JP6775005B2 - Electronic device packaging tape - Google Patents

Description

The present invention relates to a tape for an electronic device package, and more particularly to a tape for an electronic device package having a metal layer.

In recent years, electronic devices such as mobile phones and notebook PCs are required to be further thinned and miniaturized. Therefore, in order to make electronic device packages such as semiconductor packages mounted on electronic devices thinner and smaller, the number of electrodes of electronic devices and circuit boards is increased, and the pitch is also narrowed. Such electronic device packages include, for example, flip chip (FC) mounting packages.

In the flip chip mounting package, as described above, the number of electrodes is increased or the pitch is narrowed, so that an increase in the amount of heat generated is a problem. Therefore, as a heat dissipation structure of the flip chip mounting package, it has been proposed to provide a metal layer on the back surface of the electronic device via an adhesive layer (see, for example, Patent Document 1).

Further, in the flip chip mounting package, the coefficient of linear expansion of the electronic device and the coefficient of linear expansion of the circuit board may be significantly different. In this case, in the manufacturing process of the electronic device package, when the intermediate product is heated and cooled, a difference in the amount of expansion and contraction occurs between the electronic device and the circuit board. This difference causes the electronic device package to warp. As a structure for suppressing such warpage, it has been proposed to provide a metal layer on the back surface of the electronic device via an adhesive layer (see, for example, Patent Document 2).

Further, in a flip chip mounting package, it has been proposed to provide a metal layer on the back surface of an electronic device via an adhesive layer and use this metal layer as a protective layer for laser marking (see, for example, Patent Document 3). .. Further, Patent Document 3 also discloses a flip-chip type semiconductor back surface film in which a metal layer and an adhesive layer are provided on an adhesive layer of an adhesive tape in which an adhesive layer is laminated on a base material.

JP-A-2007-23502 Japanese Patent No. 5487847 Japanese Patent No. 5419226

When a flip-chip type semiconductor back surface film integrated with an adhesive tape as described in Patent Document 3 is used, the back surface of the semiconductor wafer is bonded onto the adhesive layer, and the semiconductor wafer is died into a chip shape. The semiconductor chip is separated into individual pieces, and the semiconductor chip is picked up from the adhesive tape with the adhesive layer and the metal layer adhered to the back surface, and is flip-chip connected to the substrate. Specifically, the bump and the conductive material while pressing the semiconductor chip by bringing the bump formed on the circuit surface side of the semiconductor chip into contact with the conductive material such as solder for bonding adhered to the connection pad of the substrate. By melting the semiconductor chip, electrical continuity between the semiconductor chip and the substrate is ensured, and the semiconductor chip is fixed to the adherend.

When the bumps and the conductive material are melted, if the adhesive layer is heated at a high temperature at once, there is a problem that voids are generated in the adhesive layer due to bumping of water and volatile components contained in the adhesive layer. In order to suppress the generation of this void, before connecting the flip chip, in the state of a laminated body of the metal layer, the adhesive layer and the semiconductor chip at a temperature at which the water and volatile components contained in the adhesive layer do not suddenly boil. It is conceivable to pre-cure the adhesive layer.

However, when the adhesive layer is pre-cured, the heat at this time causes the metal layer, the adhesive layer, and the laminate of the semiconductor chips to warp due to the difference in the coefficient of linear expansion between the semiconductor chip and the metal layer, resulting in a semiconductor. There is a problem that the bump of the chip and the conductive material on the substrate side cannot be connected well.

Therefore, the present invention can suppress warpage of the semiconductor, the adhesive layer, and the laminate of the semiconductor chips when the adhesive layer is pre-cured, and can be applied to the adhesive layer when the flip chip is connected. An object of the present invention is to provide a tape for an electronic device package capable of suppressing the occurrence of voids.

In order to solve the above problems, the tape for electronic device packaging according to the present invention is provided by laminating an adhesive tape having a base film and an adhesive layer on the opposite side of the pressure-sensitive adhesive layer to the base film. The metal layer is provided on the opposite side of the metal layer to the adhesive layer, and has an adhesive layer for adhering the metal layer to the back surface of the electronic device. It is characterized in that the storage elasticity at 25 ° C. after heating at 100 ° C. for 3 hours is 10 GPa or less, and the curing rate when heated at 100 ° C. for 3 hours is 10 to 100%.

The metal layer of the tape for electronic device packaging preferably contains copper or aluminum.

Further, in the tape for electronic device packaging, the adhesive layer contains (A) epoxy resin, (B) curing agent, (C) acrylic resin or phenoxy resin, and (D) surface-treated inorganic filler. It is preferable to do so.

Further, in the tape for electronic device packaging, the pressure-sensitive adhesive layer contains an acrylic acid ester represented by CH ₂ = CHCOOR (in the formula, R is an alkyl group having 4 to 18 carbon atoms) and a hydroxyl group. It is preferable to contain an acrylic polymer composed of a monomer and an isocyanate compound having a radically reactive carbon-carbon double bond in the molecule.

According to the present invention, it is possible to suppress warpage of the semiconductor, the adhesive layer, and the laminate of the semiconductor chips when the adhesive layer is pre-cured, and the adhesive layer is formed when the flip chip is connected. It is possible to suppress the generation of voids.

It is sectional drawing which shows typically the structure of the tape for electronic device package which concerns on embodiment of this invention. It is sectional drawing for demonstrating the usage method of the tape for electronic device packaging which concerns on embodiment of this invention.

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

FIG. 1 is a cross-sectional view showing a tape 10 for an electronic device package according to an embodiment of the present invention. The electronic device package tape 10 has an adhesive tape 13 composed of a base film 11 and an adhesive layer 12 provided on the base film 11, and a metal layer 14 is placed on the adhesive layer 12. And an adhesive layer 15 provided on the metal layer 14. The adhesive layer 15 may be indirectly provided on the metal layer 14 via a primer layer or the like for improving the adhesion with the metal layer 14. In this embodiment, a semiconductor chip will be described as an example of the electronic device.

It is preferable that the surface of the adhesive layer 15 opposite to the surface in contact with the metal layer 14 is protected by a separator (release liner) (not shown). The separator has a function as a protective material that protects the adhesive layer 15 until it is put into practical use. Further, the separator can be used as a supporting base material when the metal layer 14 is bonded to the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive tape 13 in the manufacturing process of the tape 10 for electronic device packaging.

The adhesive tape 13, the metal layer 14, and the adhesive layer 15 may be pre-cut into a predetermined shape according to the process of use and the apparatus. Further, the tape 10 for an electronic device package of the present invention may be in the form of being cut for each semiconductor wafer W, or may be a long tape in which a plurality of tapes cut for each semiconductor wafer W are formed. The sheet may be rolled up in a roll shape. Each component will be described below.

<Base film 11>
As the base film 11, any conventionally known one can be used without particular limitation, but when a radiation-curable material is used as the pressure-sensitive adhesive layer 12 described later, it has radiation permeability. It is preferable to use one.

For example, the materials thereof include polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-acrylic. Monopolymers or copolymers of α-olefins such as methyl acid copolymers, ethylene-acrylic acid copolymers, ionomers, or mixtures thereof, polyurethanes, styrene-ethylene-butene or penten-based copolymers, polyamide-polypolymers. Thermoplastic elastomers such as copolymers and mixtures thereof can be listed. Further, the base film 11 may be a mixture of two or more kinds of materials selected from these groups, or may be a single layer or a multi-layered film.

