KR20200117497A - Attech composition for semiconductor and attech films for semiconductor comprising the same - Google Patents

Abstract

The present invention relates to an adhesive composition for semiconductors including a thermoplastic resin, an epoxy resin, a rubber-modified epoxy resin, and a filler, and to an adhesive film for semiconductors including the same. The present invention effectively dissipates heat.

Description

Adhesive composition for semiconductors, and adhesive film for semiconductors containing the same TECHNICAL FIELD OF THE INVENTION

The present invention relates to an adhesive composition for semiconductors and an adhesive film for semiconductors comprising the same.

Today, the semiconductor industry has been miniaturized, high-integrated, high-speed, and low-cost, and a stack package method in which chips are stacked in multiple stages is gradually increasing to diversify the size of semiconductor chips and improve the degree of integration. Accordingly, new manufacturing processes such as GAL (Grind After Laser Cut) or DBG (Dicing Before Grind) are being introduced, and new alternatives such as MCP (Multi Chip Package), 16-layer stack, and 32-layer stack are also introduced. have. However, as semiconductor devices become highly integrated, more heat is generated, and this radiated heat not only deteriorates the function of the semiconductor device, but also causes malfunction of peripheral devices and substrate deterioration. Accordingly, many studies have been conducted on adhesives having high heat dissipation properties for securing stability of semiconductor devices.

Specifically, the high heat dissipation adhesive technology proposed so far has generally been a method of increasing the thermal conductivity of the adhesive by optimizing the content, size and shape of the inorganic filler contained in the adhesive. However, as the content of the inorganic filler increases, the adhesive strength with the semiconductor chip or lead frame decreases, and thus reliability such as peeling of the adhesive interface and generation of voids decreases. In addition, when the high heat dissipation adhesive as described above is applied and cured to form a film, the elongation of the film decreases as the content of the adhesive resin decreases, resulting in a problem of deteriorating workability, such as easily cracking even with a slight impact. .

For example, Korean Laid-Open Patent No. 2016-0063985 (Patent Document 1) includes conductive particles and resin, the conductive particles include flake-type particles and sinterable metal particles, and the resin is a thermoplastic resin or a thermosetting resin. A conductive film adhesive containing a is disclosed. However, Patent Document 1 contains conductive particles in an amount of 50 to 95% by weight, and as the content of the resin decreases, the elongation of the film is lowered, so that the film-type adhesive is less flexible and it is difficult to maintain the shape of the film. There may be a problem that the reliability of the product is deteriorated.

Therefore, since the heat generated from the semiconductor device is effectively released, the product reliability is excellent, and the elongation is excellent, so that the adhesion to the semiconductor wafer is appropriate, and thus the adhesive composition for semiconductors that can improve the workability of the semiconductor package process, and There is a need for research and development on the included adhesive film.

Korean Patent Application Publication No. 2016-0063985 (Publication date: 2016.6.7.)

Accordingly, the present invention is to provide an adhesive composition for semiconductors comprising a thermoplastic resin, an epoxy resin, a rubber-modified epoxy resin, and a filler.

The present invention provides an adhesive composition for a semiconductor comprising a thermoplastic resin, an epoxy resin, a rubber-modified epoxy resin and a filler.

In addition, the present invention provides an adhesive film for a semiconductor comprising; an adhesive layer comprising the adhesive composition.

The adhesive composition for semiconductors according to the present invention has excellent reliability, excellent elongation, and adequate adhesion to a wafer by effectively dissipating heat generated from a semiconductor device, thereby improving workability of a semiconductor package process.

Hereinafter, the present invention will be described in detail.

In the present specification, functional values such as'epoxy equivalent','acid value', and'hydroxyl value' of the resin can be measured by a method well known in the art, for example, a value measured by a method of titration. Can represent. In addition, the'weight average molecular weight' of the resin can be measured by a method well known in the art, for example, it can represent a value measured by the method of GPC (gel permeation chromatograph).

Adhesive composition for semiconductor

The adhesive composition for semiconductors according to the present invention includes a thermoplastic resin, an epoxy resin, a rubber-modified epoxy resin, and a filler.

Thermoplastic resin

The thermoplastic resin serves to improve coating properties and adhesion to the adhesive composition, and to impart smoothness.

The thermoplastic resin is not particularly limited as long as it can be used in the adhesive composition for semiconductors, and for example, acrylic resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, phenoxy resin, and butadiene-acrylo It may include at least one selected from the group consisting of a nitrile copolymer.

