KR20220058031A - Epoxy adhesive composition having excellent fluidity and die attach film including the same - Google Patents

Abstract

Disclosed in the present specification is an epoxy adhesive composition and a die attach film including the same. The epoxy adhesive composition includes a thermoplastic resin, an epoxy resin, an inorganic filler, and an epoxy hardener. According to the present invention, the epoxy adhesive composition satisfies processability such as sawing and picking-up, and reliability required for semiconductor packaging.

Description

EPOXY ADHESIVE COMPOSITION HAVING EXCELLENT FLUIDITY AND DIE ATTACH FILM INCLUDING THE SAME}

The present specification relates to an epoxy adhesive composition having excellent fluidity and a die attach film including the same, and more particularly, to an epoxy adhesive composition that can be used for semiconductors and the like, and a die attach film including the same.

In recent years, with the rapid miniaturization, high density, and ultra-high speed of electronic components and mobile devices, semiconductor technologies are also becoming more integrated and thinner. In particular, as the capacity of semiconductors increases, the conventional method of accumulating cells only on the semiconductor chip plane in a narrow space has reached its physical limit. By stacking the semiconductor chips in this way, a high capacity of the semiconductor is realized, and driving speed can be increased by driving the semiconductor chips as a single package. In the semiconductor package section, this is expressed as Stacked Chip Scale Package (SCSP).

The adhesive used for chip lamination in the SCSP manufacturing process is one of the key materials. In the past, epoxy paste was widely used for attaching chips, but with the development of technology, a die attach film (DAF) is mainly used. DAF used in SCSP can be broadly classified into a type of attaching a chip to a chip or a chip to a substrate, and attaching it without generating pores is one of the important tasks.

In addition, as film-over-wire (FOW), a special type of DAF that fills the bonding wire of the chip, requires a very high level of fluidity and high adhesive properties to fill between the wires, the development of a material that includes these required characteristics is difficult. It is essential.

KR 10-2013-0033561 A (2013.04.04)

In one aspect of the present invention, it is an object of the present invention to provide an epoxy-based adhesive that satisfies the high adhesive strength required for semiconductor packaging, processability and reliability such as sawing and pick-up, and a die attach film including the same.

In exemplary embodiments of the present specification, it includes a thermoplastic resin, an epoxy resin, an inorganic filler, and an epoxy curing agent, wherein the epoxy resin is a bifunctional bisphenol-based epoxy resin; bifunctional cresol novolac-based epoxy resins; And a trifunctional or tetrafunctional naphthalene-based epoxy resin; it provides an epoxy adhesive composition comprising a.

In still other exemplary embodiments of the present specification, a substrate; And it provides a die attach film (DAF; Die Attach Film) comprising a; and an adhesive layer comprising the above-mentioned epoxy adhesive composition.

The epoxy adhesive composition of the present specification may satisfy high adhesion, sawing and pick-up, and processability and reliability required for semiconductor packaging while having excellent fluidity.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

Hereinafter, exemplary embodiments of the present invention will be described in detail.

In exemplary embodiments of the present specification, it includes a thermoplastic resin, an epoxy resin, an inorganic filler, and an epoxy curing agent, wherein the epoxy resin is a bifunctional bisphenol-based epoxy resin; bifunctional cresol novolac-based epoxy resins; And a trifunctional or tetrafunctional naphthalene-based epoxy resin; it provides an epoxy adhesive composition comprising a.

In one embodiment of the present invention, the bifunctional epoxy resin implements the basic physical properties of a general epoxy resin, and the trifunctional or tetrafunctional epoxy resin is selected to further strengthen the basic physical properties of the epoxy resin.

Specifically, the presence of -OH groups in the bifunctional bisphenol-based epoxy resin affects the adhesion and flow properties of the epoxy resin, and in the bifunctional cresol novolac-based epoxy resin, -OH does not exist in the repeating structure, so adhesion properties Although it is relatively unfavorable to the benzene group, it is advantageous in terms of heat resistance, and trifunctional or tetrafunctional naphthalene-based epoxy resins have good heat resistance and increase the crosslinking density in the epoxy resin, which affects heat resistance stability and improvement of mechanical properties. .