The thickness of the base film 11 is not particularly limited and may be set as appropriate, but is preferably 50 to 200 μm.

In order to improve the adhesion between the base film 11 and the pressure-sensitive adhesive layer 12, the surface of the base film 11 is chemically or physically treated with chromic acid, ozone, flame, high piezoelectric, ionizing radiation, etc. Surface treatment may be applied.

Further, in the present embodiment, the pressure-sensitive adhesive layer 12 is provided directly on the base film 11, but a primer layer for improving adhesion, an anchor layer for improving machinability during dicing, and stress. It may be provided indirectly via a relaxation layer, an antistatic layer, or the like.

<Adhesive layer 12>
The resin used for the pressure-sensitive adhesive layer 12 is not particularly limited, and known chlorinated polypropylene resin, acrylic resin, polyester resin, polyurethane resin, epoxy resin and the like used for the pressure-sensitive adhesive may be used. However, an acrylic pressure-sensitive adhesive using an acrylic polymer as a base polymer is preferable.

Examples of the acrylic polymer include (meth) acrylic acid alkyl esters (eg, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, iso). Pentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, Alkyl groups such as octadecyl esters and eicosyl esters have 1 to 30 carbon atoms, especially linear or branched alkyl esters having 4 to 18 carbon atoms) and (meth) acrylic acid cycloalkyl esters (eg, cyclopentyl esters). , Cyclohexyl ester, etc.), or an acrylic polymer using one or more of them as a monomer component. The (meth) acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester, and all of the (meth) of the present invention have the same meaning.

The acrylic polymer contains a unit corresponding to the (meth) acrylic acid alkyl ester or other monomer component copolymerizable with the cycloalkyl ester, if necessary, for the purpose of modifying the cohesive force, heat resistance, etc. You may. Examples of such monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride. , Acid anhydride monomers such as itaconic acid anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate. , (Meta) acrylate 8-hydroxyoctyl, (meth) acrylate 10-hydroxydecyl, (meth) acrylate 12-hydroxylauryl, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and other hydroxyl group-containing monomers; Sulfonic acid groups such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid. Containing monomer; Phosphonic acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate; acrylamide, acrylonitrile and the like. One or two or more of these copolymerizable monomer components can be used. The amount of these copolymerizable monomers used is preferably 40% by weight or less of the total monomer components.

Further, since the acrylic polymer is crosslinked, a polyfunctional monomer or the like can be included as a monomer component for copolymerization, if necessary. Examples of such a polyfunctional monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. Pentaerythritol di (meth) acrylate, trimethylolpropanthry (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) Examples include acrylate. One or more of these polyfunctional monomers can also be used. The amount of the polyfunctional monomer used is preferably 30% by weight or less of the total monomer components from the viewpoint of adhesive properties and the like.

The acrylic polymer can be prepared, for example, by applying an appropriate method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or a suspension polymerization method to a mixture of one or more kinds of component monomers. The pressure-sensitive adhesive layer 12 preferably has a composition in which the content of low molecular weight substances is suppressed from the viewpoint of preventing contamination of the wafer, and from this point, the main component is an acrylic polymer having a weight average molecular weight of 300,000 or more, particularly 400,000 to 3 million. Therefore, the pressure-sensitive adhesive may be of an appropriate cross-linking type by an internal cross-linking method, an external cross-linking method, or the like.

Further, in order to control the crosslink density of the pressure-sensitive adhesive layer 12 and improve the pick-up property, for example, a polyfunctional isocyanate compound, a polyfunctional epoxy compound, a melamine compound, a metal salt compound, a metal chelate compound, and an amino resin compound. A method of cross-linking with a compound or an appropriate external cross-linking agent such as peroxide, or a method of mixing low molecular weight compounds having two or more carbon-carbon double bonds and cross-linking by irradiation with energy rays or the like. Etc., an appropriate method can be adopted. When an external cross-linking agent is used, the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive. Generally, it is preferably blended in an amount of about 10 parts by weight or less, more preferably 0.1 parts by weight to 10 parts by weight, based on 100 parts by weight of the base polymer. From the viewpoint of preventing deterioration and the like, the pressure-sensitive adhesive may contain various additives such as a pressure-sensitive adhesive and an anti-aging agent in addition to the above-mentioned components, if necessary.

As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 12, a radiation-curable pressure-sensitive adhesive is suitable. Examples of the radiation-curable pressure-sensitive adhesive include an additive-type radiation-curable pressure-sensitive adhesive in which a radiation-curable monomer component and a radiation-curable oligomer component are mixed with the above-mentioned pressure-sensitive adhesive.

Examples of the radiation-curable monomer component to be blended include urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaeristol tetra (). Examples thereof include meta) acrylate, dipentaeristol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4-butanediol di (meth) acrylate. These monomer components can be used alone or in combination of two or more.

Further, examples of the radiation-curable oligomer component include various oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based, and those having a molecular weight in the range of about 100 to 30,000 are suitable. The amount of the radiation-curable monomer component or oligomer component to be blended can be appropriately determined according to the type of the pressure-sensitive adhesive layer so that the adhesive strength of the pressure-sensitive adhesive layer can be reduced. Generally, it is, for example, about 5 parts by weight to 500 parts by weight, preferably about 70 parts by weight to 150 parts by weight, based on 100 parts by weight of a base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.

As the radiation-curable pressure-sensitive adhesive, in addition to the addition-type radiation-curable pressure-sensitive adhesive, a base polymer having a carbon-carbon double bond in the side chain or main chain or at the end of the main chain was used. Also included is an intrinsic radiation curable adhesive. Since the intrinsic radiation-curable pressure-sensitive adhesive does not need to contain an oligomer component or the like which is a low molecular weight component or does not contain a large amount, the oligomer component or the like does not move in the pressure-sensitive adhesive over time and is stable. It is preferable because a layered pressure-sensitive adhesive layer can be formed.

As the base polymer having a carbon-carbon double bond, a polymer having a carbon-carbon double bond and having adhesiveness can be used without particular limitation. As such a base polymer, one having an acrylic polymer as a basic skeleton is preferable. Examples of the basic skeleton of the acrylic polymer include the above-exemplified acrylic polymer.

The method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted, but the carbon-carbon double bond is easily introduced into the polymer side chain in terms of molecular design. is there. For example, after copolymerizing a monomer having a functional group with an acrylic polymer in advance, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is subjected to radiation curability of the carbon-carbon double bond. There is a method of condensing or adding reaction while maintaining the above.

Examples of the combination of these functional groups include a carboxylic acid group and an epoxy group, a carboxylic acid group and an aziridyl group, a hydroxyl group and an isocyanate group, and the like. Among these combinations of functional groups, the combination of a hydroxyl group and an isocyanate group is preferable because of the ease of tracking the reaction. Further, as long as the combination of these functional groups produces an acrylic polymer having the carbon-carbon double bond, the functional group may be on either side of the acrylic polymer or the compound. In the preferred combination described above, it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α, and α-dimethylbenzyl isocyanate. Further, as the acrylic polymer, a polymer obtained by copolymerizing the above-exemplified hydroxy group-containing monomer or an ether compound such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, or diethylene glucol monovinyl ether is used.

