TW202024225A - Epoxy resin composition for underfilling semiconductor device - Google Patents

Abstract

The present invention relates to an epoxy resin composition for underfilling a semiconductor device, the epoxy resin composition for underfilling the semiconductor device including: (A) a bisphenol epoxy resin; (B) a polyfunctional epoxy resin; (C) a CTBN modified epoxy resin; (D) a curing agent; and (E) a latent curing agent.

Description

Epoxy resin composition for underfilling semiconductor device

The present invention relates to an epoxy resin composition, and particularly relates to an epoxy resin composition for underfilling of semiconductor devices.

Semiconductor packaging is a technology that enables semiconductor wafers to work as electronic components. It provides necessary power to semiconductor devices, connects signals between semiconductor devices, and releases heat generated in semiconductor devices. Chemical and thermal environment changes to protect semiconductor devices. Recently, as electronic components and mobile devices are rapidly becoming thinner, higher-density, higher-functional, and ultra-high-speed, semiconductor packaging technology is gradually becoming smaller, thinner, and more concentrated.

With the rapid development of semiconductor packaging technology, there is also a need for technological development of packaging materials that can realize this technology. Underfill as one of them is one of the extremely important elements for the success of packaging technology. The underfill refers to a method of completely encapsulating the bottom of components such as ball grid array (BGA, ball grid array), chip scale package (CSP), and flip chip using insulating resin. The underfill is located between the circuit board and the semiconductor device (wafer), and is used to redistribute the stress and deformation caused by the difference in thermal expansion coefficient between the semiconductor device and the circuit substrate, and to cause moisture or other modules The impact of the electrical and magnetic environment is minimized.

In this case, in the case of defective elements such as the ball grid array and the wafer-level package, the assembly such as the ball grid array and the wafer-level package may be simply removed from the circuit board and reworked. As described above, the composition for underfilling of a semiconductor device that can be used for rework of underfilling is an epoxy resin, and a plasticizer is used for reworkability. Korean Laid-Open Patent Publication No. 2002-0036965 discloses a semiconductor element using epoxy resin and plasticizer. However, it does not mention reworkability and does not exhibit curing characteristics under normal temperature conditions. In particular, even if the plasticizer acts as a plasticizer, the epoxy resin for underfill cannot be sufficiently removed, and there is a problem that the reworkability remaining on the substrate or the like is not good. In addition, the action of the plasticizer adversely affects the heat resistance, impact resistance, and moisture resistance of the underfill coating.

Therefore, a technology for bottom packaging of semiconductor devices that has excellent reworkability, high heat resistance, high impact resistance, and high humidity resistance is essentially required.

Prior art literature

Patent literature

Patent Document 1: Korean Published Patent Publication No. 2002-0036965

technical problem

The object of the present invention is to provide an epoxy resin composition for semiconductor underfill that can easily remove assemblies such as ball grid arrays and wafer-level packages and has excellent reworkability.

Solution to the problem

The present invention provides an epoxy resin composition for underfilling semiconductor devices. The epoxy resin composition for underfilling semiconductor devices includes: (A) bisphenol epoxy resin; (B) multifunctional epoxy resin; (C) Liquid carboxyl-terminated nitrile rubber modified epoxy resin; (D) curing agent; and (E) latent curing agent.

Invention effect

Instead of the plasticizer in the conventional epoxy resin composition for underfilling semiconductor devices, the epoxy resin composition for underfilling semiconductor devices of the present invention uses liquid carboxyl terminated butadiene acrylonitrile (CTBN) modified epoxy As a result, when a semiconductor element such as a ball grid array or a wafer-level package assembly has a defect, the resin can be easily removed from the circuit board, so that the reworkability is excellent.

In addition, compared with the conventional epoxy resin composition, when the epoxy resin composition for underfilling a semiconductor device of the present invention is used, productivity can be improved by short-time thermal curing under low temperature conditions. The heat resistance, impact resistance and moisture resistance of the underfill coating will be improved.

