含量過低,如同比較例4,由於流動性不平均而發生空洞與溢流,且黏度過低以致於無法引發滲出。In particular, when comparing Example 2 and Comparative Example 4, it was found that the content of the inorganic filler decreases and the viscosity decreases, so that the flow rate increases. However, when the content of the inorganic filler is too low, as in Comparative Example 4, voids and overflow occur due to uneven fluidity, and the viscosity is too low to cause exudation.

此外,當比較實施例3與比較例5,發現黏度隨著無機填充劑的含量增加而增加,且從而使流率變慢。此時,若無機填充劑的含量過高,如同比較例5,發現空洞表現不佳。In addition, when comparing Example 3 with Comparative Example 5, it was found that the viscosity increases as the content of the inorganic filler increases, and thus the flow rate becomes slower. At this time, if the content of the inorganic filler is too high, as in Comparative Example 5, it is found that the void performance is not good.

Claims (11)

一種環氧樹脂組合物,包含: 一環氧樹脂; 一無機填充劑;及 一固化劑; 其中該環氧樹脂係為一低黏度環氧樹脂與一多官能基環氧樹脂的一環氧樹脂混合物,該低黏度環氧樹脂於25°C下具有500 cps至4,000 cps的一黏度,該多官能基環氧樹脂具有三或更多個官能基,且 該無機填充劑具有0.1微米(μm)至5微米(μm)的一平均粒徑(D50 )。An epoxy resin composition includes: an epoxy resin; an inorganic filler; and a curing agent; wherein the epoxy resin is an epoxy resin with a low viscosity epoxy resin and a multifunctional epoxy resin; Mixture, the low viscosity epoxy resin has a viscosity of 500 cps to 4,000 cps at 25 ° C, the multifunctional epoxy resin has three or more functional groups, and the inorganic filler has 0.1 micron (μm) To an average particle size (D 50 ) of 5 micrometers (μm). 如申請專利範圍第1項所述之環氧樹脂組合物,其中該無機填充劑係為具有0.2微米(μm)至3微米(μm)的一平均粒徑(D50 )的二氧化矽(silica)。The epoxy resin composition according to item 1 of the scope of patent application, wherein the inorganic filler is a silica having a mean particle diameter (D 50 ) of 0.2 micrometer (μm) to 3 micrometers (μm). ). 如申請專利範圍第1項所述之環氧樹脂組合物,其中該環氧樹脂的含量係為10至60重量份,該無機填充劑的含量係為45至70重量份,且該固化劑的含量係為5至15重量份。The epoxy resin composition according to item 1 of the scope of patent application, wherein the content of the epoxy resin is 10 to 60 parts by weight, the content of the inorganic filler is 45 to 70 parts by weight, and the curing agent is The content is 5 to 15 parts by weight. 如申請專利範圍第1項所述之環氧樹脂組合物,其中該低黏度環氧樹脂與該多官能基環氧樹脂之一重量混合比例係為1:0.1至1:0.8。The epoxy resin composition according to item 1 of the patent application scope, wherein a weight mixing ratio of one of the low viscosity epoxy resin and the multifunctional epoxy resin is 1: 0.1 to 1: 0.8. 如申請專利範圍第1項所述之環氧樹脂組合物,其中該低黏度環氧樹脂包含一由下列[化學式1]所表示的化合物,[化學式1]中,R為一具有5至10個碳原子的烴基。 [化學式1] The epoxy resin composition according to item 1 of the scope of patent application, wherein the low viscosity epoxy resin comprises a compound represented by the following [Chemical Formula 1], [Chemical Formula 1], R is a compound having 5 to 10 Carbon atom hydrocarbon group. [Chemical Formula 1] 如申請專利範圍第5項所述之環氧樹脂組合物,其中[化學式1]包含由下列[化學式2]所表示的一化合物。 [化學式2] The epoxy resin composition according to item 5 of the scope of patent application, wherein [Chemical Formula 1] includes a compound represented by the following [Chemical Formula 2]. [Chemical Formula 2] 如申請專利範圍第1項所述之環氧樹脂組合物,其中該多官能基環氧樹脂係為具有一液相雙酚A型環氧樹脂(bisphenol A-type epoxy resin)溶解於一三官能基反應性稀釋劑(reactive diluent)的一環氧樹脂、一對胺酚型環氧樹脂(p-amino phenol-type epoxy resin)或其混合物。The epoxy resin composition according to item 1 of the scope of the patent application, wherein the multifunctional epoxy resin is a bisphenol A-type epoxy resin having a liquid phase dissolved in a trifunctional A reactive diluent, an epoxy resin, a pair of p-amino phenol-type epoxy resins, or a mixture thereof. 如申請專利範圍第7項所述之環氧樹脂組合物,其中有該液相雙酚A型環氧樹脂溶解於該三官能基反應性稀釋劑的該環氧樹脂與該對胺酚型環氧樹脂的重量混合比例係為1:0.6至1:1.5。The epoxy resin composition according to item 7 of the scope of application for a patent, wherein the liquid phase bisphenol A type epoxy resin is dissolved in the trifunctional reactive diluent, the epoxy resin and the p-aminophenol type ring The weight ratio of the oxygen resin is 1: 0.6 to 1: 1.5. 如申請專利範圍第1項所述之環氧樹脂組合物,其中該環氧樹脂與該無機填充劑的一重量混合比例係為1:0.7至1:3。The epoxy resin composition according to item 1 of the scope of the patent application, wherein a weight mixing ratio of the epoxy resin and the inorganic filler is 1: 0.7 to 1: 3. 如申請專利範圍第1項所述之環氧樹脂組合物,其中該固化劑包含一胺系(amine-based)固化劑。The epoxy resin composition according to item 1 of the patent application scope, wherein the curing agent comprises an amine-based curing agent. 如申請專利範圍第1項所述之環氧樹脂組合物,其中該環氧樹脂組合物更包含至少一添加劑,該至少一添加劑係選自由一消泡劑(defoaming agent)、一著色劑(coloring agent)、一矽烷偶合劑(silane coupling agent)、一表面張力控制劑(surface tension controlling agent)、一搖變控制劑(thixotropy controlling agent)、一應力消除劑(stress relieving agent)、一分散劑(dispersing agent)及上述之組合所組成的一群組。The epoxy resin composition according to item 1 of the scope of patent application, wherein the epoxy resin composition further comprises at least one additive, the at least one additive is selected from a defoaming agent and a coloring agent. agent), a silane coupling agent, a surface tension controlling agent, a thixotropy controlling agent, a stress relieving agent, and a dispersant ( dispersing agent) and a combination of the above.
TW107125662A 2017-08-09 2018-07-25 Epoxy resin composition TWI669341B (en)

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