KR20080065844A - Adheisive composition, adehesive film and dicing die bonding film using the same - Google Patents

Abstract

An adhesive resin composition is provided to ensure an excellent circuit filling property even while retaining superior long-term storage and heat resistance. An adhesive resin composition includes (A) (meth)acrylic copolymers comprising (a) a non-functional monomer, (b) a monomer having a functional group capable of reacting with an epoxy resin at a temperature below 150 °C, and (c) a monomer containing a functional group capable of reacting with an epoxy resin at a temperature of 150 °C or higher, and (B) an epoxy resin. An adhesive film comprises a base film(10), and an adhesive layer(20) containing the adhesive resin composition, which is formed on the base film.

Description

Adhesive composition, adhesive film and dicing die bonding film using the same {ADHEISIVE COMPOSITION, ADEHESIVE FILM AND DICING DIE BONDING FILM USING THE SAME}

1 is a cross-sectional view of an adhesive film according to the present invention.

2 is a cross-sectional view of a dicing die bonding film according to the present invention.

3 is a cross-sectional view of a semiconductor device according to the present invention.

* Description of the main symbols in the drawing

Base film of 1 semiconductor chip 10 adhesive film

20 Adhesion layer of adhesive film 30 Adhesion layer of dicing die bonding film

40 Base of Dicing Die Bonding Film 50 Wiring Board

The present invention relates to an adhesive composition having excellent reliability as a member for a semiconductor package, an adhesive film using the same, and a semiconductor device using the adhesive film.

Recently, high-density mounting on semiconductor substrates is required due to high integration and high functionality of semiconductor memories, starting with flash memories mounted in mobile phones or mobile terminals. In addition, with the miniaturization and weight reduction of semiconductor memories, mounting technologies such as chip size packaging (CSP) and ball grid array (BGA) are rapidly being developed.

Among the important characteristics of electronic components mounted with semiconductor chips, connection reliability is a very important item because it is related to device quality. In particular, the connection reliability depends on the difference in the coefficient of thermal expansion between the mounted semiconductor chip and the substrate. Therefore, in order to reduce the difference of the thermal expansion coefficient, a low elastic adhesive film (hereinafter referred to as an adhesive film for a die bond) is applied.

The general characteristics required for the die-bonding adhesive film include a decrease in high temperature stress caused by a difference in high temperature expansion coefficient, adhesion on a chip and a substrate, moisture resistance, and temperature cycle resistance. Recently, in addition to the above characteristics, demands related to productivity such as storage stability of adhesives and the possibility of pressing chips and substrates at low temperatures are increasing.

In the adhesive composition used to prepare the adhesive film, various rubbers are used as the main component to improve the strength, flexibility, and adhesion of the adhesive film.

Japanese Patent Laid-Open Nos. 60-243180 and 61-138680 disclose adhesive compositions containing acrylic resins, epoxy resins, and the like, but are difficult to use in semiconductor mounting. Moreover, in rubber-epoxy resin adhesives, examples in which reactive acrylic rubber or acrylonitrile-butadiene rubber or the like is mixed with an epoxy resin are described in Japanese Patent Laid-Open Nos. 3-181580 and 7-173449. It is.

However, when using an acrylic rubber, the adhesive strength at the time of high temperature is inadequate and there existed a problem of the characteristic fall at the time of moisture absorption. In addition, when acrylonitrile-butadiene rubber is the main component, there is a problem in that the adhesion decrease after long time treatment at high temperature and the electrolytic corrosion resistance is poor. In particular, when the moisture resistance test is performed under strict conditions such as PCT (Pressure-Cooker Test) treatment, which is used for reliability evaluation of semiconductor-related components, there is a significant problem of deterioration.

On the other hand, as the wiring patterns to be applied to the wiring board become complicated and miniaturized, there is a tendency to require an adhesive film having good circuit filling property while maintaining basic high temperature adhesion to such wiring patterns. In order to meet the above requirements, it may be considered to increase the content of the low molecular weight epoxy resin, but in this case there is a problem that the strength and adhesion of the film is lowered, and the circuit filling properties when the film is stored for a long time at room temperature Difficult to maintain Japanese Patent Application Laid-Open No. 2004-35847 is an adhesive film prepared by mixing an epoxy resin with a reactive acrylic rubber. A low molecular weight polyfunctional (meth) acrylic compound is added to an adhesive composition to induce low elasticity of an adhesive circuit. It says that it can improve filling. However, this method requires a separate photoinitiator and is subject to considerable constraints on the storage stability of the adhesive film.

In addition, when manufacturing the acrylic epoxy-bonded die-bonding film, by reducing the molecular weight of the reactive acrylic rubber to induce low elasticity of the adhesive film, it is possible to improve the circuit filling properties. However, in order to improve the heat resistance of the final adhesive film, the reactive group (usually glycidyl group) should be increased in the acrylic rubber. In this case, due to the increased reactivity of the acrylic rubber gelling phenomenon is likely to occur during the adhesive production and storage stability of the adhesive film becomes a problem.

Therefore, there is a demand for an adhesive film having excellent storage safety and heat resistance as well as excellent circuit filling properties as described above.