In order to have a better understanding of the above-mentioned and other aspects of the present invention, the following specific examples are given in conjunction with the accompanying drawings to describe in detail as follows:

Hereinafter, the present invention will be described in detail.

The invention provides an epoxy resin composition for underfilling a semiconductor device.

The epoxy resin composition for underfilling of semiconductor devices may include: (A) bisphenol epoxy resin; (B) multifunctional epoxy resin; (C) liquid carboxy-terminated nitrile rubber modified epoxy resin; ( D) curing agent; and (E) latent curing agent.

(A) Bisphenol epoxy resin

The bisphenol epoxy resin contained in the epoxy resin composition for underfilling a semiconductor device of the present invention can function as a binder by reacting with a curing agent.

The bisphenol-based epoxy resin may include at least one unit derived from the compound represented by the following Chemical Formula 1 to Chemical Formula 3.

Chemical formula 1

Chemical formula 2

Chemical formula 3

The bisphenol-based epoxy resin may include a unit derived from the compound represented by the chemical formula 1 to the chemical formula 3.

The bisphenol-based epoxy resin may include a unit derived from a compound represented by the following Chemical Formula 4.

Chemical formula 4

In the chemical formula 4, R ₁ and R _{2 are the} same or different, and are each independently hydrogen or an alkyl group having 1 to 10 carbons.

The R ₁ and R _{2 are the} same or different, and may be independently hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, isopentyl, neopentyl or tert-pentyl. .

The R ₁ and R _{2 are the} same or different, and may be independently hydrogen or methyl.

The R ₁ and R ₂ may be hydrogen.

The bisphenol epoxy resin may be bisphenol A epoxy resin, bisphenol F epoxy resin or a mixture of these. Specifically, the bisphenol-based epoxy resin is included in the epoxy resin composition for underfilling of the semiconductor device, so that the heat resistance, impact resistance and moisture resistance of the semiconductor underfill coating can be improved.

In this case, the bisphenol epoxy resin may be a liquid phase bisphenol epoxy resin. In the case of underfilling, it is necessary to completely fill the fine gaps (Gap) in the element. When filling, it is necessary to suppress the formation of voids, so it has low viscosity. In order to improve the product reliability of semiconductor elements, when filling, The viscosity is controlled by preventing the underfill from flowing excessively to the outside of the semiconductor element. Therefore, it is preferable that the bisphenol epoxy resin used in the epoxy resin composition for underfilling a semiconductor device of the present invention uses a liquid phase bisphenol epoxy resin.

Under the temperature condition of 25° C., the viscosity of the bisphenol epoxy resin may be 2000 cPs to 14000 cPs. When the viscosity of the bisphenol-based epoxy resin is less than 2000cPs, it is difficult to remove the semiconductor device assembly from the circuit board, which may cause problems in reworkability. When the viscosity is greater than 14000cPs, the work Sex may be problematic.

And, the equivalent (g/eq.) of the bisphenol epoxy resin may be 80 g/eq. to 500 g/eq., specifically, it may be 160 g/eq. to 190 g/eq.

The bisphenol-based epoxy resin may be included in a weight ratio of 30 to 55 weight ratio compared with a multifunctional epoxy resin in a weight ratio of 20 to 40 weight ratio. When the content of the bisphenol epoxy resin is less than 30 weight ratio, the plasticity will be reduced after curing, and the problem of poor reworkability may occur. In the case of more than 55 weight ratio, the underfill coating There is a problem with the heat resistance.

(B) Multifunctional epoxy resin

The multifunctional epoxy resin contained in the epoxy resin composition for underfilling semiconductor devices of the present invention can reduce the viscosity of the epoxy resin composition for underfilling semiconductor devices and impart a non-clean reactive diluent The role of.

The multifunctional epoxy resin may include more than 3 functional groups in a unit structure forming a repeating unit.