Specifically, the thermoplastic resin is an acrylic resin, a weight average molecular weight (Mw) of 200,000 to 1,200,000 g/mol, a viscosity of 1,500 to 7,000 mPa·s at 25°C, and a glass transition temperature of -5 to 30°C. I can.

At this time, when the weight average molecular weight of the thermoplastic resin is within the above range, excellent heat resistance and adhesion properties can be secured, and when the viscosity is within the above range, storage stability and reliability can be improved. In addition, when the glass transition temperature of the thermoplastic resin is within the above range, the impregnation property and pickup processability of the filler may be increased.

Meanwhile, the thermoplastic resin may be included in a weight ratio of 4:6 to 6:4 with respect to the total weight of the epoxy resin and the rubber-modified epoxy resin (total amount of the epoxy resin). Specifically, the thermoplastic resin may be included in a weight ratio of 4.5:5.5 to 5.5:4.5 with respect to the total amount of the epoxy resin. When the weight ratio of the total amount of the thermoplastic resin and the epoxy resin is within the above range, adhesion and smoothness may be improved by epoxy crosslinking in the adhesive composition, thereby improving product reliability.

Epoxy resin

The epoxy resin serves to improve the heat dissipation properties and adhesion of the adhesive composition.

The epoxy resin is an epoxy resin having two or more epoxy groups in one molecule, bisphenol A type epoxy resin, bisphenol A type novolac epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, Crazole novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, N-glycidyl type epoxy resin, and alicyclic epoxy resin. I can.

Specifically, the epoxy resin is preferably a biphenyl-type epoxy resin to improve the heat dissipation properties of the adhesive composition. In particular, the epoxy resin may be a biphenyl-type epoxy resin containing an alkyl group, and may be a biphenyl-type epoxy resin containing an alkyl group having 1 to 10 carbon atoms.

For example, the biphenyl-type epoxy resin containing an alkyl group having 1 to 10 carbon atoms can be obtained by reacting epichlorohydrin with a biphenol compound by a known method. Specifically, the biphenyl-type epoxy resin containing an alkyl group having 1 to 10 carbon atoms is 4,4'-bis(2,3-epoxy propoxy)biphenyl or 4,4'-bis(2,3-epoxypropoxy) -3,3',5,5'-tetramethylbiphenyl-based epoxy resin, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3',5,5' It may be an epoxy resin obtained by reacting -tetramethyl)biphenol. More specifically, it may be an epoxy resin containing 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl as a main component.

Further, the epoxy resin may have an epoxy equivalent weight (EEW) of 100 to 200 g/eq, and a weight average molecular weight (Mw) of 150 to 1,000 g/mol. Specifically, the epoxy resin may have an epoxy equivalent of 150 to 200 g/eq and a weight average molecular weight of 180 to 700 g/mol. When the epoxy equivalent weight and the weight average molecular weight of the epoxy resin are within the above ranges, there is an effect of ensuring excellent heat conduction effect and impregnation property.

In addition, the epoxy resin may be included in the composition in an amount of 50 to 130 parts by weight based on 100 parts by weight of the thermoplastic resin. When the content of the epoxy resin is within the above range, there is an effect of improving adhesion while securing excellent heat dissipation properties of the adhesive composition.

Furthermore, the epoxy resin and the rubber-modified epoxy resin may have a weight ratio of 7:3 to 9:1. Specifically, the epoxy resin and the rubber-modified epoxy resin may have a weight ratio of 7.5:2.5 to 8.5:1.5. When the weight ratio of the epoxy resin and the rubber-modified epoxy resin is within the above range, the brittleness of the adhesive composition is reduced, thereby improving product reliability and improving heat dissipation characteristics.

Rubber modified epoxy resin

The rubber-modified epoxy resin serves to improve the adhesion of the adhesive composition and to improve the elongation of the film produced therefrom.

The rubber-modified epoxy resin is carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber, acrylonitrile-butadiene rubber (NBR), epoxy-terminated butadiene-acrylonitrile (ETBN) rubber and amine-terminated butadiene-acrylonitrile (ATBN) rubber. ) It may be an epoxy resin modified with at least one rubber selected from the group consisting of rubber. Specifically, the rubber-modified epoxy resin may be an epoxy resin modified with a carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber.