In order to solve the conventional problems as described above, an object of the present invention is to provide an adhesive composition excellent in long-term storage, heat resistance and excellent circuit filling properties.

Another object of the present invention is to provide an adhesive film including the adhesive resin composition as an adhesive layer and a method of manufacturing the same.

Still another object of the present invention is to provide a dicing die bonding film having excellent semiconductor package reliability including the adhesive film and the dicing tape.

It is still another object of the present invention to provide a semiconductor wafer using a dicing die bonding film.

Still another object of the present invention is to provide a semiconductor device using the adhesive film.

The present invention comprises a) a nonfunctional monomer, b) a monomer containing a functional group capable of reacting with the epoxy resin at less than 150 ° C, and c) a monomer containing a functional group capable of reacting with the epoxy resin at at least 150 ° C. (Meth) acrylic copolymer (A); And an adhesive resin composition comprising an epoxy resin (B).

Hereinafter, the present invention will be described in detail.

The adhesive film for acrylic-epoxy low elastic die bonds applied to a conventional semiconductor package is subjected to a three step curing process. The die-bonding film is bonded (dicing die-bonding film) with a dicing tape having a UV curable or thermosetting adhesive layer, and the dicing die-bonding film is attached to the lower surface of the wafer to proceed the dicing process. Heat or UV is irradiated after dicing to reduce the interfacial adhesion between the adhesive layer of the dicing tape and the adhesive layer of the die-bonding film, which is referred to as curing of the first stage (A stage). After that, when the diced chip is picked up using a vacuum, only the adhesive layer of the die bond film is attached to the lower surface of the chip, and the adhesive layer of the dicing tape is separated. After that, an adhesive layer is attached to the lower surface. The adhesive layer is attached to the wiring board and cured at a temperature of less than 150 ° C., that is, about 120 to 140 ° C. to maintain a gel content of 10 to 40%. It is called hardening. After the process of molding the semiconductor device (EMC) with an epoxy resin and finally thermally cured at a temperature of 150 ℃ or more, about 160 ~ 180 ℃, this is called a third stage (C stage) curing.

The present inventors in the conventional acrylic-epoxy low-elastic die-bonding adhesive composition in which the above process is carried out, when the monomer further comprises a monomer which is changed to an acid only at a temperature of 150 ℃ or more, the monomer is a B-stage (stage The present invention was found to satisfy both the storage stability of the adhesive film and the heat resistance of the final cured adhesive film by curing with epoxy resin only at a high temperature C-stage curing step without curing at the curing step. It was completed.

Therefore, the adhesive resin composition according to the present invention comprises i) an acrylic copolymer having a functional group capable of reacting with an epoxy resin, and ii) an epoxy resin composition comprising an epoxy resin, wherein the acrylic copolymer is b) a B-stage Monomer b) is involved in B-stage curing, including monomers having functional groups capable of reacting with the epoxy resin in curing, and c) monomers having functional groups capable of reacting with epoxy resin in the C-stage curing step, The monomer c) is characterized in that it is involved in C-stage curing.

Each component of the adhesive resin composition which concerns on this invention is specified by the following.

A. Acrylic Copolymer

In the composition according to the invention, the acrylic copolymer (A) comprises a) a nonfunctional monomer, b) a monomer containing a functional group capable of reacting with the epoxy resin at less than 150 ° C, and c) at least 150 ° C. Monomers containing functional groups capable of reacting.

The a) nonfunctional monomer is preferably an alkyl (meth) acrylic acid ester having an alkyl group having 1 to 12 carbon atoms or an aryl (meth) acrylic acid ester having an aryl group having 6 to 12 carbon atoms as a main resin of the acrylic copolymer (A). Do.

The alkyl (meth) acrylic acid ester having an alkyl group having 1 to 12 carbon atoms is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, As isooctyl (meth) acrylate, isononyl (meth) acrylate, monomers such as lauryl (meth) acrylate or tetradecyl (meth) acrylate may be used alone or in combination of two or more thereof, but is not limited thereto. It doesn't work.

The aryl (meth) acrylic acid ester having an aryl group having 6 to 12 carbon atoms may be used alone or in combination of two or more kinds of monomers such as phenyl methacrylate, benzyl (meth) acrylate, or phenoxy acrylate, but is not limited thereto. It doesn't work.

In addition, the a) non-functional monomer is substituted with a vinyl compound having 6 to 12 carbon atoms or a cyano substituted with an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms in order to control the glass transition temperature or to impart other functionalities. It is preferred to further include one or more comonomers selected from the group consisting of maleimide compounds.

The vinyl compound substituted with an aryl group or cyano having 6 to 12 carbon atoms may be a styrene-based vinyl compound such as styrene or alpha methyl styrene, or a vinyl cyanide compound such as acryronitrile or methacrylonitrile. It can be used, but is not limited thereto.

The maleimide compound substituted with an aryl group having 6 to 12 carbon atoms is N-alkyl maleimide compound such as N-methyl maleimide or N-butyl maleimide, or N-aryl maleimide type such as N-phenyl maleimide Compounds may be used alone or in combination of two or more, but are not limited thereto.

The content of the comonomer is not particularly limited, but is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the total monomers of the acrylic copolymer (A).

