CN109385044B - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- CN109385044B CN109385044B CN201810901737.9A CN201810901737A CN109385044B CN 109385044 B CN109385044 B CN 109385044B CN 201810901737 A CN201810901737 A CN 201810901737A CN 109385044 B CN109385044 B CN 109385044B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates 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
- C08G59/18—Macromolecules 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
- C08G59/20—Macromolecules 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates 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
- C08G59/18—Macromolecules 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
- C08G59/20—Macromolecules 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
- C08G59/22—Di-epoxy compounds
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates 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
- C08G59/18—Macromolecules 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
- C08G59/40—Macromolecules 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer 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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- 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 resin mixture of a low-viscosity epoxy resin having a viscosity of 500cps to 4,000cps at 25 ℃ and a polyfunctional epoxy resin having a functionality of three or more, and the inorganic filler has an average particle diameter of 0.1 μm to 5 μm.
Description
Technical Field
The present invention relates to an epoxy resin composition.
Background
The sealing method and the building method of the semiconductor device are also diversified according to miniaturization, lightness, thinness, and multifunctionality of electronic products. In particular, the surface mounting technology becomes the mainstream of the conventional pin type method, and as one of the surface mounting packaging technologies, there is a flip chip mounting type. This type is a technique capable of achieving miniaturization and thinning, which is not performed by a wire bonding method as in the usual case, but connects a chip surface with a substrate by solder balls or solder bumps.
However, if a thermal shock test is performed on the flip chip package mounted by such a method, it is found that there may be a defect in the reliability of the connection state between the circuit board and the solder bumps due to thermal stress caused by the difference in thermal expansion coefficient between the chip, the wiring board, and the solder balls. In order to eliminate the stress due to heating, a so-called underfill process is performed, in which a chip is mounted on a substrate and a space between the device and the substrate is filled with resin. The material used in this process is an underfill material, and most of this material has a liquid state. That is, such an underfill process is accomplished by applying an underfill material such as an epoxy resin composition into the space between the solder ball and the pad.
Such underfill materials are required to have a filling property in terms of workability so as to penetrate into a gap between the chip and the substrate, to have a small thermal expansion coefficient to some extent in terms of reliability, i.e., not much different from that of the solder ball, to have good adhesion, i.e., adhesion at the interface of the chip and the substrate, and to buffer the above-mentioned thermal stress. However, even if the filling property is excellent and the workability is improved, the epoxy resin may generate defects such as bleeding and flooding after filling. If the heat of reaction is small and sufficient volatilization and bubble removal cannot be accomplished, voids may be generated and operability defects may be generated.
Therefore, there is a need to develop an epoxy resin composition for underfill that can solve the problems of adhesion, filling property, and thermal stress, minimize the generation of defects, and have excellent workability and reliability.
[ Prior art documents ]
[ patent document ]
(patent document 1) Korean patent No.10-0529256
Disclosure of Invention
One aspect of the present invention provides an epoxy resin composition.
The present invention provides an epoxy resin composition comprising an epoxy resin, an inorganic filler and a curing agent, wherein the epoxy resin is an epoxy resin mixture of a low-viscosity epoxy resin having a viscosity of 500cps to 4,000cps at 25 ℃ and a polyfunctional epoxy resin having a functionality of three or more, and the inorganic filler has an average particle diameter of 0.1 μm to 5 μm.
Effect
The epoxy resin composition according to the embodiment of the present invention can realize excellent fluidity and fluidity by simple control of viscosity, and in particular, can secure stable workability and excellent adhesion reliability due to excellent adhesiveness, filling property and thermal stress.
Detailed Description
Hereinafter, the present invention will be described in more detail to help understanding of the present invention.
It should be understood that the words or terms used in the specification and claims of this invention should not be construed as defined in commonly used dictionaries. It should also be understood that the words or terms should be interpreted as having a meaning consistent with the technical idea of the present invention, based on the principle that the inventor can appropriately define the meaning of the words or terms to best explain the present invention.
An epoxy resin composition according to one embodiment of the present invention includes an epoxy resin, an inorganic filler, and a curing agent, wherein the epoxy resin is an epoxy resin mixture of a low-viscosity epoxy resin having a viscosity of 500cps to 4,000cps at 25 ℃ and a multifunctional epoxy resin having a functionality of three or more, and the inorganic filler has an average particle diameter of 0.1 μm to 5 μm.
