JP4851573B2 - Sheet adhesive and wafer processing tape - Google Patents

Description

  The present invention relates to a sheet-like adhesive and a wafer processing tape.

  In the manufacturing process of a semiconductor device, a semiconductor wafer is cut and separated (diced) into semiconductor chips, a separated semiconductor chip is picked up, and the bonded semiconductor chip is bonded to a lead frame or a package substrate. A (mount) process is performed.

  In recent years, as a wafer processing tape used in the manufacturing process of the semiconductor device, for example, a wafer processing tape in which an adhesive layer is provided on a base film, or a sheet-like adhesive is further provided on the adhesive layer. A wafer processing tape (dicing die bond film: DDF) having a laminated structure has been proposed and already put into practical use.

  Also, a silane coupling agent is added as a sheet-like adhesive composition for wafer processing tape in order to improve the adhesion between the semiconductor chip and the lead frame, package substrate, etc. in the die bonding (mounting) process. A method is disclosed (see Patent Document 1). However, since the silane coupling agent has a low molecular weight, the silane coupling agent present on the surface of the sheet-like adhesive enters the inside of the sheet-like adhesive with the passage of time, and the adhesive force on the surface of the sheet-like adhesive is reduced. There is a problem that a phenomenon of lowering (hereinafter referred to as bleed out) occurs.

  In order to solve the above problem, there is also disclosed a method in which silane coupling agents are reacted with each other and then added as a sheet-like adhesive composition of a wafer processing tape (see Patent Document 2).

Japanese Patent No. 3620156 Japanese Patent No. 4165065

  However, even if it is the material which reacted the silane coupling agent shown in patent document 2, since a silane coupling agent will react and react with moisture, it will be a material in the stage before manufacture of a sheet-like adhesive. The silane coupling agent must be stored under strict conditions, and the production efficiency of the sheet-like adhesive and the wafer processing tape is reduced.

  Therefore, the present invention has been made to solve the above-described problems, and is a sheet-like adhesive that is easy to store, has high production efficiency, has little deterioration of adhesive strength with time, and can be stored. An object of the present invention is to provide a wafer processing tape produced using this sheet-like adhesive.

  As a result of intensive studies on the above problems, the inventors of the present invention include a chelate-modified epoxy resin as a sheet-like adhesive composition, so that the material can be easily stored and the production efficiency is high. The present inventors have found that a sheet-like adhesive and a wafer processing tape that can be easily stored in a small amount can be produced.

That is, the sheet-like adhesive for wafer processing or die bonding process according to the first aspect of the present invention includes, as a cured resin component, a cured resin that cures with heat or high energy rays, and an epoxy curing agent that cures epoxy. wherein the said portion of the cured resin or all are chelate-modified epoxy resins, the chelating modified epoxy resin is seen containing more than 10 wt% in the curable resin component, an acrylic resin to the curable resin 100 parts by weight of component It includes a copolymer 130-270 parts by weight, if it contains a coupling agent, and wherein said coupling agent 0.1 parts by weight or less free Mukoto to the curable resin component 100 parts by mass.

The wafer processing tape according to the first aspect of the present invention is a wafer processing or die bonding step according to the first aspect of the present invention on an adhesive film in which an adhesive layer is laminated on a base film. A sheet-like adhesive is laminated on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film.

  According to the present invention, it is possible to produce a sheet-like adhesive that is easy to store, has high production efficiency, has little deterioration of adhesive strength with time, and is easy to store. In addition, by using this sheet-like adhesive to produce a wafer processing tape, it is possible to produce a wafer processing tape that is easy to store, has high production efficiency, and has little deterioration of adhesive strength over time. .

It is sectional drawing which shows the adhesive film using the sheet-like adhesive agent 12 which concerns on one Embodiment of this invention. It is sectional drawing which shows the tape for wafer processing which concerns on one Embodiment of invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view showing an adhesive film 20 using a sheet-like adhesive 12 according to an embodiment of the present invention.
As shown in FIG. 1, the adhesive film 20 has a configuration in which a sheet-like adhesive 12 according to the present invention is laminated on a release film 11. In addition, it is an adhesive film having a configuration in which a release film different from the release film 11 is further laminated on the surface of the sheet-like adhesive 12 opposite to the surface on which the release film 11 is provided. It may be wound around. Moreover, said sheet-like adhesive 12 may be cut | disconnected (pre-cut) in a predetermined shape previously according to a use process or an apparatus.