However, since the trifunctional or tetrafunctional polyfunctional epoxy resin reacts quickly with the curing agent, it is preferable to configure an appropriate amount in the epoxy resin composition.

In addition, when selecting an epoxy, it is suitable to select a low epoxy with a low equivalent in order to strengthen the flow function and suppress a decrease in adhesive properties. Preferably, the equivalent weight is 50 to 250 g/eq. Epoxy corresponding to this is a trifunctional or tetrafunctional naphthalene-based epoxy resin, and various polyfunctional naphthalene-based epoxy resins may be mixed and used.

In an exemplary embodiment, the bifunctional bisphenol-based epoxy resin is a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, a bisphenol S-type epoxy compound, a hydrogenated bisphenol A-type epoxy compound, and a hydrogenated bisphenol F-type epoxy compound. It may include one or more selected from.

In an exemplary embodiment, the bifunctional cresol novolac-based epoxy resin may include O-cresol novolac or p-/m-cresol novolac.

In an exemplary embodiment, the trifunctional or tetrafunctional naphthalene-based epoxy resin is composed of N,N,N',N'-tetraglycidyl-m-xylenediamine and triglycidyl-p-aminophenol. It may include one or more selected from the group.

In an exemplary embodiment, the epoxy resin may include, based on the total weight of the epoxy resin, 20 to 40 parts by weight of a bifunctional bisphenol-based epoxy resin; 20 to 40 parts by weight of a bifunctional cresol novolak-based epoxy resin; and 20 to 40 parts by weight of a trifunctional or tetrafunctional naphthalene-based epoxy resin.

In an exemplary embodiment, the thermoplastic resin is polyimide, polyether imide, polyester imide, polyamide, polyether sulfone, polyether ketone, polyolefin, polyvinyl chloride, phenoxy, reactive butadiene acrylonitrile copolymer rubber And (meth) may include at least one selected from the group consisting of acrylate-based resins.

The inorganic filler is intended to lower a CTE (Coefficient of Thermal Expansion) value.

In an exemplary embodiment, the inorganic filler may include at least one selected from the group consisting of silica, alumina, magnesium oxide, magnesium silicate, titanium oxide, boron nitride, zirconia, calcium carbonate, magnesium carbonate, and aluminum hydroxide. .

In an exemplary embodiment, the epoxy curing agent may include at least one selected from the group consisting of an amine-based curing agent, a phenol-based curing agent and an isocyanate-based curing agent, and an active ester curing agent.

The epoxy curing agent serves to cure the resin, and may cause an effect of improving heat resistance and adhesive properties during a curing reaction. An amine-based curing agent is usually used, but depending on the reactivity, a phenol-based curing agent, an isocyanate-based curing agent, or an active ester curing agent may be used. The amount to be added can be added by calculating the amount of active hydrogen to the equivalent of the epoxy resin.

If necessary, a curing catalyst for accelerating the reaction of the epoxy resin and the curing agent for the epoxy resin may be optionally used.

In an exemplary embodiment, the epoxy adhesive composition may further include a curing catalyst, and the curing catalyst may include at least one selected from the group consisting of an imidazole-based catalyst, a phosphine-based catalyst, and a boron-based catalyst.

In an exemplary embodiment, the epoxy adhesive composition may optionally contain a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a bleach, a colorant, a conductive agent, a release agent, a surface treatment agent, a viscosity modifier, a phosphorus-based flame retardant , and may further include additives such as flame-retardant fillers, silica fillers, and fluorine fillers.