According to the epoxy resin composition of one embodiment of the present invention, viscosity can be easily controlled, filling property and fluidity can be excellent, workability can be improved, and defects of bleeding and voids, which may be generated after filling the composition, can be minimized, and thus, excellent reliability can be obtained.
Hereinafter, the present invention will be explained in more detail.
An epoxy resin according to one embodiment of the present invention comprises an epoxy resin, an inorganic filler, and a curing agent.
< epoxy resin >
The epoxy resin according to one embodiment of the present invention includes an epoxy resin mixture composed of two or more different kinds of epoxy resins, and may include a low viscosity epoxy resin having a viscosity of 500cps to 4,000cps at 25 ℃ and a multifunctional epoxy resin having a functionality of three or more.
The content of the epoxy resin in the epoxy resin composition according to one embodiment of the present invention 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 epoxy resin is within this range, the viscosity can be easily controlled, excellent workability can be obtained, and the filling property and the fluidity can be improved.
(Low viscosity epoxy resin having a viscosity of 500cps to 4,000cps at 25 deg.C)
The epoxy resin composition according to one embodiment of the present invention includes a low viscosity epoxy resin having a viscosity of 500cps to 4,000cps at 25 ℃, and can rapidly penetrate into a gap between a chip and a substrate due to excellent fluidity, so that filling property and fluidity are improved. In this case, the viscosity can be measured by using, for example, a Brookfield viscometer.
The low viscosity epoxy resin having a viscosity of 500 to 4,000cps may have a viscosity of 1,000 to 3,500cps, more specifically 1,500 to 3,500 cps. If the epoxy resin having a viscosity within this range is contained, the viscosity can be easily controlled, the filling property and the fluidity can be improved, and the workability can be facilitated. If the epoxy resin contains a high viscosity epoxy resin having a viscosity of more than 4,000cps, the underfill may bleed out of the substrate after the underfill filling using the composition on the substrate, and a bleed generation area may be enlarged.
According to an embodiment of the present invention, the low viscosity epoxy resin having a viscosity of 500cps to 4,000cps may include a compound of the following chemical formula 1:
< chemical formula 1>
In the chemical formula 1, the first and second,
r is a hydrocarbon group of 5 to 15 carbon atoms.
Specifically, the compound of chemical formula 1 is a low-viscosity, low-chlorine-content epoxy resin, and may be a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, or a mixture resin thereof, and specifically, it may include a compound of the following chemical formula 2:
< chemical formula 2>
According to an embodiment of the present invention, the low viscosity epoxy resin having a viscosity of 500cps to 4,000cps may be contained in an amount of 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 more than this range, the viscosity may increase, thereby deteriorating flowability and filling property and lowering workability. In contrast, if the content of the low viscosity epoxy resin is less than this range, the filling property and the fluidity may be deteriorated.
(polyfunctional epoxy resin having a functionality of three or more)
The epoxy resin composition according to one embodiment of the present invention includes a multifunctional epoxy resin having a functionality of three or more, and can obtain a high Tg and increase a crosslinking density.
The multifunctional epoxy resin having a functionality of three or more may include one or more selected from the following epoxy resins: bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkylphenol novolac type epoxy resin, bisphenol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triglycidyl isocyanurate, acyclic epoxy resin, and p-aminophenol type epoxy resin. For example, the multifunctional Epoxy resin may include Epikote 152, Epikote 154, Epikote 828, and YX-4000 of Japan Epoxy Resins co., ltd.; epicron N-660, Epicron N-673 and Epicron N-695 of Dainippon Ink and Chemicals Co., Ltd; kukdo Chemistry Co., Ltd, YDCN-500-4P, YDCN-638, YH-300 and YH-325; JER630 and JER604, by Japan Epoxy Resins co., ltd.; componceran E201 and Componceran E202 from Arakawa Chemical Industries, Ltd, but are not limited thereto.