The functional group may be a hydroxyl group, an alkoxy group, a halogen group, an aldehyde group, a carbonyl group, a carboxyl group, an amine group, a nitrile group, a nitro group, an amide group, an amide group and an epoxy group.

The multifunctional epoxy resin may include at least one epoxy group as a functional group. Preferably, in order to reduce the viscosity of the epoxy resin composition for underfilling the semiconductor device, three or more epoxy groups are included as functional groups.

The multifunctional epoxy resin may be a multifunctional epoxy resin other than the bisphenol epoxy resin.

The multifunctional epoxy resin may include a unit derived from a compound represented by the following Chemical Formula 5.

Chemical formula 5

In the chemical formula 5, the R ₃ is an alkyl group having 1 to 10 carbon atoms, and n, m, and p are the same or different, and are each independently an integer of 1 to 10.

The R ₃ may be an alkyl group having 1 to 6 carbons.

The R ₃ may be methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, isopentyl, neopentyl or tert-pentyl.

The R ₃ may be an alkyl group.

The n, m, and p are the same or different, and may be an integer from 1 to 5 independently.

The n, m, and p may be integers of 1.

Under the temperature condition of 25° C., the viscosity of the multifunctional epoxy resin may be 50 cPs to 700 cPs, specifically, 100 cPs to 300 cPs. When the viscosity of the multifunctional epoxy resin is less than 50 cps, it is difficult to remove the semiconductor device assembly from the circuit board, so that reworkability may be problematic. When the viscosity is greater than 700 cPs, the high viscosity may cause work. Sexual problems, and can cause rework problems.

The epoxy equivalent of the multifunctional epoxy resin may be 105 g/eq. to 630 g/eq., specifically, 135 g/eq. to 150 g/eq. In the case where the epoxy equivalent of the multifunctional epoxy resin is less than 105g/eq., it is difficult to remove the semiconductor device assembly from the circuit board, so that reworkability may be problematic, and the epoxy equivalent is greater than 630g/eq. In the case of, the cross-linking density will be reduced, and the heat resistance, impact resistance, and moisture resistance of the underfill coating may have problems.

Based on the bisphenol epoxy resin in a weight ratio of 30 to 55 weight ratio, the multifunctional epoxy resin may include 20 weight ratio to 40 weight ratio, and specifically, may include 20 weight ratio to 35 weight ratio. When the content of the multifunctional epoxy resin is less than 20 weight ratio, the plasticity will be reduced after curing, which may cause poor reworkability. When the content is greater than 40 weight ratio, bottoms may occur. Heat resistance, impact resistance, and moisture resistance of the filled coating.

(C) Liquid carboxyl-terminated nitrile rubber modified epoxy resin

The liquid carboxyl-terminated nitrile butadiene rubber epoxy resin contained in the epoxy resin composition for underfilling semiconductor devices of the present invention reduces the glass transition temperature (Tg) of the epoxy resin composition for underfilling semiconductor devices to impart flexibility When using the epoxy resin composition for underfilling the semiconductor device to disassemble the semiconductor device assembly, the disassembly and assembly become easy, and the reworkability becomes excellent.

In particular, the liquid carboxyl-terminated nitrile rubber-modified epoxy resin is included in the epoxy resin composition for underfilling of semiconductor devices, thereby imparting flexibility and adhesion even without adding conventional plasticizers. Strength, water resistance, oil resistance and other physical properties to improve the reworkability in the process of modifying the components of the semiconductor device assembly.

The liquid carboxy-terminated nitrile rubber modified epoxy resin may include an epoxy resin modified with a trifunctional group of a trifunctional epoxy resin into a butadiene containing terminal carboxylic acid.