In the acrylic copolymer according to the present invention, b) the functional group capable of reacting with the epoxy resin at less than 150 ° C is preferably at least one selected from the group consisting of an epoxy group, a hydroxyl group, a carboxyl group and a nitrile group.

Monomers containing at least one functional group selected from the group consisting of glycidyl, hydroxy, carboxyl and nitrile groups include carboxyl group-containing monomers such as acrylic acid, methacrylic acid and itaconic acid, 2-hydroxyethyl (meth) acrylate, Monomers such as hydroxyl group-containing monomers such as 4-hydroxy butyl (meth) acrylate or epoxy-containing monomers such as glycidyl (meth) acrylate may be used alone or in combination of two or more thereof, but is not limited thereto. Do not. In particular, glycidyl (meth) acrylate is preferred in view of storage stability.

In the acrylic copolymer according to the present invention, c) a functional group capable of reacting with an epoxy resin at 150 ° C. or higher may be decomposed in a range of 150 ° C. or higher at the time of final curing to generate an acid, and may be particularly capable of reacting with an epoxy resin. Although not limited, it is preferable that it is a 2-tetrahydropyranyl group.

The monomer containing a functional group capable of reacting with the epoxy resin at 150 ° C. or higher is particularly preferably a compound of the formula (1).

In Formula 1, R ₁ Is hydrogen or a methyl group.

In the present invention, the content (b) + c) of the total monomer containing a functional group capable of reacting with the epoxy resin at less than 150 ° C. and at least 150 ° C.] is not particularly limited, but in terms of storage safety and physical property balance (meth) It is preferable that it is 0.1-10 weight part with respect to 100 weight part of all monomers of an acrylic resin.

In particular, b) the content of the monomer containing a functional group capable of reacting with the epoxy resin at less than 150 ℃ is preferably 0.1 to 7 parts by weight based on 100 parts by weight of the total monomer of the (meth) acrylic resin, 0.5 to 5 A weight part is more preferable. When the content of the monomer is less than 0.1 parts by weight, it is difficult to handle due to high Tuck during curing of the B-stage, and when it exceeds 7 parts by weight, the storage stability is greatly reduced.

In addition, c) the content of the monomer containing a functional group capable of reacting with the epoxy resin at 150 ℃ or more is preferably 0.5 to 7 parts by weight, preferably 1 to 5 parts by weight based on 100 parts by weight of the total monomer of the (meth) acrylic resin. More preferred. If the content of the monomer is less than 0.5 parts by weight, it is difficult to obtain the effect of improving heat resistance at the time of final curing, and if it exceeds 7 parts by weight, the adhesion decreases due to excessive curing.

On the other hand, the acrylic copolymer is preferably a glass transition temperature of-30 ~ 30 ℃, more preferably -20 ~ 20 ℃. When the glass transition temperature is less than -30 ° C, the modulus of elasticity is too low, and when the glass transition temperature exceeds 30 ° C, the adhesiveness is greatly reduced.

Further, the weight average molecular weight of the acrylic copolymer is preferably 200,000 to 1 million, and more preferably 300,000 to 800,000. If the molecular weight is less than 200,000, the strength and heat resistance of the adhesive film is lowered, if the molecular weight is more than 1 million, the adhesiveness and workability is lowered.

Moreover, the molecular weight distribution of the said acrylic copolymer is less than 5, Preferably it is 4.5 or less. When molecular weight distribution exceeds 5, heat resistance will fall largely by presence of a low molecular weight body.

The method for producing the acrylic copolymer is not particularly limited, and may be prepared by solution polymerization, photopolymerization, bulk polymerization, suspension polymerization or emulsion polymerization. Preferably, it is prepared using a suspension polymerization method that can minimize the amount of impurities, the polymerization temperature is preferably 30 ℃ to 100 ℃.

B. Epoxy Resin

It is preferable that the epoxy resin used for this invention uses the polyfunctional epoxy resin whose average epoxy equivalent is 180-1000. When the epoxy equivalent is less than 180, the crosslinking density is too high, so it is easy to exhibit hard properties, and when the epoxy equivalent exceeds 1000, the glass transition temperature may be lowered.

Examples of the epoxy resins usable in the present invention include cresol novolac epoxy resins, bisphenol A novolac epoxy resins, phenol novolac epoxy resins, tetrafunctional epoxy resins, biphenyl epoxy resins and triphenol methane type. An epoxy resin, an alkyl modified triphenol methane epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, a dicyclopentadiene modified phenol type epoxy resin, etc. are contained, These can be mixed and used 2 or more types.

As for the epoxy resin used for this invention, the epoxy resin of a softening point of 50 degreeC-80 degreeC is preferable. If the softening point is less than 50 ° C., since the adhesive film has a tack at room temperature, workability is degraded in the semiconductor process. If the softening point is more than 80 ° C., the adhesion property is degraded at the time of adhesion with the wafer, thereby causing voids.

Moreover, 10-200 weight part is preferable with respect to 100 weight part of acrylic copolymers, and, as for content of the said epoxy resin, 30-100 weight part is especially preferable. If it is less than 10 parts by weight, the heat resistance of the adhesive film is lowered. If it is more than 200 parts by weight, the elastic modulus of the film is excessively strong, and handleability and workability are deteriorated.