In addition, the rubber-modified epoxy resin has an epoxy equivalent (EEW) of 150 to 400 g/eq, a viscosity at 25°C of 200 to 10,000 mPa·s, and a weight average molecular weight (Mw) of 200 to 3,000 g/mol. I can. Specifically, the rubber-modified epoxy resin may have an epoxy equivalent of 160 to 300 g/eq, a weight average molecular weight of 400 to 1,500 g/mol, and a viscosity at 25°C of 1,000 to 10,000 mPa·s.

When the epoxy equivalent of the rubber-modified epoxy resin is within the above range and the weight average molecular weight is within the above range, it is possible to secure the room temperature handling property and heat resistance of the adhesive composition at the same time. In addition, when the viscosity at 25° C. of the rubber-modified epoxy resin is within the above range, there is an effect of improving the flexibility and adhesion properties of the adhesive film and improving the reliability of the product due to a relatively high degree of crosslinking.

Further, the rubber-modified epoxy resin may be included in the composition in an amount of 10 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin. Specifically, the rubber-modified epoxy resin may be included in the composition in an amount of 10 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin. When the content of the rubber-modified epoxy resin is within the above range, it is possible to minimize deterioration of heat dissipation characteristics and secure excellent adhesion.

Filler

The filler may serve to improve heat dissipation properties and modulus of a film prepared from the adhesive composition.

The filler may be an inorganic filler. Specifically, the filler may be at least one inorganic filler selected from the group consisting of aluminum oxide, silicon oxide, zinc oxide, aluminum nitride, boron nitride, silica, talc, calcium carbonate, and magnesium carbonate. More specifically, the filler may be one or more inorganic fillers selected from the group consisting of aluminum oxide, silicon oxide, and zinc oxide.

In addition, the filler may include a first filler and a second filler having different particle sizes. In this case, the first filler may have an average particle diameter (D ₅₀ ) of 0.01 μm or more and less than 1 μm, and the second filler may have an average particle diameter (D ₅₀ ) of 1 μm to 10 μm. Specifically, the first filler may have an average particle diameter (D ₅₀ ) of 0.01 μm to 0.9 μm, and the second filler may have an average particle diameter (D ₅₀ ) of 1 μm to 9 μm.

As described above, when two types of fillers having different average particle diameters are included, as in Horsefiled packing theory, the filling rate of the filler is maximized to minimize voids, thereby increasing the thermal conductivity, and the first filler and the second filler When the average particle diameter of is within the above range, there is an effect of increasing thermal conductivity while securing adhesiveness and film formation of the adhesive.

Further, the filler may be included in an amount of 70% by weight or more based on the total weight of the solid content of the adhesive composition of the present invention. Specifically, the filler may be included in an amount of 70 to 90% by weight based on the total weight of the solid content of the composition. When the content of the filler is within the above range, thermal conductivity is increased by securing a heat transfer path by the filler, and basic characteristics of the adhesive film can be secured by the minimum resin content.

In addition, the filler may be included in the composition in an amount of 600 to 2,000 parts by weight based on 100 parts by weight of the thermoplastic resin. Specifically, the filler may be included in the composition in an amount of 800 to 2,000 parts by weight based on 100 parts by weight of the thermoplastic resin. When the content of the filler is within the above range, it is possible to prevent excessive increase in brittleness of the adhesive composition by the thermoplastic resin and secure thermal conductivity by the filler.

The first filler and the second filler may be included in the composition in a weight ratio of 1:9 to 3:7. Specifically, the first filler and the second filler may be included in the composition in a weight ratio of 1.2:8.8 to 2.7:7.3. When the weight ratio of the first filler and the second filler is within the above range, it is located in the gap between the second filler having a relatively large average particle size to supplement the heat transfer path and at the same time, it is possible to fill the thermoplastic resin and the epoxy resin between the fillers. The adhesion of the semiconductor wafer can be ensured. In addition, it is possible to expect a heat dissipation effect by forming a main heat transfer path while securing fluidity when bonding a semiconductor wafer by suppressing excessive increase in the specific surface area of the adhesive composition of the present invention.

Hardener

The adhesive composition according to the present invention may further include a curing agent. At this time, the curing agent may serve to improve the modulus, durability and heat resistance of the film prepared from the adhesive composition.