More specifically, in order to improve flowability and fillability, the multifunctional epoxy resin according to an embodiment of the present invention may include an epoxy resin obtained by dissolving a liquid-phase bisphenol a-type epoxy resin in a trifunctional reactive diluent, a p-aminophenol-type epoxy resin, and a mixture thereof, and more specifically, may include a mixture of an epoxy resin obtained by dissolving a liquid-phase bisphenol a-type epoxy resin in a trifunctional reactive diluent and a p-aminophenol-type epoxy resin.
An epoxy resin obtained by dissolving a liquid bisphenol a type epoxy resin in a trifunctional reactive diluent may advantageously have low viscosity, low-temperature curability, and non-crystallinity.
According to one 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, an amino group, a nitro group, an epoxy group, an acrylic group, and an unsaturated bond.
Specifically, the trifunctional reactive diluent may contain three epoxy groups as functional groups.
More specifically, the multifunctional epoxy resin may have a viscosity of 4,000cps to 6,000cps, and may include a trifunctional reactive diluent of the following chemical formula 3:
< chemical formula 3>
In addition, the p-aminophenol type epoxy resin according to an embodiment of the present invention may include, for example, N-bis (2, 3-epoxypropyl) -4- (2, 3-epoxypropoxy) aniline resin, and may be represented by the following chemical formula 4:
< chemical formula 4>
According to an embodiment of the present invention, if a mixture resin of an epoxy resin obtained by dissolving a liquid bisphenol a type epoxy resin in a trifunctional reactive diluent and a p-aminophenol type epoxy resin is used, their weight mixing ratio may be, for example, 1:0.6 to 1:1.5, particularly 1:0.7 to 1.
According to an embodiment of the present invention, the multifunctional epoxy resin may be contained in an amount of 5 parts by weight to 20 parts by weight, more specifically 5 parts by weight to 15 parts by weight. If the content of the multifunctional epoxy resin is less than this range, heat resistance, chemical resistance and electrical properties may be insufficient, and if the content thereof is greater than this range, flame retardancy and adhesion may be reduced.
According to an embodiment of the present invention, the amount of the low viscosity epoxy resin may be greater than the amount of the multifunctional epoxy resin having a functionality of three or more in the epoxy resin.
According to an embodiment of the present invention, the mixing ratio by weight of the low viscosity epoxy resin having a viscosity of 500cps to 4,000cps and the multifunctional epoxy resin having a functionality of three or more may be 1:0.1 to 1:0.8, particularly 1:0.3 to 1: 0.6. If the mixing ratio by weight satisfies this range, the viscosity of the epoxy resin composition can be easily controlled, and excellent fluidity can be obtained, thereby improving the filling property and fluidity and obtaining a high Tg。
< inorganic Filler >
The epoxy resin composition according to one embodiment of the present invention comprises an average particle diameter (D)50) 0.1 to 5 μm, and can improve the bonding force between the resin and the inorganic filler, and the generation of bleeding due to the increase in viscosity caused by the specific surface area is reduced, while improving mechanical properties and reducing stress.
The inorganic filler may include various inorganic materials that can achieve a low coefficient of thermal expansion, but may use, for example, an average particle diameter (D)50) 0.2 to 3 μm, more specifically 0.5 to 2 μm. In this case, the average particle diameter (D) of the silica particles can be measured by, for example, a laser diffraction method50). According to the laser diffraction method, generally, particle diameters from a submicron region to about several millimeters can be measured, and results with high reproducibility and high resolution can be obtained.
According to an embodiment of the present invention, if an inorganic filler having such an average particle diameter is used together with an epoxy resin, the bonding force between the epoxy resin and the inorganic filler may be increased, the generation of bleeding due to an increase in viscosity caused by a specific surface area may be reduced, and a high-temperature thermal expansion coefficient may be reduced, thereby improving a warpage phenomenon of a package.
Further, fine silica having a small particle diameter of 1 μm or less may be used to fill the fine bump gap, and for example, cut-type silica (cut-type silica) in which large particles are cut to 1 μm or less may be used. The cut type large particles can reduce viscosity when filled with a liquid resin, and can be filled at high density.