In the intrinsic radiation-curable pressure-sensitive adhesive, the base polymer having a carbon-carbon double bond (particularly an acrylic polymer) can be used alone, but the radiation-curable monomer component does not deteriorate the properties. And photopolymerizable compounds such as oligomer components can also be blended. The blending amount of the photopolymerizable compound is usually in the range of 30 parts by weight or less with respect to 100 parts by weight of the base polymer, preferably in the range of 0 to 10 parts by weight.

The radiation-curable pressure-sensitive adhesive preferably contains a photopolymerization initiator when it is cured by ultraviolet rays or the like.

Among the above-mentioned acrylic polymers, in particular, an acrylic acid ester represented by CH ₂ = CHCOOR (in the formula, R is an alkyl group having 4 to 18 carbon atoms), a hydroxyl group-containing monomer, and intramolecules. Acrylic polymer A composed of an isocyanate compound having a radically reactive carbon-carbon double bond is preferable.

If the number of carbon atoms in the alkyl group of the acrylic acid alkyl ester is less than 4, the polarity may be high and the peeling force may be too large to reduce the pick-up property. On the other hand, when the number of carbon atoms of the alkyl group of the acrylic acid alkyl ester exceeds 18, the glass transition temperature of the pressure-sensitive adhesive layer 12 becomes too high, and the adhesive properties at room temperature deteriorate, and as a result, the metal layer during dicing. Fifteen peelings may occur.

The acrylic polymer A may contain units corresponding to other monomer components, if necessary.

In the acrylic polymer A, an isocyanate compound having a radically reactive carbon-carbon double bond is used. That is, it is preferable that the acrylic polymer has a structure in which a double bond-containing isocyanate compound is added to a polymer composed of a monomer composition such as the acrylic acid ester or a hydroxyl group-containing monomer. Therefore, it is preferable that the acrylic polymer has a radical-reactive carbon-carbon double bond in its molecular structure. As a result, the active energy ray-curable pressure-sensitive adhesive layer (ultraviolet-curable pressure-sensitive adhesive layer, etc.) that is cured by irradiation with active energy rays (ultraviolet rays, etc.) can be formed, and the peeling force between the metal layer 15 and the pressure-sensitive adhesive layer 12 can be obtained. Can be reduced.

Examples of the double bond-containing isocyanate compound include methacryloyl isocyanate, acryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like. The double bond-containing isocyanate compound can be used alone or in combination of two or more.

Further, in the active energy ray-curable pressure-sensitive adhesive, an external cross-linking agent can be appropriately used in order to adjust the pressure-sensitive adhesive strength before the activation energy ray irradiation and the adhesive strength after the activation energy ray irradiation. Specific means of the external cross-linking method include a method of adding and reacting a so-called cross-linking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, and a melamine-based cross-linking agent. When an external cross-linking agent is used, the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive. The amount of the external cross-linking agent used is generally 20 parts by weight or less (preferably 0.1 parts by weight to 10 parts by weight) with respect to 100 parts by weight of the base polymer. Further, if necessary, the active energy ray-curable pressure-sensitive adhesive may contain various conventionally known additives such as a pressure-imparting agent, an antiaging agent, and a foaming agent, in addition to the above-mentioned components.

The thickness of the pressure-sensitive adhesive layer 12 is not particularly limited and can be appropriately determined, but is generally about 5 to 200 μm. Further, the pressure-sensitive adhesive layer 12 may be composed of a single layer or a plurality of layers.

<Metal layer 14>
The metal constituting the metal layer 14 is not particularly limited, and for example, at least one selected from the group consisting of stainless steel, aluminum, iron, titanium, tin, nickel and copper is heat-dissipating and electronic device package. It is preferable from the viewpoint of preventing warpage. Among these, copper is particularly preferable from the viewpoint of high thermal conductivity and the effect of heat dissipation. Further, from the viewpoint of preventing warpage of the electronic device package 8, it is particularly preferable to contain aluminum.

The thickness of the metal layer 14 can be appropriately determined in consideration of heat dissipation, warpage prevention property of the electronic device package, workability, and the like, and is usually in the range of 2 to 200 μm. When the metal layer 14 is 200 μm or less, winding processing is easy, and when it is 50 μm or less, it is preferable because it can contribute to thinning of the electronic device package. On the other hand, from the viewpoint of heat dissipation, at least 2 μm or more is required.

A metal foil can be used as such a metal layer 14, and the metal foil may be an electrolytic foil or a rolled foil.

<Adhesive layer 15>
The adhesive layer 15 is a film made of an adhesive in advance.

The adhesive layer 15 is formed of at least a thermosetting resin, and is preferably formed of at least a thermosetting resin and a thermoplastic resin.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, and polycarbonate resin. Thermoplastic polyimide resin, polyamide resin such as 6-nylon and 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET (polyethylene terephthalate) and PBT (polybutylene terephthalate), polyamideimide resin, or fluororesin And so on. The thermoplastic resin can be used alone or in combination of two or more. Among these thermoplastic resins, acrylic resin has less ionic impurities and excellent stress relaxation property, and phenoxy resin has high toughness while achieving both flexibility and strength. This is particularly preferable because it can easily ensure reliability.

The acrylic resin is not particularly limited, and is linear or branched having 30 or less carbon atoms (preferably 1 to 18 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably 8 or 9 carbon atoms). Examples thereof include a polymer containing one or more kinds of acrylic acid or methacrylic acid ester having an alkyl group as a component. That is, in the present invention, acrylic resin has a broad meaning including methacrylic resin. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group and a 2-ethylhexyl group. , Octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group, stearyl group, octadecyl group and the like.

Further, the other monomer for forming the acrylic resin (a monomer other than the alkyl ester of acrylic acid or methacrylic acid having an alkyl group having 30 or less carbon atoms) is not particularly limited, and for example, acrylic acid. Carboxyl group-containing monomers such as methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid or crotonic acid, acid anhydride monomers such as maleic anhydride or itaconic anhydride, (meth) 2-Hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, (meth) Hydroxyl group-containing monomers such as 10-hydroxydecyl acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -methylacrylate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide -2-Methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, sulfonic acid group-containing monomers such as (meth) acryloyloxynaphthalene sulfonic acid, or 2-hydroxyethylacryloyl phosphate, etc. Examples thereof include sulfonic acid group-containing monomers. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and all have the same meaning as (meth) of the present invention.

Examples of the thermosetting resin include epoxy resin, phenol resin, amino resin, unsaturated polyester resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. The thermosetting resin can be used alone or in combination of two or more. As the thermosetting resin, an epoxy resin containing a small amount of ionic impurities and the like that corrode semiconductor elements is particularly preferable. Further, a phenol resin can be preferably used as the curing agent for the epoxy resin.

The epoxy resin is not particularly limited, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol AF type epoxy. Bifunctional epoxy such as resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluonelen type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylol ethane type epoxy resin, etc. An epoxy resin such as a resin, a polyfunctional epoxy resin, a hidden-in type epoxy resin, a trisglycidyl isocyanurate type epoxy resin, or a glycidylamine type epoxy resin can be used.

As the epoxy resin, a novolak type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type epoxy resin, and a tetraphenylolethane type epoxy resin are particularly preferable. This is because these epoxy resins are highly reactive with phenolic resins as curing agents and are excellent in heat resistance and the like.