In an exemplary embodiment, based on the total weight of the epoxy adhesive composition, 10 to 30 parts by weight of a thermoplastic resin; 10 to 40 parts by weight of an epoxy resin; 30 to 50 parts by weight of an inorganic filler; and 0.05 to 5 parts by weight of an epoxy curing agent.

When the weight part of the epoxy resin is less than 10 parts by weight, crosslinking density and adhesive cohesive force are weakened, adhesion may be lowered and heat resistance may be lowered, and if it is more than 40 parts by weight, fluidity may be lowered.

When the content of the thermoplastic resin is too small, it is difficult to expect a stress relaxation effect between the substrate and the wafer because the modulus is rapidly increased after curing of the resin composition. In addition, if the content of the thermoplastic resin is too high, fluidity may be lowered, making it difficult to remove voids during the curing process, thereby reducing product reliability.

In the case of less than 30 parts by weight of the inorganic filler, the CTE value increases, and when it exceeds 50 parts by weight, there is a problem in that fluidity is lowered, and also workability may be poor due to dispersibility and viscosity problems.

In an exemplary embodiment, the epoxy adhesive composition may be for a die attach film (DAF).

In still other exemplary embodiments of the present specification, a substrate; And it provides a die attach film (DAF; Die Attach Film) comprising a; and an adhesive layer comprising the above-mentioned epoxy adhesive composition.

In an exemplary embodiment, the thickness of the substrate may be 20 to 75 μm, and the thickness of the adhesive layer may be 5 to 70 μm.

In an exemplary embodiment, the die attach film may be for a semiconductor.

Hereinafter, specific embodiments according to exemplary embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following examples, and various types of embodiments can be embodied within the scope of the appended claims. It will be understood that the intention is to facilitate practice of the invention to those skilled in the art.

Example

An epoxy adhesive composition was prepared with the composition shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Epoxy Resin 1 YD-011 12.5 12.5 12.5 12.5 Epoxy Resin 2 YDCN500-1P 13.0 13.0 13.1 26.2 Epoxy resin 3 jer 630 - 12.1 5.7 - erisys ga-240 11.0 - 6.4 - thermoplastic resin KG-800 21.4 21.4 21.4 21.4 inorganic filler SC-2050MB 39.7 39.7 39.7 39.7 hardening accelerator DICY 1.5 1.5 1.5 1.5 curing catalyst 0.1 0.1 0.1 0.1

YD-011: bisphenol A epoxy resin (diglycidyl ether of bisphenol A),

YDCN500-1P : O-cresol novolac epoxy resin

JER 630: triglycidyl-p-aminophenol (trifunctional epoxy)

erisys ga-240: N,N,N',N'-tetraglycidyl-m-xylenediamine (tetrafunctional epoxy)

KG-8000 : Thermoplastic

SC-2050MB : Silica inorganic filler

Hardener: Dicyandiamide

Curing catalyst: Imidazole type

Specifically, as the mixed epoxy resin, the epoxy resin 1 is bisphenol A epoxy (YD-011), the epoxy resin 2 is cresol novolac epoxy (YDCN500-1P), and the epoxy resin 3 is an epoxy (multi-functional epoxy) containing a multifunctional group was prepared by mixing.

An epoxy adhesive as shown in Table 1 by mixing an acrylic ester resin (kG-8000), an inorganic filler (SC-2050MB), a curing agent (Dicyandiamide) and a curing catalyst (Imidazole-based) containing an epoxy group as a thermoplastic resin in the mixed epoxy resin A composition was prepared.

After applying the prepared composition on the release-treated polyester film, the solvent was dried and removed in a hot air dryer at 130° C. for 3 minutes to form an adhesive film for a B-Stage characteristic die attach film having a thickness of 60 μm. prepared.