C. Curing Agent

The type of curing agent used in the present invention is not particularly limited, but is selected from the group consisting of phenolic compounds, aliphatic amines, cycloaliphatic amines, tertiary amines, imidazole compounds, dicyandiamide and acid anhydrides. You can use more than one. Among them, a phenolic compound is preferable, and a polyfunctional phenol resin having two or more hydroxyl groups in particular and having a hydroxyl equivalent of 100 to 1000 is advantageous in terms of heat resistance.

When the equivalent weight of the hydroxyl group of the phenol resin is less than 100, the cured product hardness is low and the adhesive force tends to be lowered, and when it exceeds 1000, the glass transition temperature is lowered and the heat resistance becomes weak. Such polyfunctional phenol resins include bisphenol A resins, phenol novolac resins, cresol novolac resins, bisphenol A novolac resins, xylox resins, polyfunctional novolac resins, dicyclopentadiene phenol novolac resins, and aminotriols. As long as it is an azine phenol novolak resin, poly butadiene phenol novolak resin, a biphenyl type resin, or other polyfunctional resin, all can be used, and these phenol resins may be used individually or in mixture of 2 or more types.

The content of the multifunctional phenolic resin is preferably about 0.4 to 2.4 equivalents, more preferably 0.8 to 1.2 equivalents, relative to the epoxy resin. If it is outside the above range, there is a disadvantage that unreacted epoxy or phenol remains and is volatilized at a high temperature reliability test to lower the reliability of the package.

The amount of the curing agent may be used in 50 to 150 parts by weight based on 100 parts by weight of the epoxy resin. If the content is less than 50 parts by weight, there is a problem of supplying high temperature or long time heat for the reaction of the unreacted epoxy group. If the content is more than 150 parts by weight, the crosslinking density is increased, but the hygroscopicity or dielectric properties due to the unreacted hydroxyl group. The back may rise, and the disadvantage may be low storage stability.

The composition according to the invention may further comprise a coupling agent. The coupling agent can improve the adhesion between the resin and the wafer, and the resin and the silica filler interface. A coupling agent can improve adhesiveness and adhesiveness, without damaging the heat resistance of hardened | cured material by the organic functional group reacting with a resin component at the time of a hardening reaction, and also can improve moisture-heat resistance characteristics. The coupling agent may be one or more selected from the group consisting of a silane-based, titanium-based, and aluminum-based coupling agent, but a silane coupling agent is preferable in view of high cost-effectiveness. Do.

The coupling agent is for example,

Vinyl silanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, or vinyltrimethoxysilane;

methacryloxy silanes such as γ-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, or γ-methacryloxypropylmethyl dimethoxysilane;

epoxy silanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane;

glycidoxy silanes such as γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane, or γ-glycidoxypropylmethyl diethoxysilane;

N-β- (aminoethyl) -γ-aminopropyl trimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane, γ-aminopropyl triethoxysilane, 3-aminopropylmethyl Diethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyl trimethoxysilane, triaminopropyl- Amino silanes such as trimethoxysilane, or N-phenyl- [gamma] -aminopropyl trimethoxysilane;

mercapto silanes such as γ-mercaptopropyl trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, or γ-mercaptopropyl triethoxysilane;

Ureido silanes such as 3-ureidopropyl triethoxysilane, or 3-ureidopropyl trimethoxysilane; or

Sulphi can also use silane, but is not limited thereto.

Moreover, although the usage-amount of the said coupling agent is not specifically limited, 0.01-10 weight part is preferable with respect to 100 weight part of solid content resin components, and 0.1-10 weight part is especially more preferable. If the amount is 0.01 parts by weight or less, the adhesive effect is not sufficient. If the amount is 10 parts by weight or more, it causes a decrease in heat resistance due to voids or unreacted coupling agents.

The resin composition of the present invention may further include a curing accelerator to promote the curing reaction.

The curing accelerator may use one or more selected from the group consisting of an imidazole compound, triphenylphosphine (TPP), and a tertiary amine, but is not limited thereto.

The said imidazole compound is 2-methyl imidazole (2MZ), 2-ethyl-4-methyl imidazole (2E4MZ), 2-phenyl imidazole (2PZ), and 1-cyanoethyl-2-phenyl imidazole (2PZ). -CN), 2-undecyl imidazole (C11Z), 2-heptadecyl imidazole (C17Z), and 1-cyanoethyl-2-phenylimidazole trimetalate (2PZ-CNS) You can use more than one.

The content of the curing accelerator is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight based on 100 parts by weight of the epoxy resin. If the content of the curing accelerator is less than 0.1 part by weight, the crosslinking of the epoxy resin is insufficient and the heat resistance tends to be lowered. If the content of the curing accelerator exceeds 10 parts by weight, the curing reaction occurs rapidly, and the storage stability is lowered.

Although the resin composition of this invention is not specifically limited, When considering handleability improvement, heat resistance improvement, melt viscosity adjustment, etc., it is preferable to further include a filler.