Further, the phenol resin acts as a curing agent for the epoxy resin, and for example, a novolak type phenol resin such as a phenol novolac resin, a phenol aralkyl resin, a cresol novolac resin, a tert-butylphenol novolak resin, and a nonylphenol novolak resin, and a resole type. Examples thereof include phenolic resin and polyoxystyrene such as polyparaoxystyrene. The phenolic resin can be used alone or in combination of two or more. Of these phenolic resins, phenol novolac resin and phenol aralkyl resin are particularly preferable. This is because the connection reliability of the semiconductor device can be improved.

The mixing ratio of the epoxy resin and the phenol resin is preferably, for example, such that the hydroxyl groups in the phenol resin are 0.5 equivalents to 2.0 equivalents per 1 equivalent of the epoxy groups in the epoxy resin component. More preferred are 0.8 equivalents to 1.2 equivalents. That is, if the blending ratio of both is out of the above range, the curing reaction does not proceed sufficiently, and the characteristics of the cured epoxy resin product are likely to deteriorate.

Further, a thermosetting catalyst of epoxy resin and phenol resin may be used. The thermosetting accelerator is not particularly limited, and can be appropriately selected and used from known thermosetting accelerators. The thermosetting accelerator can be used alone or in combination of two or more. As the thermosetting accelerator, for example, an amine-based curing accelerator, a phosphorus-based curing accelerator, an imidazole-based curing accelerator, a boron-based curing accelerator, a phosphorus-boron-based curing accelerator, or the like can be used.

As the curing agent for the epoxy resin, it is preferable to use a phenol resin as described above, but known curing agents such as imidazoles, amines and acid anhydrides can also be used.

It is important that the adhesive layer 15 has adhesiveness (adhesiveness) to the back surface (circuit non-forming surface) of the semiconductor wafer. Therefore, in order to crosslink the adhesive layer 15 to some extent in advance, a polyfunctional compound that reacts with a functional group at the end of the molecular chain of the polymer may be added as a crosslinking agent. As a result, the adhesive properties at high temperatures can be improved and the heat resistance can be improved.

The cross-linking agent is not particularly limited, and a known cross-linking agent can be used. Specifically, for example, in addition to isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, and peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, and metal salts. Examples thereof include a system cross-linking agent, a carbodiimide-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, and an amine-based cross-linking agent. As the cross-linking agent, an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent is suitable. In addition, the cross-linking agent can be used alone or in combination of two or more.

In the present invention, instead of using a cross-linking agent, or while using a cross-linking agent, it is also possible to carry out the cross-linking treatment by irradiation with an electron beam, ultraviolet rays, or the like.

Other additives can be appropriately added to the adhesive layer 15 as needed. Examples of other additives include fillers, flame retardants, silane coupling agents, ion trapping agents, bulking agents, antiaging agents, antioxidants, surfactants and the like.

The filler may be either an inorganic filler or an organic filler, but the inorganic filler is preferable. By blending a filler such as an inorganic filler, it is possible to improve the thermal conductivity of the adhesive layer 15 and adjust the elastic modulus. Examples of the inorganic filler include ceramics such as silica, clay, gypsum, calcium carbonate, barium sulfate, alumina, beryllium oxide, silicon carbide, aluminum nitride, silicon nitride, aluminum, copper, silver, gold, nickel, chromium, and the like. Examples thereof include metals such as lead, tin, zinc, palladium and solder, alloys, and various inorganic powders made of carbon and the like. The filler can be used alone or in combination of two or more. Among them, silica or alumina is preferable as the filler, and molten silica is particularly preferable as the silica. The average particle size of the inorganic filler is preferably in the range of 0.001 μm to 80 μm. The average particle size of the inorganic filler can be measured by, for example, a laser diffraction type particle size distribution measuring device.

The blending amount of the filler (particularly the inorganic filler) is preferably 98% by weight or less (0% by weight to 98% by weight) with respect to the organic resin component, and particularly in the case of silica, 0% by weight to 70% by weight. In the case of a functional inorganic filler such as heat conduction or conductivity, it is preferably 10% by weight to 98% by weight.

Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. The flame retardant can be used alone or in combination of two or more. Examples of the silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like. The silane coupling agent can be used alone or in combination of two or more. Examples of the ion trap agent include hydrotalcites, bismuth hydroxide and the like. The ion trap agent can be used alone or in combination of two or more.

The adhesive layer 15 contains (A) epoxy resin, (B) curing agent, (C) acrylic resin or phenoxy resin, and (D) surface-treated inorganic filler, in particular from the viewpoint of adhesiveness and reliability. It is preferable to do so.

By using the epoxy resin (A), high adhesiveness, water resistance, and heat resistance can be obtained. As the epoxy resin, the above-mentioned known epoxy resin can be used. As the curing agent (B), the above-mentioned known curing agent can be used.

(C) Acrylic resin has both flexibility and strength and high toughness. A preferable acrylic resin is obtained by polymerizing a monomer having a Tg (glass transition temperature) of −50 ° C. to 50 ° C. and having an epoxy group, a glycidyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group or a carboxyl group as a crosslinkable functional group. It is a crosslinkable functional group-containing (meth) acrylic copolymer. Further, if it contains acrylonitrile or the like and exhibits rubber properties, higher toughness can be obtained.
Further, the phenoxy resin (C) has a long molecular chain and a structure similar to that of the epoxy resin, and acts as a flexible material in a composition having a high crosslink density and imparts high toughness, so that it has high strength. However, a toughness composition can be obtained. The preferred phenoxy resin has a main skeleton of bisphenol A type, and other commercially available phenoxy resins such as bisphenol F type phenoxy resin, bisphenol A / F mixed phenoxy resin and brominated phenoxy resin can be mentioned as preferable ones.

Examples of the surface-treated inorganic filler (D) include an inorganic filler surface-treated with a coupling agent. As the inorganic filler, the above-mentioned known inorganic filler can be used, but silica and alumina are preferable. By surface-treating with a coupling agent, the dispersibility of the inorganic filler is improved. Therefore, since it is excellent in fluidity, the adhesive force with the metal layer can be improved. Further, since the inorganic filler can be highly filled, the water absorption rate can be lowered and the moisture resistance can be improved.

For example, in the surface treatment of an inorganic filler with a silane coupling agent, the hydroxyl group existing on the surface of the inorganic filler and the silane coupling agent are treated by dispersing the inorganic filler in the silane coupling agent solution by a known method. This is done by reacting a hydrolyzed group such as an alkoxy group with a hydrolyzed silanol group to form a Si—O—Si bond on the surface of the inorganic filler.

The thickness of the adhesive layer 15 is not particularly limited, but is usually preferably 3 μm or more, more preferably 5 μm or more, and preferably 100 μm or less in order to contribute to the thinning of the semiconductor package, from the viewpoint of handleability. More preferably, it is 50 μm or less. Further, the adhesive layer 15 may be composed of a single layer or a plurality of layers.

The adhesive layer 15 has a storage elastic modulus of 10 GPa or less at 25 ° C. after heating at 100 ° C. for 3 hours. The storage elastic modulus was measured by heating the adhesive layer at 100 ° C. for 3 hours and cooling it sufficiently, and then using a dynamic viscoelasticity measuring device, measuring from 0 ° C. at a heating rate of 5 ° C./min and a frequency of 1 Hz. However, it is a value when the temperature reaches 25 ° C.