Under the temperature condition of 25° C., the viscosity of the liquid carboxy-terminated nitrile rubber modified epoxy resin may be 1000 cPs to 5000 cPs, specifically, it may be 2000 cPs to 3000 cPs. When the viscosity of the liquid carboxyl-terminated nitrile rubber modified epoxy resin is less than 1000 cPs, it is difficult to remove the semiconductor device assembly from the circuit board, which may cause problems with reworkability. When the viscosity is greater than 5000 cPs, Workability problems caused by high viscosity.

The epoxy equivalent of the liquid carboxy-terminated nitrile rubber modified epoxy resin may be 110 g/eq. to 850 g/eq., specifically, it may be 175 g/eq. to 205 g/eq. When the epoxy equivalent of the liquid carboxyl-terminated nitrile rubber modified epoxy resin is less than 110g/eq., it is difficult to remove the semiconductor device assembly from the circuit board, which may cause problems in reworkability due to high modulus The impact resistance problem occurs due to the amount. When the epoxy equivalent is greater than 850g/eq., the crosslinking density will decrease, which will cause the heat resistance of the underfill coating.

Based on the bisphenol epoxy resin in a weight ratio of 30 to 55 weight ratio, the liquid carboxy-terminated nitrile rubber modified epoxy resin may be contained in a weight ratio of 5 to 20 weight ratio. In the case where the content of the liquid carboxy-terminated nitrile rubber modified epoxy resin is less than 5 weight ratio, the epoxy resin for underfilling semiconductor devices cannot be imparted with flexibility after curing, resulting in poor reworkability. High modulus causes impact resistance problems. In the case where the content of the liquid carboxy-terminated nitrile rubber modified epoxy resin is greater than 20 weight ratio, the heat resistance of the underfill coating may occur.

(D) Curing agent

The curing agent contained in the epoxy resin composition for underfilling a semiconductor device of the present invention reacts with the bisphenol epoxy resin to cure the epoxy resin composition for underfilling a semiconductor device.

The curing agent may include at least one selected from phenolic curing agents and amine curing agents.

In addition, the curing agent may be a liquid phase curing agent. As described above, preferably, in order to control the viscosity, the underfill of the semiconductor device uses a curing agent in a liquid phase instead of a curing agent in a solid phase.

1. Phenolic curing agent

The phenolic curing agent improves the chemical resistance, water resistance and heat resistance of the epoxy resin composition for underfilling of semiconductor devices.

The phenolic curing agent may be a novolac resin in a solvent-free liquid phase. Specifically, the phenol-based curing agent may include a phenol resin.

Under the temperature condition of 25°C, the viscosity of the phenolic curing agent may be 1500 cPs to 3500 cPs. In the case where the viscosity of the phenol-based curing agent is greater than 3500 cPs, (re)workability problems occur due to the high viscosity.

The hydroxyl equivalent of the phenol curing agent may be 100 g/eq. to 200 g/eq., specifically, it may be 139 g/eq. to 143 g/eq. When the hydroxyl equivalent of the phenolic curing agent is less than 100g/eq., there may be problems with the reworkability of the underfill coating, and when the hydroxyl equivalent is greater than 200g/eq., the bottom of the semiconductor device may be used. The problem of heat resistance of epoxy resin composition for filling.

2. Amine curing agent

The amine curing agent increases the crosslinking density of the epoxy resin composition for underfilling of semiconductor devices, thereby improving the chemical resistance, water resistance and heat resistance of the underfill coating.

The amine curing agent may include a fatty amine compound (or polymer).

The amine curing agent may be an aliphatic amine compound (or polymer) containing primary amines at both ends, specifically, may be an aliphatic polyetheramine compound (or polymer) containing primary amines at both ends.

Preferably, on the heat resistance, impact resistance, and moisture resistance of the epoxy resin composition for underfilling the semiconductor device, the amine curing agent contains polyoxypropylene diamine having primary amines at both ends.

The amine curing agent may include a compound represented by the following Chemical Formula 6.

Chemical formula 6

In the chemical formula 6, q is a number from 10 to 50.

The q is a number from 30 to 40.