  Next, a wafer processing tape (dicing die bonding film) in which the sheet-like adhesive 12 according to the present invention and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer is laminated on the base film will be described. . FIG. 2 is a cross-sectional view showing a wafer processing tape 10 according to an embodiment of the present invention.

  As shown in FIG. 2, a wafer processing tape 10 according to one embodiment of the present invention includes a pressure-sensitive adhesive film 13 including a film-like base film 13 a and a pressure-sensitive adhesive layer 13 b formed thereon, and the pressure-sensitive adhesive film 13. And a sheet-like adhesive 12 laminated on the film 13. Thus, in the wafer processing tape 10, the base film 13a, the pressure-sensitive adhesive layer 13b, and the sheet-like adhesive 12 are formed in this order.

  The pressure-sensitive adhesive layer 13b may be composed of a single pressure-sensitive adhesive layer, or may be composed of a laminate of two or more pressure-sensitive adhesive layers. Further, FIG. 2 shows a wafer processing tape 10 in which a release film 11 is provided on a sheet-like adhesive 12.

  The pressure-sensitive adhesive film 13 and the sheet-like adhesive 12 may be cut (pre-cut) into a predetermined shape in advance according to the use process and the apparatus. The wafer processing tape 10 of the present invention includes a form cut for each semiconductor wafer and a form obtained by winding a plurality of long films formed in a roll shape.

  Hereinafter, each component of the adhesive film 20 and the wafer processing tape 10 of this embodiment will be described in detail.

(Release film)
The release film 11 is used for the purpose of improving the handleability of the sheet adhesive 12.

  Examples of the release film 11 include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polychloride chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, and a polybutylene terephthalate film. , Polyurethane film, ethylene / vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film A fluororesin film or the like is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient.

The surface tension of the release film 11 is preferably 40 mN / m or less, and more preferably 35 mN / m or less. Such a release film 11 having a low surface tension can be obtained by appropriately selecting the material, and can also be obtained by applying a release treatment by applying a silicone resin or the like to the surface of the film. .
The film thickness of the release film 11 is usually 5 to 300 μm, preferably 10 to 200 μm, and particularly preferably about 20 to 150 μm.

(Sheet adhesive)
The sheet-like adhesive 12 is attached to the back surface of the semiconductor chip when the semiconductor chip is picked up after the semiconductor wafer is bonded and diced, and serves as an adhesive for fixing the chip to the substrate or the lead frame. It is what is used.

  The sheet-like adhesive 12 includes a cured resin that is cured by heat or high energy rays, and a part or all of the cured resin is made of a chelate-modified epoxy resin. That is, this cured resin may be a chelate-modified epoxy resin alone, or may be another cured resin including a chelate-modified epoxy resin and an epoxy resin that is not chelate-modified.

  The chelate-modified epoxy resin may be obtained by reacting a chelate component containing a metal oxide and / or metal hydroxide with an epoxy component having two or more epoxy groups in the molecule.

Magnesium oxide as a metal oxide and / or metal hydroxide, calcium oxide, zinc oxide, titanium oxide, cadmium oxide, lead oxide, magnesium hydroxide, calcium hydroxide and the like Ru are preferably used.

Examples of the epoxy component include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), Ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene) ), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, o Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as cibisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol Polyglycidyl ethers of polyhydric alcohols such as polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid , Suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalate , Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid And glycidyl methacrylate homopolymers or copolymers; epoxy compounds having a glycidylamino group such as N, N-diglycidylaniline and bis (4- (N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene Epoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis ( 3,4-epoxy-6-methylcyclohexylmethyl) epoxides of cyclic olefin compounds such as adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and complex such as triglycidyl isocyanurate A ring compound or the like is preferably used.