When the storage elastic modulus at 25 ° C. after heating at 100 ° C. for 3 hours is 10 GPa or less, the adhesive layer 15 is pre-cured in the state of the laminated body of the metal layer 14, the adhesive layer 15 and the semiconductor chip C. Since the warp of the laminate caused by the difference in linear expansion coefficient between the semiconductor chip C and the metal layer 14 due to heat is not retained even after cooling, the warp of the laminate after pre-curing does not occur. It can be suppressed. Further, if the adhesive layer is cured until the storage elastic modulus at 25 ° C. after heating at 100 ° C. for 3 hours becomes 10 GPa or less, it is possible to suppress the generation of voids when performing flip chip connection. it can.

The storage elastic modulus can be adjusted by the molecular weight of the polymer or the like, and generally, the lower the molecular weight, the lower the storage elastic modulus. Further, the storage elastic modulus can be adjusted by blending a plasticizer, a filler, or the like, and further, the storage elastic modulus of the meta) acrylic copolymer can be widely adjusted by a cross-linking agent.

The adhesive layer 15 has a curing rate of 10 to 100% when heated at 100 ° C. for 3 hours. If the curing rate of the adhesive layer 15 when heated at 100 ° C. for 3 hours is 10 to 100%, it is possible to suppress the generation of voids in the adhesive layer 15 when the flip chip is connected. The curing rate can be determined as follows using a differential scanning calorimetry (DSC). First, using a differential scanning calorimeter (DSC), the total calorific value (H0) from the pre-cured sample of the adhesive layer 15 and the residual calorific value (Ht) from the cured product sample when heated at 100 ° C. for 3 hours. taking measurement. Then, the curing rate is calculated by the following formula (4).
Curing rate (%) = (H0-Ht) / H0 × 100 (4)
H0: Total calorific value Ht: Residual calorific value

Further, the adhesive layer 15 has a peeling force (23 ° C., peeling angle 180 degrees, linear speed 300 mm / min) of 0.3 N or more from the metal layer 14 in the B stage (uncured or semi-cured state). Is preferable. If the peeling force is less than 0.3 N, peeling occurs between the semiconductor wafer W or the semiconductor chip C and the adhesive layer 15 or between the adhesive layer 15 and the metal layer 14 when dicing the semiconductor wafer W. This may result in chipping of the semiconductor chip C.

ここで、ｄはフィルムの密度である。
吸水率が１．５ｖｏｌ％を超えると、吸水した水分によりはんだリフロー時にパッケージクラックを生じるおそれがある。The water absorption rate of the adhesive layer 15 is preferably 1.5 vol% or less. The method for measuring the water absorption rate is as follows. That is, using an adhesive layer 15 (film-like adhesive) having a size of 50 × 50 mm as a sample, the sample is dried at 120 ° C. for 3 hours in a vacuum dryer, allowed to cool in a desiccator, and then the dry mass is measured. Let's call it M1. The sample is immersed in distilled water at room temperature for 24 hours and then taken out, the surface of the sample is wiped off with a filter paper, and the sample is quickly weighed to obtain M2. The water absorption rate is calculated by the following equation (1).

Here, d is the density of the film.
If the water absorption rate exceeds 1.5 vol%, package cracks may occur during solder reflow due to the absorbed water.

ここで、ｄはフィルムの密度である。
飽和吸湿率が１．０ｖｏｌ％を超えると、リフロー時の吸湿により蒸気圧の値が高くなり、良好なリフロー特性が得られないおそれがある。The saturated hygroscopicity of the adhesive layer 15 is preferably 1.0 vol% or less. The method for measuring the saturated hygroscopicity is as follows. That is, using a circular adhesive layer 15 (film-like adhesive) having a diameter of 100 mm as a sample, the sample was dried at 120 ° C. for 3 hours in a vacuum dryer, allowed to cool in a desiccator, and then the dry mass was measured to obtain M1. To do. The sample is absorbed in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 168 hours, then taken out and quickly weighed to obtain M2. The saturated hygroscopicity is calculated by the following equation (2).

Here, d is the density of the film.
If the saturated moisture absorption rate exceeds 1.0 vol%, the value of the vapor pressure becomes high due to the moisture absorption during reflow, and good reflow characteristics may not be obtained.

The residual volatile content of the adhesive layer 15 is preferably 3.0 wt% or less. The method for measuring the residual volatile components is as follows. That is, an adhesive layer 15 (film-like adhesive) having a size of 50 × 50 mm was used as a sample, the initial mass of the sample was measured to obtain M1, and the sample was heated at 200 ° C. for 2 hours in a hot air circulation constant temperature bath. Weigh it to M2. The residual volatile content is calculated by the following formula (3).
Residual volatile content (wt%) = [(M2-M1) / M1] x 100 (3)
If the residual volatile content exceeds 3.0 wt%, the solvent may volatilize due to heating during packaging, voids may be generated inside the adhesive layer 15, and package cracks may occur.

The ratio of the linear expansion coefficient of the metal layer 14 to the linear expansion coefficient of the adhesive layer 15 (the linear expansion coefficient of the metal layer 14 / the linear expansion coefficient of the adhesive layer 15) is preferably 0.2 or more. If the ratio is less than 0.2, peeling is likely to occur between the metal layer 14 and the adhesive layer 15, package cracks may occur during packaging, and reliability may decrease.

(Separator)
The separator is for improving the handleability of the adhesive layer 15 and protecting the adhesive layer 15. As the separator, polyester (PET, PBT, PEN, PBN, PTT) -based, polyolefin (PP, PE) -based, copolymer (EVA, EEA, EBA) -based, and these materials are partially substituted, and further. A film with improved adhesiveness and mechanical strength can be used. Further, it may be a laminate of these films.

The thickness of the separator is not particularly limited and may be set as appropriate, but is preferably 25 to 50 μm.

(Tape 10 for electronic device package)
A method for manufacturing the electronic device package tape 10 according to the present embodiment will be described. First, the adhesive layer 15 can be formed by using a conventional method in which a resin composition is prepared and formed into a film-like layer. Specifically, for example, the resin composition is applied onto an appropriate separator (release paper, etc.) and dried (when thermosetting is required, heat treatment is performed and dried as necessary). Examples thereof include a method of forming the adhesive layer 15. The resin composition may be a solution or a dispersion. Next, the obtained adhesive layer 15 and the separately prepared metal layer 14 are bonded together. As the metal layer 14, a commercially available metal foil may be used. After that, the adhesive layer 15 and the metal layer 14 are pre-cut into a circular label shape having a predetermined size using a push-cutting blade to remove unnecessary portions around the adhesive layer 15.

Next, the adhesive tape 13 is produced. The base film 11 can be formed by a conventionally known film forming method. Examples of the film-forming method include a calendar film-forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry laminating method. Next, the pressure-sensitive adhesive layer composition is applied onto the base film 11 and dried (by heat-crosslinking if necessary) to form the pressure-sensitive adhesive layer 12. Examples of the coating method include roll coating, screen coating, and gravure coating. The pressure-sensitive adhesive layer composition may be directly applied to the base film 11 to form the pressure-sensitive adhesive layer 12 on the base film 11, or the surface of the pressure-sensitive adhesive layer composition may be peeled off. After applying to a release paper or the like to form the pressure-sensitive adhesive layer 12, the pressure-sensitive adhesive layer 12 may be transferred to the base film 11. As a result, the adhesive tape 13 in which the adhesive layer 12 is formed on the base film 11 is produced.