The amine equivalent of the amine curing agent may be 0.3 meq./g to 3 meq./g. When the amine equivalent of the amine curing agent is less than 0.3 meq./g, the crosslink density based on the crosslinking reaction with the bisphenol epoxy resin will decrease, resulting in the chemical resistance of the underfill coating , Water resistance, heat resistance, etc., when the amine equivalent is greater than 3meq./g, reworkability problems occur due to over-curing.

Based on the bisphenol epoxy resin in a weight ratio of 30 to 55 weight ratio, the curing agent may be included in a weight ratio of 10 to 20 weight ratio. When the content of the curing agent is less than 10 weight ratio, the reworkability and impact resistance of the epoxy resin composition for underfilling semiconductor devices may occur. When the content is more than 20 weight ratio, There is a concern that the heat resistance of the underfill coating will decrease.

In addition, in order to have excellent physical properties of the underfill coating, the epoxy resin composition for underfilling of semiconductor devices may be used to contain the phenolic curing agent and the amine curing agent in a weight ratio of 5:1 to 10:1. In the case where the weight ratio of the phenolic curing agent to the amine curing agent is less than 5:1, the curability in the low temperature state will be problematic, and the heat resistance, water resistance, impact resistance, etc. of the underfill coating Physical properties are problematic. When the weight ratio is greater than 10:1, the underfill film becomes hard due to over-curing, and reworkability becomes poor.

(E) Latent curing agent

The latent curing agent contained in the epoxy resin composition for underfilling a semiconductor device of the present invention is a curing agent that starts a curing reaction by external stimuli such as heat, light, pressure, moisture, etc., and is included in the underfilling of the semiconductor device. The epoxy resin composition, therefore, compared with the conventional epoxy resin composition for underfilling of semiconductor devices, it can be realized at low temperature (60°C or less), preferably at normal temperature (15°C-25°C) Short time heat curing.

In addition to the functional group, the latent curing agent contains active hydrogen in the molecule, thereby smoothly dispersing into the epoxy resin, and improving the performance of the epoxy resin composition for underfilling a semiconductor device of the present invention. Storage stability under normal temperature conditions can also achieve rapid curing under normal temperature conditions.

The latent curing agent may include at least one selected from a microcapsule type latent curing agent, an amine adduct type latent curing agent, dicyandiamide (DICYANDIAMIDE) and derivatives thereof.

Also, the latent curing agent may be a liquid phase. Compared with a solid-phase latent curing agent, when included in the epoxy resin composition for underfilling a semiconductor device of the present invention, dispersibility can be improved.

The microcapsule-type latent curing agent refers to the curing agent as the core and is covered by a polymer material such as epoxy resin, polyurethane resin, polystyrene resin, polyimide resin, or cyclodextrin as a shell. , Thereby reducing the contact between epoxy resin and curing agent. The derivatives of dicyandiamide combine various compounds with dicyandiamide, and can be reactants with epoxy resins, plastic compounds, or reactants with acrylic compounds.

As commercial products of the microcapsule type latent curing agent, "Xinxing Therapy (authorized trademark)" X-3721, HX-3722 (above, manufactured by Asahi Kasei Chemical Co., Ltd.), etc. can be used.

In the case of the microcapsule-type latent curing agent, the curing agent is surrounded by a capsule, and under a certain temperature condition, the capsule is broken and the reactive catalyst contained therein flows out and starts to react. Therefore, it has the effect of curing at low temperature and excellent storage stability.

The amine adduct type latent curing agent may further include an amine ring as a reaction product of an amine compound and an epoxy compound for the purpose of simplifying the room temperature curing of the epoxy resin composition for underfilling a semiconductor device of the present invention Oxygen tube type latent curing agent.

Specifically, the amine adduct type latent curing agent is a compound having a primary, secondary or tertiary amino group or a variety of active ingredients such as imidazole derivatives to make it react with a compound that can react with it to achieve high A substance that is molecularized and insoluble at storage temperature.