Examples of the filler include organic fillers and inorganic fillers, and inorganic fillers are preferable in view of characteristics. As the inorganic filler, silica, aluminum hydroxide, calcium carbonate, magnesium hydroxide, aluminum oxide, talc, aluminum nitride, or the like is preferable. In particular, spherical silica is particularly preferable in terms of good dispersibility in the resin composition and uniform adhesion in the film.

Although content of a filler is not specifically limited, 0.5-150 weight part is preferable with respect to 100 weight part of solid content resin except a filler, and 5-100 weight part is more preferable. If the content is less than 0.5 parts by weight, the effect of improving the heat resistance and handleability due to the addition of the filler is not sufficient. If the content exceeds 150 parts by weight, the effect of improving workability and adhesion is reduced.

The average particle diameter of the filler is preferably 0.005 µm to 5 µm, and more preferably 0.01 µm to 1 µm. If the average particle diameter is less than 0.005 μm, the filler is easily aggregated in the adhesive film and appearance defects occur. If the average particle diameter is more than 5 μm, the filler is easily protruded from the adhesive film to the surface, and the chip is damaged during the thermocompression bonding with the wafer. The improvement effect of a performance may fall.

The present invention also provides a base film; And

It is related with the adhesive film formed on the said base film, and containing the adhesive layer containing the adhesive resin composition which concerns on this invention.

Examples of the base film of the adhesive film according to the present invention include polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyimide film, and the like. Plastic films can be used. Moreover, it is preferable to perform a mold release process on the surface of the said base film. Alkyl-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based, or waxy-based waxes are used as the release agent used for the surface release treatment. Particularly, release agents such as alkyd-based, silicone-based, or fluorine-based materials are preferable because they have heat resistance.

The thickness of a base film is 10-500 micrometers normally, Preferably it is about 20-200 micrometers.

The adhesive layer of the adhesive film may contain the adhesive resin composition according to the present invention to satisfy the storage stability of the adhesive film and the heat resistance of the final cured adhesive film at the same time.

Although the thickness of the said contact bonding layer is not specifically limited, It is preferable that the thickness of the heat-hardened contact bonding layer is 5-200 micrometers, and it is more preferable that it is about 10-100 micrometers.

The present invention also comprises the first step of producing a resin varnish by dissolving or dispersing the adhesive resin composition according to the invention in a solvent;

A second step of applying the resin varnish to the base film; And

A third step of removing the solvent by heating the base film coated with the resin varnish

It relates to a method for producing an adhesive film comprising a.

In the first step is to prepare a resin varnish, considering the process time shortening and dispersibility,

Mixing a solvent, a filler and a coupling agent a);

B) adding and mixing an epoxy resin and a curing agent to the mixture of step a); And

Mixing the (meth) acrylic copolymer and a curing accelerator into the mixture of step b) c)

It is preferable to include.

The solvent for varnishing is typically methyl ethyl ketone (MEK), acetone, toluene, dimethyl formamide (DMF), methyl cellosolve (MCS), tetrahydrofuran (THF), or N Methylpyrrolidone (NMP) and the like can be used. Although it is preferable to use a low boiling point solvent in consideration of the heat resistance of a base film, a high boiling point solvent may be used in order to improve coating film property, and these solvents may be used in mixture of 2 or more types.

In addition, in order to improve the dispersibility in the adhesive film when the filler is used, a ball mill, bead mill, three rolls, or a high speed disperser may be used alone or in combination. Can also be used. Examples of the material of the balls and beads include glass, alumina, zirconium, and the like, and in terms of dispersibility of the particles, balls or beads made of zirconium are preferable.

In the method for producing an adhesive film according to the present invention, the second step is a step of applying the resin varnish to the base film.

The method of applying the resin varnish to the base film is not particularly limited. For example, the knife coat method, the roll coat method, the spray coat method, the gravure coat method, the curtain coat method, the comma coat method, the lip coat method, etc. can be used.

In the manufacturing method of the adhesive film according to the present invention, the third step is a step of removing the solvent by heating the base film is coated with the resin varnish. It is preferable that heating conditions at this time are about 5 to 20 minutes at 70-250 degreeC.

The invention also provides a dicing tape; And

It relates to a dicing die bonding film comprising the adhesive film according to the present invention laminated on the dicing tape.

The dicing tape is

Base film; And

It is preferable to include the adhesion layer formed on the said base film.

The base film of the dicing tape is polyethylene film, polypropylene film, polytetrafluoroethylene film, polyethylene terephthalate film, polyurethane film, ethylene vinyl acetone film, ethylene-propylene copolymer film, ethylene-ethyl acrylate copolymer film, Or an ethylene-methyl acrylate copolymer film etc. can be used and you may surface-treat, such as a primer application | coating, a corona treatment, an etching treatment, and a UV treatment as needed. Moreover, when hardening an adhesive by ultraviolet irradiation, the thing with good light transmittance can be selected.

Although the thickness of the said dicing tape base material does not have a restriction | limiting in particular, Considering a handleability or a packaging process, 60-160 micrometers, Preferably 80-120 micrometers is good.

As an adhesive layer of a dicing tape, a conventional ultraviolet curing adhesive or a thermosetting adhesive can be used. In the case of an ultraviolet curable adhesive, ultraviolet-ray is irradiated from the base material side, the cohesion force of an adhesive is raised and adhesive force is reduced, In the case of a thermosetting adhesive, temperature is added and a adhesive force is reduced.