After that, the adhesive tape 13 is laminated on the separator provided with the circular metal layer 14 and the adhesive layer 15 so that the metal layer 14 and the adhesive layer 12 are in contact with each other, and in some cases, the adhesive tape 13 also has a predetermined size. The tape 10 for an electronic device package is made by pre-cutting into a circular label shape or the like.

<How to use>
Next, a method of manufacturing a semiconductor device using the electronic device package tape 10 of the present embodiment will be described with reference to FIG.

The semiconductor device manufacturing method includes a step of attaching the semiconductor wafer W on the adhesive tape-integrated electronic device package tape 10 (mounting step) and a step of dicing the semiconductor wafer W to form a semiconductor chip C (dicing). Step), a step of peeling the laminate of the metal layer 14, the adhesive layer 15, and the semiconductor chip C from the adhesive layer 12 of the adhesive tape 13 (pickup step), and a step of pre-curing the obtained laminate (step). A pre-curing step) and a step of flip-chip connecting the semiconductor chip C onto the adherend 16 (flip-chip connecting step) are included at least.

[Mounting process]
First, a separator arbitrarily provided on the adhesive tape-integrated electronic device package tape 10 is appropriately peeled off, and the semiconductor wafer W is attached to the adhesive layer 15 as shown in FIG. 2 (A). Then, this is adhered and held and fixed (mounting process). At this time, the adhesive layer 15 is in an uncured state (including a semi-cured state). Further, the adhesive tape-integrated electronic device package tape 10 is attached to the back surface of the semiconductor wafer W. The back surface of the semiconductor wafer W means a surface opposite to the circuit surface (also referred to as a non-circuit surface, a non-electrode forming surface, or the like). The sticking method is not particularly limited, but a crimping method is preferable. The crimping is usually performed while pressing with a pressing means such as a crimping roll.

[Dicing process]
Next, as shown in FIG. 2B, dicing of the semiconductor wafer W is performed. As a result, the semiconductor wafer W is cut into a predetermined size and individualized (small pieces) to manufacture the semiconductor chip C. Dicing is performed, for example, from the circuit surface side of the semiconductor wafer W according to a conventional method. Further, in this step, for example, a cutting method called full-cut that cuts up to the electronic device package tape 10 can be adopted. The dicing apparatus used in this step is not particularly limited, and conventionally known dicing apparatus can be used. Further, since the semiconductor wafer W is adhesively fixed to the electronic device package tape 10 with excellent adhesion, chip chipping and chip skipping can be suppressed, and damage to the semiconductor wafer W can also be suppressed. When expanding the tape 10 for an electronic device package integrated with an adhesive tape, the expansion can be performed using a conventionally known expanding device.

[Pickup process]
As shown in FIG. 2C, the semiconductor chip C is picked up and the semiconductor chip C is peeled off from the adhesive tape 13 together with the adhesive layer 15 and the metal layer 14. The pick-up method is not particularly limited, and various conventionally known methods can be adopted. For example, a method in which each semiconductor chip C is pushed up from the base film 11 side of the electronic device package tape 10 by a needle and the pushed-up semiconductor chip C is picked up by a pickup device and the like can be mentioned.

[Pre-curing process]
Pre-curing is performed by pre-curing the adhesive layer 15 in the laminated body of the metal layer 14, the adhesive layer 15 and the semiconductor chip C so that the adhesive layer 15 does not suddenly boil in the subsequent flip chip connecting step. The conditions for pre-curing may be appropriately set within a range in which the adhesive layer 15 does not suddenly boil, but it is preferable to heat at 100 to 150 ° C. for about 4 hours to 15 minutes.

[Flip chip connection process]
As shown in FIG. 2D, the picked up semiconductor chip C is fixed to an adherend 16 such as a substrate by a flip chip bonding method (flip chip mounting method). Specifically, the semiconductor chip C is always attached to the adherend 16 in a form in which the circuit surface (also referred to as a surface, a circuit pattern forming surface, an electrode forming surface, etc.) of the semiconductor chip C faces the adherend 16. Fix according to the law. For example, first, flux is attached to the bump 17 as a connecting portion formed on the circuit surface side of the semiconductor chip C. Next, the bump 17 of the semiconductor chip C is brought into contact with the conductive material 18 (solder or the like) for joining attached to the connection pad of the adherend 16 and pressed to melt the bump 17 and the conductive material 18. The electrical conduction between the semiconductor chip C and the adherend 16 can be ensured, and the semiconductor chip C can be fixed to the adherend 16 (flip chip bonding step). At this time, a gap is formed between the semiconductor chip C and the adherend 16, and the gap distance thereof is generally about 30 μm to 300 μm. After the semiconductor chip C is flip-chip bonded (flip-chip connected) on the adherend 16, the flux remaining on the facing surface or the gap between the semiconductor chip C and the adherend 16 is washed and removed to form the gap. Fill with a sealing material (sealing resin, etc.) and seal.

As the adherend 16, various substrates such as a lead frame and a circuit board (wiring circuit board, etc.) can be used. The material of such a substrate is not particularly limited, and examples thereof include a ceramic substrate and a plastic substrate. Examples of the plastic substrate include an epoxy substrate, a bismaleimide triazine substrate, a polyimide substrate and the like. Further, a chip-on-chip structure can be obtained by using another semiconductor chip as the adherend 16 and connecting the semiconductor chip C with a flip chip.

<Example>
Next, in order to further clarify the effect of the present invention, Examples and Comparative Examples will be described in detail, but the present invention is not limited to these Examples.

(1) Preparation of Adhesive Tape The following was prepared as a base film.
(Base film a-1)
Zinc ionomer a (density 0.96 g / cm ³ , zinc ion content 4 mass) of ethylene-methacrylic acid-ethyl metaacrylic acid (mass ratio 8: 1: 1) ternary copolymer synthesized by radical polymerization method %, Chlorine content less than 1% by mass, Vicat softening point 56 ° C, melting point 86 ° C) melted at 140 ° C and molded into a long film with a thickness of 100 μm using an extruder. A material film a-1 was produced.

(Adhesive layer composition b-1)
A copolymer composed of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and methacrylic acid as an acrylic copolymer (A1) having a functional group, having a ratio of 2-ethylhexyl acrylate of 55 mol% and a mass average molecular weight of 750,000. Was prepared. Next, 2-isocyanatoethyl methacrylate was added so that the iodine value was 25, and an acrylic copolymer (a1) having a glass transition temperature of −50 ° C., a hydroxyl value of 10 gKOH / g, and an acid value of 5 mgKOH / g. Was prepared.
To 100 parts by mass of the acrylic copolymer (a1), 3 parts by mass of Coronate L (manufactured by Toso Co., Ltd., trade name) was added as a polyisocyanate, and Esacure KIP 150 (manufactured by Lamberti, trade name) was added as a photopolymerization initiator. ) Was added in an amount of 3 parts by mass, and the mixture was dissolved in ethyl acetate and stirred to obtain a pressure-sensitive adhesive layer composition b-1.