For example, the epoxy compound used in the preparation of the amine adduct type latent curing agent may include polyglycidyl ether, polyglycidyl ester, polyglycidyl ether ester, glycidyl amine compound, monofunctional epoxy compound (butyl Glycidyl ether, phenyl glycidyl ether) or polyfunctional epoxy compounds (novolak resin, cresol novolak resin, etc.), but not limited to these.

In addition, the amine compound used in the preparation of the amine adduct type latent curing agent contains at least one active hydrogen capable of reacting with an epoxy group in the molecule, as long as it contains at least one amine group in the molecule. use. Specifically, it is preferable that the compound having a tertiary amine group in the molecule increases the curing reactivity with the epoxy resin under normal temperature conditions.

For example, the amine compound may include dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylaminopropylamine. Oxazine, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-dimethylaminoethanol, 1-methyl-2-dimethylamino Ethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3 -Phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3- Butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-benzene Oxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2, 4,6-Tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoglycol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzene Biimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, etc.

As commercial products of the amine adduct type latent curing agent, "Fuji Therapeutics (authorized trademark)" FXR-1030, FXR-1081, FXR 1000, FXR 1110, FXR 1120 (above, manufactured by T&K Toka), etc. can be used.

The derivatives of dicyandiamide refer to the combination of dicyandiamide and various compounds, and can be reactants with epoxy resins, plastic compounds, or acrylic compounds.

When dicyandiamide is used as the latent curing agent, DICY-7, DICY-15 (above, manufactured by Japan Epoxy Co., Ltd.), etc. may be used as marketed products.

Based on the bisphenol epoxy resin in a weight ratio of 30 to 55 weight ratio, the latent curing agent may be included in a weight ratio of 7 to 35 weight ratio, and specifically, it may be included in a weight ratio of 7 to 30 weight ratio. When the content of the latent curing agent is less than 7 weight ratio, under the temperature condition of 150 ℃, uncuring occurs within 3 minutes, so the physical properties such as heat resistance and impact resistance will be reduced. In this case, the room temperature stability is not good, and the problem of shortening the use time may occur.

The curing agent and the latent curing agent may be included in a weight ratio of 0.4:1 to 2:1. When the weight ratio of the curing agent to the latent curing agent is less than 0.4:1, rapid curing under normal temperature conditions cannot be achieved, and the physical properties such as heat resistance and impact resistance of the underfill coating will be reduced. In the case of :1, the stability under normal temperature conditions is not good, so the use time will be shorter.

(F) Other additives

The epoxy resin composition for underfilling a semiconductor device of the present invention contains additives for stability under normal temperature conditions, suppression and removal of air bubbles in the resin, and for improving adhesion.

The additives may include stabilizers, defoamers, adhesion enhancers, and the like.

The stabilizer imparts stability to the epoxy resin composition for underfilling of semiconductor devices under normal temperature conditions, and can provide excellent long-term storage and reworkability, and the stabilizer may contain boron in order to achieve the effect Acid ester compound.

Based on the bisphenol epoxy resin in a weight ratio of 30 to 55 weight ratio, the stabilizer may be included in a weight ratio of 1 to 5 weight ratio. In the case where the content of the stabilizer is less than 1 weight ratio, the stability under normal temperature conditions will be reduced, so that (re)workability problems may occur. When the content is greater than 5 weight ratio, failures may occur. Curing, etc., lead to the problem of reduced heat resistance and impact resistance.

The defoaming agent suppresses and removes bubbles generated in the epoxy resin for underfilling the semiconductor device, and the defoaming agent may include polyalkylsiloxane.

Based on the bisphenol epoxy resin in a weight ratio of 30 to 55 weight ratio, the defoamer may be included in a weight ratio of 0.1 to 5 weight ratio. When the content of the defoamer satisfies the above range, physical properties such as impact resistance, heat resistance, and corrosion resistance of the underfill plating film can be improved by removing air bubbles in the epoxy resin for underfilling semiconductor devices.