  Cured resins that are optionally used in addition to chelate-modified epoxy resins include epoxy resins that are not chelate-modified, acrylic resins, silicone resins, phenol resins, thermosetting polyimide resins, polyurethane resins, melamine resins, urea resins, and mixtures thereof. Alternatively, modified products may be mentioned, but it is particularly preferable to use an epoxy resin in terms of excellent heat resistance, workability, and reliability.

  The sheet adhesive 12 includes an epoxy curing agent that cures at least the chelate-modified epoxy resin. In addition, when the epoxy resin which is not chelate modified | denatured is included as hardening resin used arbitrarily other than a chelate modified epoxy resin, it is preferable to use an epoxy hardening | curing agent also about this epoxy resin. For example, a phenolic resin can be used as the epoxy curing agent. As the phenolic resin, a condensate of phenols such as alkylphenol, polyhydric phenol, naphthol and aldehydes is used without particular limitation. The phenolic hydroxyl group contained in these phenolic resins can easily undergo an addition reaction with the epoxy group of the epoxy resin by heating to form a cured product having high impact resistance.

  Phenol resins include phenol novolak resin, o-cresol novolak resin, p-cresol novolak resin, t-butylphenol novolak resin, dicyclopentadiene cresol resin, polyparavinylphenol resin, bisphenol A type novolak resin, or modifications thereof. A thing etc. are used preferably.

  In addition, a thermally activated latent epoxy resin curing agent can also be used as the curing agent. This curing agent is a type of curing agent that does not react with the epoxy resin at room temperature but is activated by heating at a certain temperature or more and reacts with the epoxy resin.

  As an activation method, a method of generating active species (anions and cations) by a chemical reaction by heating, a dispersion that is stably dispersed in the epoxy resin near room temperature, is compatible with and dissolved in the epoxy resin at high temperatures, and a curing reaction is performed. There are a method for starting, a method for starting a curing reaction by elution at a high temperature with a molecular sieve encapsulated type curing agent, a method using a microcapsule, and the like.

  Examples of the thermally active latent epoxy resin curing agent include various onium salts, high melting point active hydrogen compounds such as dibasic acid dihydrazide compounds, dicyandiamide, amine adduct curing agents, and imidazole compounds.

  Moreover, a hardening accelerator etc. can also be used as an adjuvant. There is no restriction | limiting in particular as a hardening accelerator which can be used for this invention, For example, a tertiary amine, imidazoles, a quaternary ammonium salt etc. can be used. Examples of imidazoles preferably used in the present invention include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenyl-4,5-dihydroxymethylimidazole etc. are mentioned, These can also use 1 type (s) or 2 or more types together. Imidazoles are commercially available from Shikoku Kasei Kogyo Co., Ltd. under the trade names 2MZ, 2E4MZ, 2PZ-CN, 2PZ-CNS, 2PHZ.

  The chelate-modified epoxy resin and the optionally used cured resin and the epoxy curing agent are referred to as a cured resin component in this specification, and the sheet-like adhesive 12 contains 10 mass of the chelate-modified epoxy resin in the cured resin component. Contain more than%. If it is less than 10% by mass, the adhesive force is insufficient and package cracks are likely to occur.

  Moreover, it is preferable that the sheet adhesive 12 contains a polymer, and a phenoxy resin, an acrylic copolymer, etc. can be used as a polymer. It is preferable to use an acrylic copolymer from the viewpoint of excellent flexibility, and a glass transition temperature (Tg) of −10 ° C. or higher and 30 ° C. or lower is preferable. If the glass transition temperature is lower than −10 ° C., film formation becomes difficult, and if it exceeds 30 ° C., the film flexibility is lowered.

  The polymerization method of the acrylic copolymer is not particularly limited, and examples thereof include pearl polymerization, solution polymerization, suspension polymerization, and the like, and the copolymer can be obtained by these methods. Suspension polymerization is preferable because of its excellent heat resistance. Examples of such an acrylic copolymer include SG-708-6 (trade name, manufactured by Nagase ChemteX Corporation).