According to an embodiment of the present invention, the amount of the inorganic filler may play a decisive role in increasing the bonding force of the inorganic filler with the epoxy resin and in obtaining a low high-temperature thermal expansion coefficient, and for example, the amount of the inorganic filler may be 45 parts by weight to 70 parts by weight, particularly 50 parts by weight to 65 parts by weight. If the content of the inorganic filler is within the above content range, the bonding force of the inorganic filler to the resin may be increased, the chip crack may be prevented, and the generation of the bleeding may be minimized. If the content of the inorganic filler is less than the above range, the thermal expansion coefficient may become large and cracks may be generated during the thermal shock test, and if the content is more than the above range, the viscosity is increased too much and defects of workability may be generated. If a solvent is used to reduce the viscosity, the physical properties after curing may be adversely affected and voids may be created when volatilization and bubble control are not adequately accomplished during the underfill process.
According to an embodiment of the present invention, the mixing ratio of the epoxy resin mixture and the inorganic filler may be 1:0.7 to 1:3 by weight. Specifically, the weight mixing ratio of the low-viscosity epoxy resin and the inorganic filler may be 1:1.1 to 1: 2. When the mixing ratio by weight is within this range, the bonding force of the inorganic filler to the resin may be increased, and the generation of bleeding may be minimized. More specifically, when the content of the inorganic filler is too low, voids and overflow may be generated due to imbalance of fluidity, and a viscosity too low may cause bleeding. In addition, if the content of the inorganic filler is too large, voids may be generated.
< curing agent >
The epoxy resin composition according to one embodiment of the present invention may include a curing agent to control the curing rate.
The curing agent may be an amine curing agent, particularly an amine curing agent having a viscosity of less than 300 cps. In this case, control of the reaction may be facilitated as compared with the case where other kinds of curing agents (for example, acid anhydride curing agents) are used. More specifically, the curing agent may include at least one material selected from the group consisting of polyoxypropylene diamine, modified fatty amine, and modified alicyclic amine. For example, as a commercially available amine-based curing agent, XHL-0245 by Shin-A T & C can be used.
According to one embodiment of the present invention, the content of the curing agent in the epoxy resin composition may be 5 parts by weight to 15 parts by weight, and within the above range, it is possible to easily control the curing rate, and appropriate curing properties may be ensured, whereby the workability may be improved.
< additives >
The epoxy resin composition according to an embodiment of the present invention may contain various additives as needed in addition to the above components within a range not impairing the object of the present invention. For example, an antifoaming agent for easily removing bubbles, a coloring agent such as carbon black for improving the appearance of a product, and the like, a silane coupling agent such as glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane for improving mechanical properties and adhesion, a tension control agent for improving penetration properties, a thixotropic control agent such as fumed silica for improving thixotropy and plasticity, a stress relieving agent such as silica powder, rubber powder, and surface-modified silica powder, or a dispersing agent for improving agglomeration of an inorganic filler may be additionally used.
According to one embodiment of the invention, the additive may be present in an amount of 0.1 to 5 parts by weight, in particular 0.5 to 3 parts by weight. In particular, the dispersant and the defoamer may improve a void improvement effect and agglomeration of the inorganic filler, and the content of each of the dispersant and the defoamer may be in the range of 0.1 to 0.7 parts by weight, respectively.
Meanwhile, the epoxy resin composition according to an embodiment of the present invention may be prepared, for example, by the following method: the epoxy resin, the inorganic filler, the curing agent and other additives are injected at one time or successively, and stirred, mixed and dispersed while being heated as needed. Examples of the device for mixing, stirring and dispersing of the mixture are not particularly limited, but a mixture pulverizer having a stirring device and a heating device, a three-axis roll mill, a ball mill, a vacuum mortar, a planetary mixer, or the like may be used, or an appropriate combination of these devices may be used.
Meanwhile, the molding process may use a conventional dispensing process, and may be cured in an oven at 130 ℃ for about 30 minutes. According to circumstances, the curing temperature may be changed and the curing time may be shortened by controlling the curing catalyst.
In view of the gap-filling property and the process workability of the resin composition, the viscosity of the epoxy resin composition according to one embodiment of the present invention may be, for example, 5,000cps to 50,000cps, specifically 10,000cps to 30,000cps, more specifically 12,000cps to 25,000cps, if the viscosity is measured at 10rpm at 25 ℃ using a Brookfield viscometer. With the viscosity within the above range, the workability and defect generation rate as well as the filling property can be improved. If the viscosity of the epoxy resin composition of the present invention is less than 5,000cps, resin bleeding due to flooding may be generated, and if the viscosity is more than 50,000cps, the gap-filling time is too long and the workability during the dispensing process may be deteriorated.