<Adhesive tape (1)>
The prepared pressure-sensitive adhesive layer composition b-1 is applied to a release liner made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 10 μm, and dried at 110 ° C. for 3 minutes. , The pressure-sensitive adhesive tape (1) having the pressure-sensitive adhesive layer formed on the base material film was produced by laminating with the base film a-1.

(2) Preparation of Adhesive Layer (Adhesive Layer Composition c-1)
10 parts by mass of acrylonitrile butadiene rubber (acrylonitrile content 40% by mass), 17 parts by mass of novolak type epoxy resin (manufactured by DIC Corporation, trade name "N-775", epoxy equivalent 195, softening point 78 ° C.), liquid bisphenol A Type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Corporation, trade name "YD-128", Mw400, epoxy equivalent 190) 40 parts by mass, phenol resin as a curing agent (manufactured by Meiwa Kasei Co., Ltd., trade name "H-4") 32 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive layer composition solution.

(Adhesive layer composition c-2)
80 parts by mass of acrylic resin (Nagase Chemtex Co., Ltd., trade name "Taisan Resin SG-P3", Mw 850,000, Tg 12 ° C) and 10 mass of naphthalene type epoxy resin (manufactured by DIC Corporation, trade name "HP-4700") 10 parts by mass of a phenol resin (manufactured by Meiwa Kasei Co., Ltd., trade name "MEH7851") as a curing agent was dissolved in methyl ethyl ketone to prepare an adhesive layer composition solution.

(Adhesive layer composition c-3)
100 parts by mass of acrylic resin (manufactured by Nagase Chemtex Co., Ltd., "Taisan Resin SG-70L", Tg-13 ° C.) and cresol novolac type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name "EOCN-1020", epoxy Equivalent 198, softening point 64 ° C) 353 parts by mass, liquid bisphenol A type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name "YD-128", Mw400, epoxy equivalent 190) 46 parts by mass, imidazole as a curing agent Shikoku Kasei Kogyo Co., Ltd., trade name "2PHZ-PW") 3 parts by mass, silica filler (Admatex Co., Ltd., trade name "SO-C2", average particle size 0.5 μm) 330 parts by mass to methyl ethyl ketone It was dissolved or dispersed to prepare an adhesive layer composition solution.

(Adhesive layer composition c-4)
100 parts by mass of bisphenol A type phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name "YP-50S", Mw 60,000, Tg 84 ° C) and cresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name "EOCN-" 1020 ”, epoxy equivalent 198, softening point 64 ° C) 40 parts by mass, liquid bisphenol A type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name“ YD-128 ”, Mw400, epoxy equivalent 190) 100 parts by mass, curing agent Imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name "2PHZ-PW") 1.5 parts by mass, silica filler (manufactured by Admatex Co., Ltd., trade name "SO-C2", average particle size 0.5 μm) 200 The parts by mass were dissolved or dispersed in methyl ethyl ketone to prepare an adhesive layer composition solution.

(Adhesive layer composition c-5)
10 parts by mass of acrylonitrile butadiene rubber (acrylonitrile content 40% by mass), 17 parts by mass of novolak type epoxy resin (manufactured by DIC Corporation, trade name "N-775", epoxy equivalent 195, softening point 78 ° C.), liquid bisphenol A Type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Corporation, trade name "YD-128", Mw400, epoxy equivalent 190) 40 parts by mass, phenol resin as a curing agent (manufactured by Meiwa Kasei Co., Ltd., trade name "H-4") 25 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive layer composition solution.

(Adhesive layer composition c-6)
100 parts by mass of bisphenol A type phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name "YP-50S", Mw 60,000, Tg 84 ° C) and cresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name "EOCN-" 1020 ”, epoxy equivalent 198, softening point 64 ° C) 50 parts by mass, liquid bisphenol A type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name“ YD-128 ”, Mw400, epoxy equivalent 190) 100 parts by mass, curing agent Imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name "2PHZ-PW") 1.0 part by mass, silica filler (manufactured by Admatex Co., Ltd., trade name "SO-C2", average particle size 0.5 μm) 200 The parts by mass were dissolved or dispersed in methyl ethyl ketone to prepare an adhesive layer composition solution.

(Adhesive layer composition c-7)
100 parts by mass of acrylic resin (manufactured by Nagase ChemteX Corporation, trade name "Taisan Resin SG-708-6", Tg 6 ° C) and solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "Epicoat 1004", Softening point 97 ° C) 280 parts by mass, phenol resin as a curing agent (manufactured by Mitsui Chemicals Co., Ltd., trade name "Milex XLC-4L", melting point 62 ° C) 306 parts by mass, silica filler (manufactured by Admatex Co., Ltd., trade name) "SO-C2" (average particle size 0.5 μm) 237 parts by mass was dissolved or dispersed in methyl ethyl ketone to prepare an adhesive layer composition solution.

(Adhesive layer composition c-8)
100 parts by mass of acrylic resin (manufactured by Nagase Chemtex Co., Ltd., "Taisan Resin SG-70L", Tg-13 ° C.) and cresol novolac type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name "EOCN-1020", epoxy Equivalent 198, softening point 64 ° C) 260 parts by mass, liquid bisphenol A type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name "YD-128", Mw400, epoxy equivalent 190) 46 parts by mass, imidazole as a curing agent 1 part by mass of Shikoku Kasei Kogyo Co., Ltd., trade name "2PHZ-PW") and 330 parts by mass of silica filler (Admatex Co., Ltd., trade name "SO-C2", average particle size 0.5 μm) are added to methyl ethyl ketone. It was dissolved or dispersed to prepare an adhesive layer composition solution.

<Adhesive layer (1)>
The adhesive layer composition c-1 is applied to a separator made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 5 μm, dried at 110 ° C. for 5 minutes, and then placed on the separator. An adhesive film on which the adhesive layer (1) was formed was produced.

<Adhesive layer (2)>
The adhesive layer composition c-2 is applied to a separator made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 5 μm, dried at 110 ° C. for 5 minutes, and then placed on the separator. An adhesive film on which the adhesive layer (2) was formed was produced.

<Adhesive layer (3)>
The adhesive layer composition c-3 is applied to a separator made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 5 μm, dried at 110 ° C. for 5 minutes, and then placed on the separator. An adhesive film on which the adhesive layer (3) was formed was produced.

<Adhesive layer (4)>
The adhesive layer composition c-4 is applied to a separator made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 5 μm, dried at 110 ° C. for 5 minutes, and then placed on the separator. An adhesive film on which the adhesive layer (4) was formed was produced.

<Adhesive layer (5)>
The adhesive layer composition c-5 is applied to a separator made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 5 μm, dried at 110 ° C. for 5 minutes, and then placed on the separator. An adhesive film on which the adhesive layer (5) was formed was produced.

<Adhesive layer (6)>
The adhesive layer composition c-6 is applied to a separator made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 5 μm, dried at 110 ° C. for 5 minutes, and then placed on the separator. An adhesive film on which the adhesive layer (6) was formed was produced.

<Adhesive layer (7)>
The adhesive layer composition c-7 is applied to a separator made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 5 μm, dried at 110 ° C. for 5 minutes, and then placed on the separator. An adhesive film on which the adhesive layer (7) was formed was produced.

<Adhesive layer (8)>
The adhesive layer composition c-8 is applied to a separator made of a release-treated polyethylene-terephthalate film so that the thickness after drying is 5 μm, dried at 110 ° C. for 5 minutes, and then placed on the separator. An adhesive film on which the adhesive layer (8) was formed was produced.