  The weight average molecular weight of the acrylic copolymer is preferably 50,000 or more, particularly preferably in the range of 200,000 to 1,000,000. If the molecular weight is too low, film formation will be insufficient, and if it is too high, compatibility with other components will deteriorate, resulting in hindering film formation.

  Moreover, it is preferable that 130-270 mass parts of acrylic resin copolymers are included with respect to 100 mass parts of the said cured resin components. When the amount of the acrylic resin copolymer is less than 130 parts by mass, the amount of cure shrinkage increases, and therefore, package cracks are likely to occur.

  The sheet-like adhesive 12 includes, as other components, polyimide resin, polyamide resin, polyetherimide resin, polyamideimide resin, polyester resin, polyester resin, polyesterimide resin, phenoxy resin, polysulfone resin, and polyethersulfone resin. Polyphenylene sulfide resin, polyether ketone resin, chlorinated polypropylene resin, acrylic resin, polyurethane resin, epoxy resin, polyacrylamide resin, melamine resin, and the like, and mixtures thereof can be used.

  Further, the sheet-like adhesive 12 may contain a filler. Examples of the filler include silica such as crystalline silica, fused silica, and synthetic silica, and inorganic filler such as alumina and glass balloon. By adding an inorganic filler to the curable protective film forming layer, the hardness of the cured adhesive can be improved. In addition, the thermal expansion coefficient of the adhesive after curing can be brought close to the thermal expansion coefficient of the semiconductor wafer, whereby the warpage of the semiconductor wafer can be reduced. Silica is preferable as the filler, and in particular, a type in which an α-ray source that causes malfunction of the semiconductor device is removed as much as possible is optimal. As the shape of the filler, any of a spherical shape, a needle shape, and an amorphous type can be used, but a spherical filler capable of closest packing is particularly preferable.

Since the sheet-like adhesive 12 includes a chelate-modified epoxy resin, it has a good adhesive force, and thus it is not necessary to use a coupling agent. However, if the amount of the coupling agent is small, it is less affected by deterioration due to water absorption and deterioration due to aging due to the bleed-out phenomenon of the sheet-like adhesive 12, so that further improvement of the adhesive strength when it does not deteriorate For this purpose, a small amount of a coupling agent can be added. In this case, the silane coupling agent is preferably 0.1 parts by mass or less with respect to 100 parts by mass of the cured resin component . A silane coupling agent is preferable as the coupling agent. As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β-aminoethyl-γ- Examples include aminopropyltrimethoxysilane.

As the varnishing solvent, it is preferable to use methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol or the like having a relatively low boiling point. Moreover, you may add a high boiling point solvent for the purpose of improving coating-film property. Examples of the high boiling point solvent include dimethylacetamide, dimethylformamide, methylpyrrolidone, cyclohexanone and the like.
The thickness of the sheet adhesive 12 may be set as appropriate, but is preferably about 5 to 100 μm.

  In order to increase the breaking strength of the sheet-like adhesive 12, it is effective to increase the polymer, decrease the filler, and decrease the epoxy resin (solid). In order to reduce the peeling force of the sheet-like adhesive 12 from the release film 11, it is effective to reduce the amount of polymer and the amount of epoxy resin (liquid).

(Adhesive film)
The adhesive film 13 is not particularly limited, and has a sufficient adhesive force so that the semiconductor wafer does not peel off when the semiconductor wafer is diced. When the semiconductor chip is picked up after dicing, the sheet-like adhesive is easily used. Any material may be used as long as it exhibits a low adhesive strength so that it can be peeled off from the surface. For example, what provided the adhesive layer 13b on the base film 13a can be used conveniently.

The base film 13a of the adhesive film 13 can be used without particular limitation as long as it is a conventionally known one. However, when a radiation curable material is used as the adhesive layer 13b described later, It is preferable to use a material having permeability.
For example, as the material, polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic Α-olefin homopolymer or copolymer such as acid methyl copolymer, ethylene-acrylic acid copolymer, ionomer or a mixture thereof, polyurethane, styrene-ethylene-butene or pentene copolymer, polyamide-polyol Listed are thermoplastic elastomers such as copolymers, and mixtures thereof. Moreover, the base film 13a may be a mixture of two or more materials selected from these groups, or may be a single layer or a multilayer.
The thickness of the base film 13a is not particularly limited and may be set appropriately, but is preferably 50 to 200 μm.