Experimental example

(1) Measurement of Die Shear Strength

The adhesive film obtained in the above example was laminated with a UV dicing film using a rubber roll laminating machine. This film was mounted on a wafer having a diameter of 8 inches and a thickness of 50 μm at 70°C. The specimen was wafer diced to a chip size of 5 mm x 5 mm using DFD-651 of Disco. After UV curing the specimen at 400mJ, a chip with an adhesive film was manufactured using Shinkawa's SPA-210. After placing a wafer mirror of 10 mm x 10 mm size on a hot plate at 130 °C, the prepared specimen was compressed for 2 seconds at a pressure of 2 kgf and cured in a drying oven at 180 °C for 2 hours. Specimens were prepared before and after leaving the thus-prepared specimens in a thermo-hygrostat under conditions of 85° C. and 85% relative humidity for 24 hours. And the force was measured while pushing the wafer chip at a speed of 50 μm/s using a die share tester DAGE 4000, and the results are shown in Table 2.

(2) Viscosity measurement

The adhesive film obtained in the above example was laminated using a rubber roll laminator until it became 600 μm thick. After preparing an 8 mm circular specimen for this film, the viscosity was measured using ARES-G2 manufactured by TA, and the results are shown in Table 2.

(3) Water Absorption Measurement

The adhesive film obtained in the above example was laminated using a rubber roll laminating machine until it became 1000 μm thick. A specimen is prepared by cutting this film into a size of 50 mm x 50 mm. After curing the specimen in a drying oven at 180° C. for 2 hours, the weight (A) was measured. In addition, the specimen was left in a thermo-hygrostat under conditions of 85° C. and 85% relative humidity for 24 hours, and then the weight (B) was measured, and the moisture absorption was measured using the following formula, and the results are shown in Table 2.

Calculation formula: Water Absorption(%) = ((B-A)/A)*100

(4)Sawing Castle

The adhesive film obtained in the above example was laminated with a UV dicing film using a rubber roll laminating machine. This film was mounted on a wafer having a diameter of 8 inches and a thickness of 50 μm at 70° C. to prepare a specimen. The prepared specimen was subjected to wafer dicing to a chip size of 5 mm x 5 mm using Disco's DFD-651, and the results are shown in Table 2. At this time, the sawing performance evaluation criteria are as follows.

○ : Chip appearance defect due to flying and water immersion is less than 0% of the total wafer area

△: Chip appearance defects due to flying and water immersion less than 5% of the total wafer area

X: Chip appearance defects due to flying and water immersion exceed 5% of the total wafer area

(5) Pick-up

The adhesive film obtained in the above example was laminated with a UV dicing film using a rubber roll laminator. This film was mounted on a wafer having a diameter of 8 inches and a thickness of 50 μm at 70° C. to prepare a specimen. The specimen was wafer diced to a chip size of 5 mm x 5 mm using DFD-651 of Disco. After UV curing the produced specimen at 400mJ, pickup was performed using Shinkawa's SPA-210, and the results are shown in Table 2.

At this time, the pick-up evaluation criteria are as follows.

○: Pickup success rate 100%

△ : Pickup success rate 90% ~ 100%

X: Pickup success rate less than 90%

(6) Substrate fillability

The adhesive film obtained in the above example was cut to a size of 10 mm × 10 mm, and then laminated on a cover glass at 70°C. This specimen was compressed for 1 second at 130°C and 10 kgf pressure on a printed wiring circuit board (PCB) using Shinkawa's SPA-210 to prepare a specimen. Thereafter, the prepared specimen was evaluated for substrate fillability using a microscope, and the results are shown in Table 2 below.

In this case, the evaluation criteria of the substrate fillability are as follows.

○: 70% or more of substrate fillability

△: 30 to 70% of substrate fillability

X: Substrate fillability 30% or less

Example 1 Example 2 Example 3 comparative example Die Shear 85/85*0hr 199 187 194 178 Strength 85/85*24hr 96 86 90 76 Viscosity Pa.s (@130) 1860 1943 1910 2105 Water Absorption % 0.38 0.44 0.42 0.51 Sawing Castle ○ ○ ○ ○ pick-up ○ △ ○ △ Substrate fillability ○ ○ ○ Ⅹ

Referring to Table 2, when only the bifunctional epoxy composition was used as in Comparative Example 1, it was confirmed that the mechanical properties and workability were lowered as compared with Examples.