(3) Metal layer The following metal layers were prepared.
<Metal layer (1)>
F0-WS (trade name, manufactured by Furukawa Electric Co., Ltd., copper foil, thickness 12 μm, surface roughness Rz 1.3um)

(4) Preparation of Tape for Electronic Device Package <Example 1>
The adhesive layer (1) and the metal layer (1) obtained as described above were bonded to each other under the conditions of a bonding angle of 120 °, a pressure of 0.2 MPa, and a speed of 10 mm / s to prepare a single-sided adhesive film. The adhesive tape (1) is pre-cut into a shape that can be attached to the ring frame, and the single-sided adhesive film is pre-cut into a shape that can cover the wafer, and the adhesive layer of the adhesive tape (1) and the metal layer of the single-sided adhesive film. The sides were bonded to each other so that the adhesive layer was exposed around the single-sided adhesive film to prepare the tape for the electronic device package of Example 1.

<Examples 2 to 4, Comparative Examples 1 to 4>
For electronic device packages of Examples 2 to 4 and Comparative Examples 1 to 4 by the same method as in Example 1 except that the combination of the adhesive tape, the adhesive layer composition, and the metal layer is the combination shown in Table 1. A tape was made.

The following measurements and evaluations were performed on the electronic device package tapes according to Examples 1 to 4 and Comparative Examples 1 to 4. The results are shown in Table 1.

(Storage modulus)
The storage elastic modulus of the adhesive layer used in each Example and each Comparative Example at 25 ° C. was measured as follows. On a polyethylene terephthalate (PET) separator having a thickness of 25 μm, the adhesive layer composition related to the adhesive layer used in each Example and Comparative Example was applied and dried so that the film thickness after drying was 30 μm. After that, it is bonded on a polyethylene terephthalate (PET) separator having a thickness of 25 μm, the adhesive layer is peeled off from the separator, and the adhesive layers are bonded to each other to prepare a test piece having a thickness of 1 mm, a width of 5 mm, and a length of 25 mm. did. After heating the obtained test piece at 100 ° C. for 3 hours, the distance between chucks was set to 15 mm using a dynamic viscoelasticity measuring device (manufactured by UBM Co., Ltd., trade name: Rheogel-E4000), and 0 ° C. The measurement was started at a temperature rising rate of 5 ° C./min and a frequency of 1 Hz, and the value at the time when the temperature reached 25 ° C. was defined as the storage elastic modulus. The measurement results are shown in Table 1.

(Curing rate)
The curing rate was determined as follows using a differential scanning calorimeter (DSC). First, using a differential scanning calorimeter (DSC), the total calorific value (H0) from the pre-cured sample of the adhesive layer 15 and the residual calorific value (Ht) from the cured product sample when heated at 100 ° C. for 3 hours. It was measured. Then, the curing rate was calculated by the following formula (4). The results are shown in Table 1.
Curing rate (%) = (H0-Ht) / H0 × 100 (4)

(Warp evaluation)
An adhesive layer of the tape for electronic device packaging according to each example and each comparative example is attached to the back surface of a silicon wafer with bumps (bump: copper pillar and solder, bump height: about 40 μm) having a thickness of 200 μm, and dicing is performed. , 7.5 mm × 7.5 mm was divided into evaluation chips. After irradiating the adhesive layer with an air-cooled high-pressure mercury lamp (80 W / cm, irradiation distance 10 cm) at 200 mJ / cm ² from the base film side of the adhesive tape, the metal layer, the adhesive layer, and the laminate of the silicon chips are subjected to. The adhesive layer was pre-cured by heating at 100 ° C. for 3 hours. For 10 sufficiently cooled laminates, the laminate was placed on a flat table, one side of the laminate was pressed, and the height of the warp was measured with a caliper, and the average value was taken as the amount of warp. Those having a warp amount of less than 1 mm were evaluated as non-defective products, those having a warp amount of 1 mm or more and less than 3 mm were evaluated as Δ, and those having a warp amount of 3 mm or more were evaluated as defective products. The results are shown in Table 1.

(Void evaluation)
A glass epoxy substrate (glass epoxy substrate: thickness 420 μm, copper wiring: thickness 9 μm, 80 μm pitch) was prepared, and for the above laminate having a warp amount of less than 3 mm, a flip chip bonder (Shinkawa Co., Ltd., trade name “LFB-2301”) was prepared. A bump of a semiconductor chip was mounted on a glass epoxy substrate (mounting condition: crimp head temperature 260 ° C./10 seconds / 1 MPa) to obtain a semiconductor device for evaluation.

An external image was taken using an ultrasonic diagnostic imaging device (Hitachi Power Solutions Co., Ltd., trade name "FS300III"). Using the image processing software Adobe Photoshop (registered trademark), the void portion of the adhesive layer was identified by color tone correction and digradation, and the proportion of the void portion was calculated from the histogram. The area of the adhesive layer on the chip was set to 100%, and the proportion occupied by the void portion was evaluated according to the following criteria.
Void part occupies 10% or less: As a good product ◎
Void part occupies more than 10% and less than 20%: ○ as a good product
Void part occupies more than 20%: × as defective product

As shown in Table 1, the tapes for electronic device packaging according to Examples 1 to 4 had a storage elastic modulus of 10 GPa or less after heating at 100 ° C. for 3 hours, and were heated at 100 ° C. for 3 hours. Since the curing rate of the adhesive layer was 10 to 100%, good results were obtained in both the warp evaluation and the void evaluation.

On the other hand, the tapes for electronic device packaging according to Comparative Examples 1 and 4 have a curing rate of less than 10% when heated at 100 ° C. for 3 hours, resulting in inferior results in void evaluation. became. Further, the tapes for electronic device packaging according to Comparative Examples 2 and 3 were inferior in the warp evaluation because the storage elastic modulus of the adhesive layer after heating at 100 ° C. for 3 hours was larger than 10 GPa.

10: Tape for electronic device packaging 11: Base film 12: Adhesive layer 13: Adhesive tape 14: Metal layer 15: Adhesive layer

Claims (4)

An adhesive tape having a base film and an adhesive layer,
A metal layer laminated on the opposite side of the pressure-sensitive adhesive layer to the base film, and
It is provided on the opposite side of the metal layer to the adhesive layer, and has an adhesive layer for adhering the metal layer to the back surface of the electronic device.
The adhesive layer is an electronic device package having a storage elastic modulus of 10 GPa or less after heating at 100 ° C. for 3 hours and a curing rate of 10 to 100% when heated at 100 ° C. for 3 hours. Tape for. The tape for an electronic device package according to claim 1, wherein the metal layer contains copper or aluminum. 1 or claim 1, wherein the adhesive layer contains (A) an epoxy resin, (B) a curing agent, (C) an acrylic resin or a phenoxy resin, and (D) a surface-treated inorganic filler. The tape for an electronic device package according to claim 2. The pressure-sensitive adhesive layer contains an acrylic acid ester represented by CH ₂ = CHCOOR (in the formula, R is an alkyl group having 4 to 18 carbon atoms), a hydroxyl group-containing monomer, and a radical reactivity in the molecule. The tape for an electronic device package according to any one of claims 1 to 3, which contains an acrylic polymer composed of an isocyanate compound having a carbon-carbon double bond.

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