The curing agent may be used without limitation as long as it is applied to a semiconductor adhesive and does not deteriorate physical properties. For example, one or more compounds selected from the group consisting of phenol resins, amine resins and acid anhydride resins may be used. Can include. Specifically, the curing agent may be a xylok phenol resin, and the xylok phenol resin is a phenol-aralkyl resin obtained by reacting phenol with dimethoxyparazainene or bis(methoxymethyl)biphenyl. I can.

At this time, the commercially available products of the xyloc phenol resin include MEH-7800-S and MEH-7800-SS of Maywa Plastic Industries, but are not limited thereto.

In addition, the curing agent may have a hydroxyl value (OHv) of 100 to 300 g/eq, and a melting viscosity at 150° C. of 0.01 to 2 Pa·s. When the hydroxyl value of the curing agent is within the above range, there is an effect of securing adhesion and reliability through sufficient curing with an epoxy with a smaller amount of curing agent. When the viscosity at 150°C is within the above range, die bonding process There is an effect that it is possible to fill in steps of a printed circuit board or chip by resin flow.

The curing agent may be included so that the equivalent ratio of the epoxy resin (epoxy resin and rubber-modified epoxy resin) is 0.8 to 1.5. Specifically, the curing agent may be included so that the equivalent ratio with the epoxy resin is 1.0 to 1.4. When the content of the curing agent is within the above range, it is possible to prevent the problem of deteriorating the reliability of the product due to deterioration when exposed to high temperatures during the semiconductor manufacturing process or when the product is used, which is caused by the remaining amount of unreacted epoxy resin or curing agent remaining in the adhesive layer.

Hardening accelerator

The adhesive composition according to the present invention may further include a curing accelerator. At this time, the curing accelerator controls the curing speed of the adhesive composition, and serves to improve the durability and heat resistance of the film produced therefrom.

The curing accelerator may include at least one selected from the group consisting of a phosphorus compound, a boron compound, a phosphorus-boron compound, and an imidazole compound. Specifically, the curing accelerator may be a phosphate-based compound.

In addition, commercially available products of the curing accelerator include 2MZ-A, C11Z-A, 2MA-OK, 2PHZ, 2P4MHZ, 2PZ-CN, 2E4MZ-A, 2PHZ-PW, etc. from Sakukhwasung, and TPP, TBP, TPP from Hoko Chemical -K, TPPMK, TPPO, DPPE, DPPB, and the like, but are not limited thereto.

Further, the curing accelerator may be included in the composition in an amount of 0 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin. Specifically, the curing accelerator may be included in the composition in an amount of 0.01 to 1.5 parts by weight based on 100 parts by weight of the thermoplastic resin. When the content of the curing accelerator is within the above range, it is possible to secure reliability through a sufficient curing reaction during the semiconductor packaging process, and at the same time, storage stability at room temperature.

additive

The adhesive composition for semiconductors of the present invention is selected from the group consisting of plasticizers, defoaming agents, thickeners, dispersants, anti-settling agents, coupling agents, and solvents within a range that does not degrade physical properties with respect to the use of the product to be used, conditions of the semiconductor manufacturing process, etc. It may further appropriately contain more than one type of additive.

The plasticizer serves to increase the plasticity of the adhesive composition. In addition, the plasticizer may be, for example, a phthalic acid ester system such as di-2-ethylhexylphthalate, dioctylphthalate, diisononylphthalate, and dibutylphthalate; Phosphoric acid esters such as tricresyl phosphate, trixylyl phosphate, and triphenyl phosphate; Fatty acid esters such as di-2-ethylhexyl adipate and di-2-ethylhexyl sebacate; Epoxy systems such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate and epoxidized polybutadiene; Or a mixture of these, etc. are mentioned.

The antifoaming agent serves to suppress or eliminate phenomena such as pinholes or popping by suppressing the generation of bubbles generated during the manufacture of the adhesive layer. In addition, the antifoaming agent may be used without particular limitation as long as it is used in the adhesive composition and does not cause deterioration in physical properties. For example, commercial products of the antifoaming agent include BYK's BYK-011, BYK-015, BYK-072, Air Product's DF-21, Munzing's agitan 281, and Sannovco's Foamster-324.

The thickener serves to improve workability by adjusting the viscosity of the adhesive composition. In addition, the thickener may be, for example, wax, polyvinyl chloride (PVC), polyurethane (PU), a fluidity modifier, and a thermoplastic plastic.