According to the epoxy resin composition of one embodiment of the present invention, the viscosity is easily controlled, excellent fluidity and fluidity can be obtained, and in particular, excellent adhesion, filling property and thermal stress can be provided, and stable workability and excellent adhesion reliability can be ensured. If such an epoxy resin composition is used as an underfill material for manufacturing a semiconductor device, more specifically, as an underfill for flip chips, excellent reliability can be ensured.
Hereinafter, the present invention will be explained in more detail with reference to embodiments. Embodiments according to the present invention may be modified into various other types, and the scope of the present invention should not be limited to the embodiments described below. The embodiments of the present invention are provided to fully explain the present invention to those skilled in the art.
Examples
Example 1
The epoxy resin, inorganic filler, curing agent and additives were used in the compositions (parts by weight) shown in table 1 below to prepare epoxy resin compositions.
Specifically, an epoxy resin mixture of an amine-based curing agent, a low viscosity epoxy resin, and a multifunctional epoxy resin is mixed in a planetary mixer. Silica having an average particle diameter of about 0.3 μm and carbon black were put into a planetary mixer and mixed, and additives such as a silane compound, a dispersant and an antifoaming agent were added to the mixture and stirred, thereby preparing an epoxy resin composition.
Example 2
An epoxy resin composition was prepared by performing the same method as example 1, except that the amounts of the epoxy resin and the inorganic filler were changed as shown in table 1 below.
Example 3
An epoxy resin composition was prepared by performing the same method as example 1, except that the amounts of the epoxy resin and the inorganic filler were changed as shown in table 1 below.
Example 4
An epoxy resin composition was prepared by performing the same method as example 1 except that the amounts of the low-viscosity epoxy resin and the multifunctional epoxy resin were changed as shown in table 1 below.
Comparative example 1
An epoxy resin composition was prepared by performing the same method as example 1, except that a multifunctional epoxy resin having a functionality of three or more was not used and the amount of a low viscosity epoxy resin was increased as shown in the following table 1.
Comparative example 2
An epoxy resin composition was prepared by performing the same method as example 1, except that a high-viscosity epoxy resin having a viscosity of 5,000cps to 6,000cps was used instead of a low-viscosity epoxy resin having a viscosity of 2,000cps to 3,000cps as shown in the following table 1.
Comparative example 3
An epoxy resin composition was prepared by performing the same method as example 1, except that silica having an average particle size of about 10 μm was used instead of silica having an average particle size of about 0.3 μm as shown in the following table 1.
Comparative example 4
An epoxy resin composition was prepared by performing the same method as example 1, except that the amounts of the epoxy resin and the inorganic filler were changed as shown in table 1 below.
Comparative example 5
An epoxy resin composition was prepared by performing the same method as example 1, except that the amounts of the epoxy resin and the inorganic filler were changed as shown in table 1 below.
[ Table 1]
Examples of the experiments
1) Viscosity of the oil
The viscosity was determined by using a Brookfield viscometer of the conical Plate (Cone & Plate) type at 25 ℃.
2) Flow rate of flow
The underfill was filled into the package (bump gap 18 μm) on a glass plate on a 100 ℃ plate.
3) Voids
After the underfill was filled into the package (bump gap 18 μm) on a hot plate at a temperature of 100 ℃, the gap was checked through the glass plate with the naked eye and a microscope.
4) Oozing out
After the underfill was filled onto the wiring board of the package on a hot plate at a temperature of 100 ℃, the size of the underfill flowing out of the glass plate was measured by using a microscope.
[ Table 2]
| Classification | Example 1 | Comparative example 1 | Comparative example 2 |
| Viscosity (cps)10rpm | 24,000cps | 9,000cps | 11,000cps |
| Flow rate (seconds) | 21 | 11 | 15 |
| Voids | X | X | X |
| Overflow | X | Y | Y |
| Exudation (Filet) | 288μm | 454μm | 376μm |
As shown in table 2 above, example 1 of the present invention has a viscosity in a specific range of 12,000cps to 25,000cps and generation of voids and flooding is less compared to comparative examples 1 and 2.