The adhesion enhancer can increase the adhesion of the semiconductor device underfill using the epoxy resin composition for underfilling the semiconductor device. In order to achieve the effect, the adhesion enhancer may include an epoxy resin The bonding force is usually used silane coupling agent.

Based on the bisphenol epoxy resin in a weight ratio of 30 to 55 weight ratio, the adhesion enhancer may be included in a weight ratio of 0.1 to 5 weight ratio. When the content of the adhesion strength enhancer satisfies the range, the adhesion strength of the underfill of the semiconductor device is improved, and after the rework, the underfill operation of the semiconductor device is smoothly performed on the circuit board.

Hereinafter, the present invention will be explained in more detail through examples.

However, these embodiments are only used to help the understanding of the present invention, and the scope of the present invention is not limited to these embodiments.

Example 1 to Example 4

The epoxy resin composition was prepared by the combination and compounding shown in Table 1 below.

Comparative example 1

The epoxy resin composition was prepared by the combination and compounding shown in Table 2 below.

Table 1 distinguish Example 1 Example 2 Example 3 Example 4 Example 5 Bisphenol epoxy resin 42.0 42.0 42.0 42.0 42.0 Multifunctional epoxy resin 25.0 25.0 25.0 25.0 25.0 Liquid carboxyl-terminated nitrile rubber modified epoxy resin 6.0 18.0 6.0 6.0 6.0 Hardener Phenol curing agent 11.5 11.5 11.5 11.5 11.5 Amine curing agent 1.5 1.5 1.5 1.5 1.5 Latent curing agent Amine adduct type 11.5 11.5 23.0 11.5 - Microcapsule type - - - - 7.5 stabilizer 1.5 1.5 1.5 0 1.5 Defoamer 0.5 0.5 0.5 0.5 0.5 Adhesion enhancer 0.5 0.5 0.5 0.5 0.5

Table 2 distinguish Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Bisphenol epoxy resin 42.0 42.0 42.0 42.0 42.0 42.0 42.0 42.0 Multifunctional epoxy resin 25.0 25.0 25.0 25.0 25.0 25.0 15 42 Liquid carboxyl-terminated nitrile rubber modified epoxy resin - - 25 6 6 6 6 6 Phenoxy resin - 6 - - - - - - Hardener Phenol curing agent 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 Amine curing agent 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Imidazole curing agent - - - 0.5 - - - - Latent curing agent 11.5 - - - 5 40 11.5 11.5 stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Foaming agent 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Adhesion enhancer 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

The structures used in the examples and comparative examples are as follows.

Bisphenolic epoxy resin: Formaldehyde polymer with (chloromethyl)oxirane and phenol, CAS NO.9003-36-5

Multifunctional epoxy resin: YH-300 (Guodu Chemical)

Liquid carboxyl-terminated nitrile rubber modified epoxy resin: KR-207 (Guodu Chemical)

Phenol curing agent: Formaldehyde polymer with 2-(2-propenyl)phenol, CAS NO.27924-97-6

Amine curing agent: Polyoxypropylenediamine, CAS NO.9046-10-0

Latent curing agent (amine adduct type): prepared by T&K Toka, Fujicure FXR-1081

Latent curing agent (microcapsule type): manufactured by Asahi Chemical, NOVACURE HXA-3932HP

Imidazole curing agent: 1-(2-Cyanoethyl)-2-ethyl-4-methylimidazole (1-(2-Cyanoethyl)-2-ethyl-4-methylimidazole), manufactured by Shikoku Chemicals, 2E4MZ-CN, CAS NO.23996-25-0

Stabilizer: borate compound

Defoamer: Polymethylalkylsiloxane (Polymethylalkylsiloxane)

Adhesion enhancer: 3-glycidoxypropyl trimethoxysilane ((3-glycidoxypropyl) trimethoxysilane)

Experimental example

The following evaluation conditions were used to evaluate the physical properties of the epoxy resin composition for underfilling of semiconductor devices and the cured product (underfill coating) prepared in Examples 1 to 5 and Comparative Examples 1 to 8 Presented in Table 3 and Table 4 below.