The dispersant serves to improve the dispersibility of each component in the adhesive composition. In addition, the dispersant is not particularly limited as long as it is a dispersant or dispersion stabilizer commonly used in adhesives, and commercially available dispersants include BYK's DISPERBYK-110, DISPERBYK-180 and DISPERBYK-199, or Shin-Etsu Silicone's KBM-403, etc. Can be mentioned.

The anti-settling agent serves to prevent the sedimentation of raw materials constituting the adhesive composition so that the prepared adhesive layer has a uniform composition, and any conventional one that can be used in the adhesive may be used without particular limitation. For example, the anti-settling agent may include aluminum stearate, silica, organoclay, polyamide, and the like.

When the composition is blended, the coupling agent serves to improve adhesion due to chemical bonding between the surface of an inorganic material such as a filler and an organic material such as a thermoplastic resin, an epoxy resin, or a rubber-modified epoxy resin. At this time, the coupling agent may be used without particular limitation as long as it is a conventional one that can be used for an adhesive, and for example, a silane coupling agent may be used. The silane coupling agent is, for example, epoxy-containing 2-(3,4 epoxy cyclohexyl)-ethyltrimethoxysilane, 3-glycidoxytrimethoxysilane, 3-glycidoxypropyltriethoxysilane ; N-2(aminoethyl)3-amitopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltrie containing amine groups Toxoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysili-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-amino Propyltrimethoxysilane; 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltriethoxysilane containing mercapto; And 3-isocyanate propyl triethoxysilane containing isocyanate.

The solvent serves to improve workability by adjusting the viscosity of the adhesive composition. The solvent is, for example, an aromatic hydrocarbon-based solvent such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone and ethyl propyl ketone; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and ethyl ethoxy propionate; And alcohol solvents such as n-butanol, propanol, and 1-methoxy-2-propanol; And the like.

For example, the additive may be included in an amount of 0.0001 to 20 parts by weight based on 100 parts by weight of the thermoplastic resin, but is not limited thereto, and a range in which the function can be improved without impairing the physical properties of the adhesive composition for semiconductors of the present invention. It can be appropriately selected and included within.

As described above, the adhesive composition for semiconductors according to the present invention effectively releases heat generated from a semiconductor device to improve product reliability, and has excellent elongation and good adhesion to semiconductor wafers, thereby improving workability of the semiconductor package process. I can make it.

The adhesive composition for semiconductors of the present invention may further include other additives within a range that does not impair physical properties according to a usage mode and method, and may be prepared and used in any formulation through this. For example, the adhesive composition for semiconductors may be manufactured and used in the form of a liquid, paste, gel, or film, but is not limited thereto.

Adhesive film for semiconductor

The adhesive film for semiconductors according to the present invention may include an adhesive layer including the adhesive composition for semiconductors as described above.

Adhesive layer

The adhesive layer is deposited on a semiconductor wafer and serves to adhere the cut chip onto a substrate or other semiconductor chip.

The adhesive layer includes the adhesive composition for a semiconductor of the present invention as described above.

In this case, the thickness of the adhesive layer is not particularly limited as long as it can be applied to the adhesive layer of an adhesive film for semiconductors, but may be, for example, 1 to 20 μm. Specifically, the thickness of the adhesive layer may be 2 to 20 μm, or 5 to 20 μm. When the thickness of the adhesive layer is within the above range, the film forming property becomes poor, the amount of deformation and stress due to heat shrinkage increase, causing warpage of the semiconductor chip, and the reliability of the semiconductor package by increasing the amount of organic solvent in the adhesive layer. The problem of lowering the value can be prevented.

The adhesive film for semiconductor may further include a base film and an adhesive layer. Specifically, the adhesive film for semiconductor may include a form in which a base film, an adhesive layer, and an adhesive layer are sequentially stacked.

The base film is not particularly limited as long as it can be used as a base film for an adhesive film for semiconductors. For example, the base film is polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ionomer copolymer, ethylene-vinyl alcohol copolymer , Polybutene, a copolymer of styrene, and the like, but are not limited thereto.

The adhesive layer supports the wafer during the sawing process and is separated from the adhesive layer during the pickup process. The adhesive layer is not particularly limited as long as it can be used for an adhesive film for semiconductors, and may be, for example, an ultraviolet curable type or a non-ultraviolet type.

The adhesive film for semiconductors may further include a release film. Specifically, the adhesive film for semiconductors may include a form in which a base film, an adhesive layer, an adhesive layer, and a release film are sequentially stacked.