Particularly, the epoxy resin composition of example 1 had a suitable viscosity of 24,000cps in terms of viscosity, and was good in fluidity, filling property and fluidity, and thus was excellent in workability.
Meanwhile, when the size of the underfill agent flowing out of the glass plate after the underfill agent is filled is compared, the bead size of example 1 is 288 μm, but the bead sizes of comparative example 1 (which does not contain the multifunctional epoxy resin) and comparative example 2 (which uses the high-viscosity epoxy resin instead of the low-viscosity epoxy resin) are 370 μm to 460 μm, which are 1.3 times to 1.6 times as large as that of example 1.
In addition, table 3 below shows the experimental results of varying the amounts of the low viscosity epoxy resin and the multifunctional epoxy resin having a functionality of three or more.
[ Table 3]
| Classification | Example 1 | Example 4 |
| Viscosity (cps)10rpm | 24,000cps | 51,000cps |
| Flow rate (seconds) | 21 | 56 |
| Voids | X | Y |
| Overflow | X | X |
| Exudation (Flange) | 288μm | 230μm |
As shown in table 3 above, it was found that the viscosity, flow rate and voids were significantly changed according to the changes in the amounts of the low-viscosity epoxy resin and the multifunctional epoxy resin.
Specifically, the viscosity of the epoxy resin composition of example 1 was 24,000cps at 10rpm, but in the epoxy resin composition of example 4 (in which the content of the multifunctional epoxy resin was significantly greater than the amount of the low-viscosity epoxy resin), the viscosity of the composition was found to increase significantly to 51,000 cps. Accordingly, the flow rate of example 1 was found to be more than twice the flow rate of example 4.
Further, no voids were observed in the epoxy resin composition of example 1, but voids were generated in the epoxy resin composition of example 4.
Meanwhile, table 4 shows the experimental results according to the average particle size of silica.
[ Table 4]
| Classification | Example 1 | Comparative example 3 |
| Viscosity (cps)10rpm | 24,000cps | 27,000cps |
| Flow rate (seconds) | 21 | 31 |
| Voids | X | Y |
| Overflow | X | X |
| Exudation (Flange) | 288μm | 231μm |
As shown in Table 4 above, when the epoxy resin composition of example 1, which used silica having an average particle diameter of 0.3 μm, and the composition of comparative example 3, which used silica having an average particle diameter of about 10 μm, were compared, differences in flow rate and voids were found.
Specifically, 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 by about 1.5 times as compared with the flow rate of example 1.
Further, when the voids were observed through the glass plate with the naked eye and a microscope after the underfill agent was filled, no voids were generated in the case of using the epoxy resin composition of example 1, in which example 1 used silica having an average particle diameter of about 0.3 μm. In contrast, it was found that voids were generated in the case of using the epoxy resin composition of comparative example 3, wherein comparative example 3 used silica having an average particle diameter of about 10 μm.
In addition, table 5 below shows the experimental results of the weight mixing ratio of the epoxy resin mixture and the inorganic filler.
[ Table 5]
As shown in table 5 above, it was found that the viscosity, flow rate, voids, bleeding and flooding were significantly changed depending on the weight mixing ratio of the epoxy resin mixture and the inorganic filler.
Specifically, when example 2 and comparative example 4 were compared, it was found that the content of the inorganic filler was decreased and the viscosity was decreased, thereby increasing the flow rate. However, when the content of the inorganic filler in comparative example 4 is too low, voids and overflow are generated due to imbalance of fluidity, and the viscosity is too low to cause bleeding.
Further, when example 3 and comparative example 5 are compared, it is found that the viscosity increases as the content of the inorganic filler increases, thereby slowing down the flow rate. At this time, if the content of the inorganic filler is too large as in comparative example 5, a defect in terms of voids is found.