Physical property evaluation and measurement conditions

The physical properties of the prepared epoxy resin composition for underfilling of semiconductor devices and the cured product were measured by the following methods.

1. Viscosity (cps): measured by Brookfield viscometer at 25°C

2. Flow rate (sec): the time required to fill the bottom of the evaluation element

3. Void: After filling the bottom of the evaluation component, confirm whether the space is included before and after curing

4. Pot-life: Under normal temperature conditions, the time it takes for the viscosity to rise twice compared with the initial viscosity

5. Reworkability: The underfill is taken out after heating the evaluation element at a temperature of 250°C

6. Adhesion: Passed Die Shear TEST or Lap Shear Test evaluation

table 3 distinguish Example 1 Example 2 Example 3 Example 4 Example 5 Viscosity (cps) 10rpm 3000 5700 4600 2900 4200 Flow rate (sec) 9 12 11 9 11 Space (void) × × × × × Tg 56 28 67 55 62 valid period 3 3 0.5 1 3 Reworkability ○ ○ ○ ○ ○ Bonding force (kgf) 5 3 7 5 5

Table 4 distinguish Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Viscosity (cps) 10rpm 1,500 7,800 5,200 2,100 2,400 4,300 4,400 1,700 Flow rate (sec) 8 37 12 8 8 11 11 7 Reactivity Curing Curing Curing Curing Uncured Curing Curing Curing Space (void) × ○ × × × × × ○ Tg 92 88 41 61 - 57 65 39 valid period 3 3 3 >1 4 >1 3 3 Reworkability × △ ○ × - ○ △ ○ Bonding force (kgf) 9 10 2 1 - 5 5 >1

Above, the present invention only describes the described embodiments in detail. Those of ordinary skill in the technical field to which the present invention belongs can make various modifications and modifications within the scope of the technical idea of the present invention. Such modifications and modifications belong to the scope of protection of the invention. .

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Claims (6)

An epoxy resin composition for underfilling a semiconductor device, which is characterized in that it comprises: (A) Bisphenol epoxy resin; (B) Multifunctional epoxy resin; (C) Liquid carboxyl-terminated nitrile rubber modified epoxy resin; (D) Curing agent; and (E) Latent curing agent. The epoxy resin composition for underfilling of semiconductor devices as described in item 1 of the scope of patent application, wherein the (A) bisphenol epoxy resin, The (B) multifunctional epoxy resin and the (C) liquid carboxyl-terminated nitrile rubber modified epoxy resin. The epoxy resin composition for underfilling semiconductor devices as described in item 1 of the scope of patent application, wherein: The (B) multifunctional epoxy resin contains 3 or more functional groups in a unit structure forming a repeating unit, These functional groups include at least one selected from the group consisting of a hydroxyl group, an alkoxy group, a halogen group, an aldehyde group, a carbonyl group, a carboxyl group, an amine group, a nitrile group, a nitro group, an amide group, an amide group, and an epoxy group. The epoxy resin composition for underfilling a semiconductor device as described in the first item of the scope of patent application, wherein the (D) curing agent and the (E) latent curing agent are included in a weight ratio of 0.4:1 to 2:1. The epoxy resin composition for underfilling a semiconductor device as described in item 1 of the patent application, wherein the (D) curing agent contains a phenol curing agent and an amine curing agent in a weight ratio of 5:1 to 10:1 . The epoxy resin composition for underfilling semiconductor devices as described in item 1 of the scope of patent application, wherein the (E) latent curing agent comprises a microcapsule type latent curing agent, an amine adduct type latent curing agent, and a double At least one of cyanamide and its derivatives.