The release film is not particularly limited as long as it can be applied to an adhesive film for semiconductors. For example, the release film includes plastic films such as polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, and polyimide film. However, it is not limited thereto. In addition, the release film may have a release-treated surface with a release agent such as an alkylide-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based, or wax-based release agent, but is not limited thereto. In this case, the release film may have an average thickness of 5 to 500 µm, or 10 to 200 µm, but is not limited thereto.

The semiconductor adhesive film may have a tensile elongation of 50 to 350% and a vertical thermal conductivity of 2.0 W/m·K or more. Specifically, the adhesive film for semiconductors may have a tensile elongation of 70 to 300% and a vertical thermal conductivity of 2.0 to 10.0 W/m·K.

The adhesive film for semiconductors according to the present invention as described above has excellent reliability by effectively dissipating heat generated from semiconductor devices including the adhesive layer, excellent elongation, and adequate adhesion to the wafer, so that the workability of the semiconductor package process Can improve.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[Experimental Example]

Preparation Example 1. Preparation of filler dispersion

100 parts by weight of alumina having an average particle diameter (D ₅₀ ) of 3.0 μm, 25 parts by weight of alumina having an average particle diameter (D ₅₀ ) of 0.5 μm, 1 part by weight of a silane coupling agent and 69 parts by weight of methyl ethyl ketone were added to the reactor, and at room temperature for 1 hour After stirring for 2 hours using a ball mill to disperse to prepare a filler dispersion (dispersion liquid-1).

Preparation Examples 2 and 3. Preparation of filler dispersion

A filler dispersion (dispersion-2 or dispersion-3) was prepared in the same manner as in Preparation Example 1, except that the contents of each component described in Table 1 were used.

Composition (parts by weight) Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 1st filler (alumina, D ₅₀ 0.5㎛ 25 - 6.7 Second filler (alumina, D ₅₀ 3.0㎛) 100 100 100 Additive (silane coupling agent) 1.2 One 1.7 Methyl ethyl ketone (MEK) 69 55.4 91.6 Mass ratio of the first filler: the second filler 1:4 - 1:1.5

Examples 1 to 9 and Comparative Examples 1 to 6. Preparation of adhesive composition

The composition was used as shown in Tables 2 and 3, and specifically, a thermoplastic resin, an epoxy resin, a rubber-modified epoxy resin, and a solvent were mixed at room temperature for 1 hour. Then, a filler dispersion and a curing agent were added to prepare a mixture. Then, a curing accelerator and an additive (silane coupling agent) were sequentially added and stirred at room temperature for 1 hour to prepare an adhesive composition.

(Part by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Thermoplastic resin 15 15 15 15 15 15 15 Epoxy resin 12 12 11.3 12.8 12 9.8 12 Rubber Modified Epoxy Resin A 3 3 3.8 2.3 3 5.3 3 Rubber Modified Epoxy Resin B - - - - - - - Hardener 10 10 10 9.9 10 10 10 Hardening accelerator 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Dispersion-1 166.08 123.26 166.14 165.95 95.17 166.34 - Dispersion-2 - - - - - - 166.08 Dispersion -3 - - - - - - - additive 2.1 1.7 2.1 2.1 1.4 2.1 2.1 solvent 35 14.5 35.1 34.9 1.1 35.2 35 total 208.28 165.06 208.44 208.15 136.67 208.64 208.28

(Part by weight) Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Thermoplastic resin 15 15 15 15 - 15 15 15 Epoxy resin 12 12 15 - 12.7 21 7.8 12 Rubber Modified Epoxy Resin A 3 - - 14 2.6 3 9 3 Rubber Modified Epoxy Resin B - 3 - - - - - - Hardener 10 10 9.9 9.9 10 10.1 12 10 Hardening accelerator 0.1 0.1 0.1 0.1 0.1 0.11 0.12 0.1 Dispersion-1 - 166.08 165.76 165.18 170.83 170.83 167.55 394.368 Dispersion-2 - - - - - - - - Dispersion -3 166.08 - - - - - - - additive 2.1 2.1 2.1 1.9 2.1 2.3 2.2 4.5 solvent 35 35 34.8 34 35 37 33 144.4 total 208.28 208.28 207.86 206.08 233.33 222.34 213.67 438.968

Hereinafter, components and physical properties of each component used in Examples and Comparative Examples are shown in Table 4 below.