As a method of manufacturing a dicing die bonding film according to the present invention as described above, a method of hot roll laminating and a laminating press of a dicing tape and an adhesive film may be used. This is preferred. Hot roll lamination conditions are preferably a pressure of 0.1 to 10 kg _f / cm ² at 10 to 100 ℃.

The present invention also relates to a semiconductor wafer in which the adhesive film of the dicing die bonding film according to the present invention is attached to one side of the wafer, and the dicing tape of the dicing die bonding film is fixed to the wafer ring frame.

In the semiconductor wafer as described above, the adhesive film of the dicing die bonding film is attached to the back surface of the wafer at a lamination temperature of 0 to 180 ° C., and the dicing tape of the dicing die bonding film is fixed to the wafer ring frame. Can be prepared.

In addition, the present invention

Wiring board; And

The present invention relates to a semiconductor device including a semiconductor chip mounted on the wiring board using the adhesive resin composition according to the present invention.

The manufacturing process of the semiconductor device will be described below.

The semiconductor wafer with the dicing die bonding film mentioned above is cut | disconnected completely using a dicing apparatus, and it divides into individual chips.

Subsequently, if the dicing tape is an ultraviolet curing adhesive, the substrate side is irradiated with ultraviolet rays to cure, and if it is a thermosetting adhesive, the temperature is raised to cure the adhesive. As mentioned above, the adhesive hardened | cured by ultraviolet-ray or heat falls, and the adhesive force of an adhesive falls and it becomes easy to pick up a chip in a post process. At this time, a dicing die bonding film can be stretched as needed. When such an expanding process is performed, the spacing between chips is determined to facilitate pick-up, and a misalignment occurs between the adhesive layer and the pressure-sensitive adhesive layer, thereby improving pickup performance. Then, chip pick-up is performed. At this time, the adhesive layer of a semiconductor wafer and a dicing die bonding film peels from the adhesive layer of a dicing die bonding film, and the chip | tip with only an adhesive bond layer can be obtained. The obtained chip | tip with the said adhesive bond layer is affixed on the semiconductor substrate. The adhesion temperature of a chip is 100-180 degreeC normally, an adhesion time is 0.5-3 second, and an adhesion pressure is 0.5-2 kg _f / cm <^2> .

After the above process, a semiconductor device is obtained through a wire bonding and molding process.

The manufacturing method of a semiconductor device is not limited to the said process, Arbitrary process may be included and the order of a process may be changed. For example, UV curing can be performed by dicing ▶ expanding process or by dicing ▶ expanding ▶ ultraviolet light process. The chip attach process may further include a heating or cooling process.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the Examples are only for illustrating the present invention and the scope of the present invention is not limited to the following Examples.

<Production of Acrylic Copolymer>

Production Example  One

30 parts by weight of n-butylacrylate (BA), ethylacrylate (EA), as shown in Table 1, in a 1L reactor equipped with a refrigeration system to allow nitrogen gas to be refluxed and to facilitate temperature control. ) 34 parts by weight, acryllonitril (AN) 30 parts by weight, 3 parts by weight of glycidyl methacrylate (GMA) and 2-tetrahydropyranyl methacrylate (THPMA) A mixture of monomers composed of 3 parts by weight was added thereto to obtain spherical acrylic copolymer beads through suspension polymerization. The obtained spherical acrylic beads were dried in a 40 ° C. vacuum oven for 24 hours and dissolved in a methyl ethyl ketone solution to prepare an acrylic copolymer solution having a solid content of 15% and a weight average molecular weight of 400,000.

Production Example  2-6

In Preparation Example 1, based on the composition of the acrylic copolymer a as shown in Table 1, a part of each component was not added or partially added to prepare an acrylic copolymer b-f. The results are shown in Table 1.

Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 a b c d e f Copolymer Composition (parts by weight) n-BA 30 30 30 30 30 30 EA 34 34 36.95 37 37 30 AN 30 30 30 30 30 30 GMA 3 2 0.05 3 3 10 THPMA 3 4 0 0 0 0 Weight average molecular weight (only) 40 45 80 80 40 30 Molecular weight distribution 3.8 3.6 4.1 4.2 3.7 3.9 Glass transition temperature (C) 5 5 7 7 7 8

Example 1

100 parts by weight of the acrylic resin of Production Example 1, 25 parts by weight of YDCN-500-80P (Kukdo Chemical, cresol novolac-type epoxy resin, epoxy equivalent 205, softening point of 80 ° C.), KPH, which is a phenol resin as a curing agent of epoxy resin. 15 parts by weight of -F2001 (Koloon emulsified, phenol novolac, hydroxyl equivalent 106, softening point 88 ℃), 1 part by weight of A-187 (GE Toshiba Silicone, γ-glycidoxypropyltrimethoxysilane), a silane coupling agent 0.01 parts by weight of 2PZ (chemical compound, 2-phenyl imidazole) as an accelerator, and 10 parts by weight of UFP-80 (denka, spherical silica, average particle diameter: 75 nm) were mixed with methyl ethyl ketone (MEK) and mixed with varnish. Was prepared. The adhesive composition was applied to a base film (SKC, RS-21G) having a thickness of 38 μm, dried at 110 ° C. for 5 minutes to prepare an adhesive film having a coating thickness of 20 μm. This adhesive film was laminated at 5 kg _f / cm ² with a dicing tape (Srion Tech 6360-00) at 30 ° C. using a laminator (Fujishoko Co., Ltd.) to obtain an adhesive film for semiconductors.