In addition, in the case of the multifunctional epoxy composition as an Example, it was confirmed that the most excellent mechanical properties and processability when using the tetrafunctional epoxy alone as in Example 1.

Claims (14)

a thermoplastic resin, an epoxy resin, an inorganic filler, and an epoxy curing agent;
The epoxy resin is
bifunctional bisphenol-based epoxy resin;
bifunctional cresol novolac-based epoxy resins; and
A trifunctional or tetrafunctional naphthalene-based epoxy resin; containing, the epoxy adhesive composition. The method of claim 1,
The bifunctional bisphenol-based epoxy resin is at least one selected from the group consisting of a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, a bisphenol S-type epoxy compound, a hydrogenated bisphenol A-type epoxy compound, and a hydrogenated bisphenol F-type epoxy compound. comprising, an epoxy adhesive composition. The method of claim 1,
An epoxy adhesive composition comprising the bifunctional cresol novolak-based epoxy O-cresol novolak or p-/m-cresol novolak. The method of claim 1,
The trifunctional or tetrafunctional naphthalene-based epoxy resin is one selected from the group consisting of N,N,N',N'-tetraglycidyl-m-xylenediamine, and triglycidyl-p-aminophenol An epoxy adhesive composition comprising the above. The method of claim 1,
The epoxy resin is based on the total weight of the epoxy resin,
20 to 40 parts by weight of a bifunctional bisphenol-based epoxy resin;
20 to 40 parts by weight of a bifunctional cresol novolak-based epoxy resin; and
20 to 40 parts by weight of a trifunctional or tetrafunctional naphthalene-based epoxy resin; Containing, an epoxy adhesive composition. The method of claim 1,
The thermoplastic resin is polyimide, polyether imide, polyester imide, polyamide, polyether sulfone, polyether ketone, polyolefin, polyvinyl chloride, phenoxy, reactive butadiene acrylonitrile copolymer rubber and (meth)acrylate. An epoxy adhesive composition comprising at least one selected from the group consisting of a resin-based resin. The method of claim 1,
The inorganic filler comprises at least one selected from the group consisting of silica, alumina, magnesium oxide, magnesium silicate, titanium oxide, boron nitride, zirconia, calcium carbonate, magnesium carbonate, and aluminum hydroxide, epoxy adhesive composition. The method of claim 1,
The epoxy curing agent comprises at least one selected from the group consisting of an amine-based curing agent, a phenol-based curing agent and an isocyanate-based curing agent, and an active ester curing agent, an epoxy adhesive composition. The method of claim 1,
The epoxy adhesive composition further comprises a curing catalyst,
The curing catalyst comprises at least one selected from the group consisting of an imidazole-based catalyst, a phosphine-based catalyst, and a boron-based catalyst, the epoxy adhesive composition. The method of claim 1,
Based on the total weight of the epoxy adhesive composition,
10 to 30 parts by weight of a thermoplastic resin;
10 to 40 parts by weight of an epoxy resin;
30 to 50 parts by weight of an inorganic filler; and
An epoxy adhesive composition comprising; 0.05 to 5 parts by weight of an epoxy curing agent. The method of claim 1,
The epoxy adhesive composition is for a die attach film (DAF; Die Attach Film), the epoxy adhesive composition. write; and
12. A die attach film comprising a; an adhesive layer comprising the epoxy adhesive composition according to any one of claims 1 to 11 (DAF; Die Attach Film). 13. The method of claim 12,
The thickness of the substrate is 20 to 75 μm,
The thickness of the adhesive layer is 5 to 70 μm, a die attach film (DAF; Die Attach Film). 13. The method of claim 12,
The die attach film is for semiconductors, die attach film (DAF; Die Attach Film).