Component ingredient Thermoplastic resin Acrylic Copolymer(Rubber), Mw: 850,000g/mol, Viscosity: 4,000mPa·s at 25℃ Epoxy resin Tetra Methyl Biphenyl Epoxy resin(4,4-Bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl)), Cas.no 85954-11-6, Mw: 372 g /mol, EEW: 180-192g/eq Rubber Modified Epoxy Resin A Carboxylic Terminated Butadiene Acrylonitrile(CTBN) modified Epoxy resin, EEW: 175-205g/eq, viscosity: 2,000-3,000 mPa·s at 25℃, Mw: 570 g/mol Rubber Modified Epoxy Resin B Carboxylic Terminated Butadiene Acrylonitrile(CTBN) modified Epoxy resin, EEW: 530-630g/eq Hardener Xylin-based phenolic resin (Phenol-aralkyl resin), Cas no. 176669-91-3, OHv: 167-180g/eq, viscosity: 35mPa·s at 25°C, Mw: 400 g/mol Hardening accelerator Triphenyl phosphate (TPP), MP: 82℃, BP: 200℃@2.0kPa First filler Spherical alumina (Alumina (Al ₂ O ₃ )), D ₅₀ : 3.0 μm, thermal conductivity 20-30 w/mk. Specific surface area 1.67 m ² /g 2nd filler Spherical alumina (Alumina (Al ₂ O ₃ )), D ₅₀ : 0.5㎛, thermal conductivity 20-30 w/mK Additive (silane coupling agent) 3-Glycidoxypropyl triethoxysilane, Cas no. 2530-83-8, Refractive Index: 1.427 (@25℃) solvent MEK (Methyl Ethyl Ketone)

Test Example: Evaluation of physical properties

The adhesive compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were coated on a PET film, dried at 80° C. for 5 minutes, and dried at 100° C. for 5 minutes to prepare an adhesive layer.

A photocurable dicing tape (manufacturer: KCC, product name: DF-1300) was laminated on one side of the adhesive layer prepared at room temperature to prepare an adhesive film for a semiconductor package. The physical properties of the manufactured adhesive film for a semiconductor package were measured in the following manner, and the results are shown in Tables 5 and 6.

(1) tensile elongation

Tensile elongation was evaluated according to ASTM D 638, and as measurement conditions, a specimen width of 10 mm, a grip distance of 50 mm, and a tensile speed of 500 mm/min were evaluated.

(2) Wafer adhesion

In order to measure the adhesion of the adhesive film to the wafer, a peel force of 180° was tested using a universal testing machine according to JIS Z 0237 and KSA 1107 standards.

(3) pickup characteristics

The wafer after the cutting and cleaning process was irradiated with ultraviolet rays of 150 mJ/cm ² using an ultraviolet irradiation device, and then left at room temperature for 20 minutes, and the pick-up characteristics were evaluated using a die attach equipment (Secron, SDB-30US). Specifically, the pickup process was set under conditions of 10 mm × 10 mm chip, 10 pins, and 5 mm extension, and then performed on 100 chips in the center of the wafer in the range of 200 to 800 µm with a pin stroke. The case where all chips were picked up by the pickup process was evaluated as ○, the case where all the chips were picked up by two to three pickup processes was evaluated as △, and the case where four or more pickup processes were required was evaluated as X.

(4) Lead heat resistance

The adhesive film was laminated at 80° C. on a polyimide film (manufacturer: SKC KOLON PI, product name: IF70), cut into 15 mm x 75 mm, and laminated on a slide glass at 120° C. to prepare a specimen. The specimen was cured at 175° C. for 2 hours, stored at 85° C. and 85% relative humidity for 24 hours, immersed in a 260° C. lead bath for 30 seconds, and then it was confirmed whether bubbles were generated through microscopic observation. Specifically, in the specimen, no bubbles were expressed as Pass, and those with bubbles were indicated as Void.