Example 2

A varnish was prepared in the same manner as in Example 1, except that the acrylic copolymer of Preparation Example 2 was used.

Comparative Example 1

A varnish was prepared in the same manner as in Example 1, except that the acrylic copolymer of Preparation Example 3 was used.

Comparative Example 2

A varnish was prepared in the same manner as in Example 1, except that the acrylic copolymer of Preparation Example 4 was used.

Comparative Example 3

A varnish was prepared in the same manner as in Example 1, except that the acrylic copolymer of Preparation Example 5 was used.

Comparative Example 4

A varnish was prepared in the same manner as in Example 1, except that the acrylic copolymer of Preparation Example 6 was used.

Example Comparative example Composition (parts by weight) One 2 One 2 3 4 Acrylic copolymer 100 (a) 100 (b) 100 (c) 100 (d) 100 (e) 100 (f) Epoxy resin 25 25 25 25 25 25 KPH-F2001 15 15 15 15 15 15 2PZ 0.01 0.01 0.01 0.01 0.01 0.01 A-187 One One One One 0 0 UFP-80 10 10 10 10 10 10

Physical properties of the adhesive compositions of Examples 1 to 2 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 3 below.

<Evaluation method of film>

(1) Evaluation of preservation safety

The difference was evaluated by measuring the gel content immediately after preparation of the adhesive film and the gel content after storage for one month in the dark at room temperature. The gel content was measured by extracting about 0.3 g of adhesive from the adhesive film, immersing it in 100 g of ethyl acetate for 3 days, separating the insoluble parts, drying for 4 hours in an oven at 70 ° C., and weighing it. Was calculated.

(2) Circuit filling

PCB having a 10 μm height difference was used as the substrate. The die bonding film (20 um) was cut to 25 mm × 25 mm and laminated at 60 ° C. with the chip in a tape mounter (DS hole). The chip on which the PCB and die bonding are attached was pressed at 130 ° C. and 1.5 kg for 1 second. The fill rate was calculated by calculating the amount of film flowing and flowing between the circuit patterns of the PCB. If the purchase rate is more than 70% was excellent, 50% ~ 70% level was good, less than 50% was treated as bad.

(3) moisture resistance

The film adhered to the wafer was treated at 121 ° C., 100% humidity, and 2 atmospheres of pressure (PCT, Pressure Cooker Test) after 72 hours to observe the presence or absence of peeling, and the peeling was good.

(4) heat resistance

After bonding the chip to the PCB substrate with a die-bonding film, the sample was left at -55 ° C. for 15 minutes, and the process of leaving the sample at 125 ° C. for 15 minutes was carried out for 5 cycles in a constant temperature and humidity chamber (85 ° C. and 85%). After 72 hours, the sample is passed through an IR reflow apparatus having a temperature set so that the maximum temperature of the sample surface is maintained at 260 ° C. for 20 seconds, and the process of leaving the sample at room temperature for cooling is repeated three times. Cracks were observed by ultrasonic microscopy. It was good that defects, such as peeling and a crack, did not generate | occur | produce, and made one or more defects into defects.

Properties Example Comparative example One 2 One 2 3 4 Preservation safety 5 5 One 10 8 40 Circuit filling Great Great Bad Bad Great Great Moisture resistance Good Good Bad Good Bad Good Heat resistance Good Good Bad Good Bad Good

As shown in Table 3, in the adhesive films of Examples 1 to 2 prepared according to the present invention, the storage stability and heat resistance were excellent, and the circuit filling property was also excellent. In Comparative Example 1, the storage stability was excellent, but the reactive group was insufficient, and thus the heat resistance was insufficient, and the circuit filling was also insufficient due to the high molecular weight. In Comparative Example 2, the storage stability and the heat resistance are good, but the circuit filling is insufficient due to the high molecular weight. In Comparative Example 3, the circuit filling property was improved due to the decrease in molecular weight, but the heat resistance was insufficient due to the trade-off characteristic. In the case of Comparative Example 4, the heat resistance is improved due to the increase in the glycidyl group content, which is a reactive group, and the case where the circuit filling property is improved due to the low molecular weight, or the storage stability is largely insufficient.

The adhesive composition and adhesive film for semiconductors according to the present invention have good storage safety and heat resistance and at the same time excellent circuit filling properties. Moreover, the adhesive film of this invention can manufacture the semiconductor device which was excellent in the adhesive reliability between a chip | tip and a board | substrate, and excellent in the reliability which has heat resistance and moisture resistance.