Claims (8)
1. An epoxy resin composition comprising an epoxy resin, an inorganic filler and a curing agent,
wherein the epoxy resin is an epoxy resin mixture of a low-viscosity epoxy resin having a viscosity of 500cps to 4,000cps at 25 ℃ and a multifunctional epoxy resin having a functionality of three or more, and
the average particle diameter (D) of the inorganic filler50) Is 0.1 μm to 5 μm,
wherein the mixing ratio by weight of the low-viscosity epoxy resin to the polyfunctional epoxy resin is 1:0.1 to 1:0.8,
wherein the polyfunctional epoxy resin having a functionality of three or more is a mixture of an epoxy resin obtained by dissolving a liquid-phase bisphenol A type epoxy resin in a trifunctional reactive diluent, and a p-aminophenol type epoxy resin, and
the mixing ratio by weight of the epoxy resin and the inorganic filler is 1:0.7 to 1: 3.
2. The epoxy resin composition of claim 1, wherein the inorganic filler is an average particle diameter (D)50) 0.2 to 3 μm silica.
3. The epoxy resin composition according to claim 1, 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 content of the curing agent is 5 to 15 parts by weight.
4. The epoxy resin composition of claim 1, wherein the low viscosity epoxy resin comprises a compound represented by the following chemical formula 1:
< chemical formula 1>
In the chemical formula 1, the first and second,
r is a hydrocarbon group of 5 to 15 carbon atoms.
5. The epoxy resin composition according to claim 4, wherein chemical formula 1 includes a compound represented by the following chemical formula 2:
< chemical formula 2>
6. The epoxy resin composition according to claim 1, wherein in the mixture, a mixing ratio by weight of an epoxy resin obtained by dissolving a liquid-phase bisphenol a type epoxy resin in a trifunctional reactive diluent to a p-aminophenol type epoxy resin is from 1:0.6 to 1: 1.5.
7. The epoxy resin composition of claim 1, wherein the curing agent comprises an amine curing agent.
8. The epoxy resin composition according to claim 1, wherein the epoxy resin composition further comprises at least one additive selected from the group consisting of an antifoaming agent, a coloring agent, a silane coupling agent, a surface tension controlling agent, a thixotropic controlling agent, a stress relieving agent and a dispersing agent.
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| CN101921458A (en) * | 2010-08-05 | 2010-12-22 | 宏昌电子材料股份有限公司 | Unleaded epoxy resin composite for printed circuit copper clad laminate |
| TW201233730A (en) * | 2011-02-03 | 2012-08-16 | Namics Corp | Semiconductor resin-molding material |
| JP2015189847A (en) * | 2014-03-28 | 2015-11-02 | 日立化成株式会社 | Underfill material, electronic component encapsulated by the underfill material and manufacturing method therefor |
| CN105732983A (en) * | 2014-12-25 | 2016-07-06 | 信越化学工业株式会社 | Liquid underfill material composition for sealing semiconductor and flip-chip semiconductor device |
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| KR100529256B1 (en) | 2002-12-20 | 2005-11-17 | 제일모직주식회사 | Liquid Epoxy Resin Composition for Encapsulation of Semiconductor |
| KR100655052B1 (en) * | 2003-12-30 | 2006-12-06 | 제일모직주식회사 | Liquid Epoxy Resin Composition for Underfill Application |
| KR101234847B1 (en) * | 2008-12-30 | 2013-02-19 | 제일모직주식회사 | Liquid epoxy resin composition for underfilling semiconductor device and semiconductor device using the same |
| JP5163912B2 (en) * | 2010-02-16 | 2013-03-13 | 信越化学工業株式会社 | Epoxy resin composition and semiconductor device |
| CA2907767A1 (en) * | 2013-03-28 | 2014-10-02 | Mitsubishi Chemical Corporation | Composition for interlayer filler of layered semiconductor device, layered semiconductor device, and process for producing layered semiconductor device |
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| CN101921458A (en) * | 2010-08-05 | 2010-12-22 | 宏昌电子材料股份有限公司 | Unleaded epoxy resin composite for printed circuit copper clad laminate |
| TW201233730A (en) * | 2011-02-03 | 2012-08-16 | Namics Corp | Semiconductor resin-molding material |
| JP2015189847A (en) * | 2014-03-28 | 2015-11-02 | 日立化成株式会社 | Underfill material, electronic component encapsulated by the underfill material and manufacturing method therefor |
| CN105732983A (en) * | 2014-12-25 | 2016-07-06 | 信越化学工业株式会社 | Liquid underfill material composition for sealing semiconductor and flip-chip semiconductor device |
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