(5) heat dissipation characteristics

To evaluate the heat dissipation characteristics of the adhesive film, cut into 12.7mm × 12.7mm, cured at 175℃ for 2 hours, and measure the vertical thermal conductivity using a thermal conductivity tester (manufacturer: NETZSCH, model name: LFA-457). I did.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Filler (% by weight) to the total weight of solids 80 75 80 80 70 80 80 Weight ratio of the first filler/second filler 20/80 20/80 20/80 20/80 20/80 20/80 0/100 Weight ratio of thermoplastic resin/(epoxy resin+rubber modified epoxy resin) 50/50 50/50 50/50 50/50 50/50 50/50 50/50 Epoxy resin/rubber modified epoxy resin weight ratio 80/20 80/20 75/25 85/15 80/20 65/35 80/20 Tensile elongation (%) 153 233 186 77 374 430 178 Wafer adhesion (gf/Inch) 159 171 164 133 183 203 174 Pickup characteristics ○ ○ ○ ○ ○ ○ ○ Lead heat resistance Pass Pass Pass Pass Pass Void Pass Heat dissipation characteristics (W/mK) 2.59 2.15 2.44 2.61 1.69 2.44 1.62

Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Filler (% by weight) to the total weight of solids 80 80 80 80 86 77 78 90 Weight ratio of the first filler/second filler 40/60 20/80 20/80 20/80 20/80 20/80 20/80 20/80 Weight ratio of thermoplastic resin/(epoxy resin+rubber modified epoxy resin) 50/50 50/50 50/50 50/50 0/100 38/62 47/53 50/50 Epoxy resin/rubber modified epoxy resin weight ratio 80/20 80/20 100/0 0/100 83/17 88/12 46/54 80/20 Tensile elongation (%) 45 191 17 138 Not measurable 9 343 30 Wafer adhesion (gf/Inch) 111 144 102 163 Not measurable 194 155 82 Pickup characteristics ○ △ ○ △ Not measurable X X ○ Lead heat resistance Void Void Void Pass Not measurable Pass Void Void Heat dissipation characteristics (W/mK) 1.88 2.47 2.6 1.54 Not measurable 2.64 1.65 2.63

As shown in Tables 5 and 6, the adhesive film including the adhesive layer prepared from the adhesive composition of Examples 1 to 9 exhibits a tensile elongation of 30% or more, a wafer adhesion of 80 gf/inch or more, and excellent heat dissipation properties. Do. In particular, the adhesive film of Examples 1 to 5, wherein the content of the filler is more than 70% by weight based on the total weight of the solid content, the content ratio of the epoxy resin and the rubber-modified epoxy resin is appropriate, and the content ratio of the first filler and the second filler is appropriate. Silver has excellent tensile elongation, pickup characteristics, lead heat resistance and heat dissipation characteristics.

On the other hand, the adhesive film including the adhesive layer prepared from the adhesive composition of Comparative Example 1 not containing the rubber-modified epoxy resin had a problem that a low tensile elongation of 20% or less and a void phenomenon appeared. In addition, the adhesive film including the adhesive layer prepared from the adhesive composition of Comparative Example 2 that does not contain an epoxy resin lacks pick-up properties and heat dissipation properties. Furthermore, the adhesive composition of Comparative Example 3 that does not contain a thermoplastic resin has insufficient resin content, making it difficult to form a film, so that physical properties cannot be measured. In addition, the adhesive film including the adhesive layer prepared from the adhesive composition of Comparative Example 4 containing a large amount of the epoxy resin compared to the thermoplastic resin has a problem that the elongation is insufficient, and the adhesive layer is broken during the pick-up evaluation. In addition, compared to the thermoplastic resin, the adhesive layer prepared from the adhesive composition of Comparative Example 5 containing a rubber-modified epoxy resin had excessive tack characteristics, making it difficult to proceed with pickup, and the curing degree of the entire film was reduced, resulting in insufficient lead heat resistance.

Claims (5)

A semiconductor adhesive composition comprising a thermoplastic resin, an epoxy resin, a rubber-modified epoxy resin and a filler. The method according to claim 1,
The composition is based on 100 parts by weight of the thermoplastic resin,
An adhesive composition for a semiconductor comprising 50 to 130 parts by weight of an epoxy resin, 10 to 50 parts by weight of a rubber-modified epoxy resin, and 600 to 2,000 parts by weight of a filler. The method according to claim 1,
The filler includes a first filler and a second filler,
The first filler has an average particle diameter of 0.01 μm or more and less than 1 μm,
The second filler has an average particle diameter of 1 μm to 10 μm, an adhesive composition for a semiconductor. Containing, an adhesive film for semiconductors; an adhesive layer comprising the adhesive composition of any one of claims 1 to 3. The method of claim 4,
The adhesive film has a tensile elongation of 50 to 350% and a vertical thermal conductivity of 2.0 W/m·K or more, an adhesive film for a semiconductor.