Claims (25)

(meth) comprising a) a nonfunctional monomer, b) a monomer containing a functional group capable of reacting with the epoxy resin at less than 150 ° C., and c) a monomer containing a functional group capable of reacting with the epoxy resin at at least 150 ° C. Acrylic copolymer (A); And Epoxy Resin (B) Adhesive resin composition comprising a. The method of claim 1, The non-functional monomer is an adhesive resin composition characterized by being an alkyl (meth) acrylic acid ester having an alkyl group having 1 to 12 carbon atoms or an aryl (meth) acrylic acid ester having an aryl group having 6 to 12 carbon atoms. The method of claim 1, The non-functional monomer further comprises at least one comonomer selected from the group consisting of a vinyl compound substituted with an aryl group or cyano having 6 to 12 carbon atoms, and a maleimide compound substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Adhesive resin composition comprising a. The method of claim 1, Adhesive group, wherein the functional group capable of reacting with the epoxy resin at less than 150 ℃ is at least one selected from the group consisting of an epoxy group, a hydroxyl group, a carboxyl group and a nitrile group. The method of claim 1, Adhesive group, characterized in that the functional group capable of reacting with the epoxy resin at 150 ℃ or more is a 2-tetrahydropyranyl group. The method of claim 1, Adhesive resin composition characterized in that the monomer containing a functional group capable of reacting with the epoxy resin at 150 ℃ or more is a compound of the formula (1). [Formula 1]

Wherein R ₁ is hydrogen or a methyl group. The method of claim 1, Adhesive resin composition, characterized in that the content of the total monomer containing a functional group capable of reacting with the epoxy resin at less than 150 ℃ and more than 150 ℃ is 0.1 to 10 parts by weight relative to 100 parts by weight of the total monomers of the (meth) acrylic resin. The method of claim 7, wherein Adhesive resin composition, characterized in that the content of the monomer containing a functional group capable of reacting with the epoxy resin at less than 150 ℃ is 0.1 to 7 parts by weight based on 100 parts by weight of the total monomers of the (meth) acrylic resin. The method of claim 7, wherein Adhesive resin composition, characterized in that the content of the monomer containing a functional group capable of reacting with the epoxy resin at 150 ℃ or more is 0.5 to 7 parts by weight based on 100 parts by weight of the total monomers of the (meth) acrylic resin. The method of claim 1, The adhesive resin composition of (meth) acrylic-type resin whose glass transition temperature is -30-30 degreeC, and a weight average molecular weight is 200,000-1 million. The method of claim 1, Epoxy resin is an adhesive resin composition, characterized in that the polyfunctional epoxy resin having an average epoxy equivalent of 180 to 1000. The method of claim 1, The content of the epoxy resin is an adhesive resin composition, characterized in that 10 to 200 parts by weight based on 100 parts by weight of the (meth) acrylic resin. The method of claim 1, Adhesive resin composition, characterized in that it further comprises 50 to 150 parts by weight of curing agent per 100 parts by weight of epoxy resin. The method of claim 13, The hardening | curing agent has a 2 or more hydroxyl group, and is an adhesive resin composition characterized by being a polyfunctional phenol resin whose hydroxyl equivalent is 100-1000. The method of claim 1, An adhesive resin composition further comprising 0.01 to 10 parts by weight of a coupling agent based on 100 parts by weight of the solid resin component. The method of claim 15, The coupling agent is an adhesive, characterized in that at least one silane coupling agent selected from the group consisting of vinyl silane, methacryloxy silane, epoxy silane, glycidoxy silane, amino silane, mercapto silane, ureido silane, and sulfido silane. Resin composition. The method of claim 1, Adhesive resin composition, characterized in that it further comprises 0.001 to 10 parts by weight of a curing accelerator based on 100 parts by weight of epoxy resin. The method of claim 17, Curing accelerators 2-methyl imidazole (2MZ), 2-ethyl-4-methyl imidazole (2E4MZ), 2-phenyl imidazole (2PZ), 1-cyanoethyl-2-phenyl imidazole (2PZ-CN) At least one imidine selected from the group consisting of 2-undecyl imidazole (C11Z), 2-heptadecyl imidazole (C17Z), and 1-cyanoethyl-2-phenylimidazole trimetalate (2PZ-CNS) Adhesive resin composition characterized by the above-mentioned. The method of claim 1, Adhesive resin composition, characterized in that it further comprises 0.5 to 150 parts by weight of filler with respect to 100 parts by weight of solid resin. The method of claim 19, Filler is an adhesive resin composition, characterized in that the silica having an average particle diameter of 0.005㎛ to 5㎛. Base film; And An adhesive layer formed on the said base film and containing the adhesive resin composition of any one of Claims 1-20. Adhesive film comprising a. A first step of preparing a resin varnish by dissolving or dispersing the adhesive resin composition according to any one of claims 1 to 20 in a solvent; A second step of applying the resin varnish to the base film; And A third step of removing the solvent by heating the base film coated with the resin varnish Method for producing an adhesive film comprising a. Dicing tape; And The adhesive film according to claim 21 laminated on the dicing tape Dicing die bonding film comprising a. A semiconductor wafer, wherein an adhesive film of the dicing die bonding film according to claim 23 is attached to one side of the wafer, and the dicing tape of the dicing die bonding film is fixed to the wafer ring frame. Wiring board; And The semiconductor device containing the semiconductor chip mounted on the said wiring board using the adhesive resin composition of Claim 1.

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