The resin used for the pressure-sensitive adhesive layer 13b of the pressure-sensitive adhesive film 13 is not particularly limited, and known chlorinated polypropylene resins, acrylic resins, polyester resins, polyurethane resins, epoxy resins and the like used for pressure-sensitive adhesives can be used. Can be used.
It is preferable to prepare a pressure-sensitive adhesive by appropriately blending an acrylic pressure-sensitive adhesive, a radiation polymerizable compound, a photopolymerization initiator, a curing agent and the like into the resin of the pressure-sensitive adhesive layer 13b. The thickness of the pressure-sensitive adhesive layer 13b is not particularly limited and may be appropriately set, but is preferably 5 to 30 μm.

A radiation-polymerizable compound can be blended in the pressure-sensitive adhesive layer 13b and can be easily peeled off from the sheet adhesive 12 by radiation curing. As the radiation polymerizable compound, for example, a low molecular weight compound having at least two photopolymerizable carbon-carbon double bonds in a molecule that can be three-dimensionally reticulated by light irradiation is used.
Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6 hexanediol diacrylate Acrylate, polyethylene glycol diacrylate, oligoester acrylate, and the like are applicable.

In addition to the above acrylate compounds, urethane acrylate oligomers can also be used. The urethane acrylate oligomer includes a polyol compound such as a polyester type or a polyether type, and a polyvalent isocyanate compound (for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diene). A terminal isocyanate urethane prepolymer obtained by reacting isocyanate, 1,4-xylylene diisocyanate, diphenylmethane 4,4-diisocyanate, etc., with an acrylate or methacrylate having a hydroxyl group (for example, 2-hydroxyethyl) Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, etc.) Obtained by the reaction.
The pressure-sensitive adhesive layer 13b may be a mixture of two or more selected from the above resins.

  When using a photopolymerization initiator, for example, isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenyl Propane or the like can be used. The blending amount of these photopolymerization initiators is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the acrylic copolymer.

(Example)
Next, examples of the present invention will be described, but the present invention is not limited to these examples.

(Method for producing sheet adhesive)
Methyl ethyl ketone was added to the sheet-like adhesive compositions 1A to 1H having the composition shown in Table 1 below, and the mixture was stirred and mixed to prepare an adhesive varnish. The adhesive varnishes of the prepared sheet adhesive compositions 1A to 1H were coated on the release film 11 so that the thickness after drying was 20 μm, dried at 110 ° C. for 3 minutes, and each sheet adhesive Agent 12 was prepared. Next, the release film 11 was peeled from the sheet-like adhesive 12 to produce sheet-like adhesives in Examples 1 to 5 shown in Table 2 below and Comparative Examples 1 to 3 shown in Table 3 below.

  In Table 1, the unit of the blending ratio of each component is part by mass. Moreover, the epoxy resin (1) is EP-49-23 (trade name, manufactured by ADEKA Corporation, chelate-modified bisphenol F type epoxy resin, epoxy equivalent 175 g / eq), and the epoxy resin (2) is RE303S (Japan) Kayaku Co., Ltd. trade name, bisphenol F type epoxy resin, epoxy equivalent 165 g / eq). The phenol resin is Milex XLC-LL (trade name, manufactured by Mitsui Chemicals, hydroxyl equivalent 175 g / eq, water absorption 1.8%, heating weight reduction rate at 350 ° C. 4%). The curing accelerator is Curesol 2PZ (trade name, 2-phenylimidazole manufactured by Shikoku Kasei Co., Ltd.). The acrylic resin is SG-708-6 (trade name, manufactured by Nagase ChemteX Corporation, weight average molecular weight 700,000, glass transition temperature 6 ° C.). The silane coupling agent is Z-6044 (trade name, 3-glycidoxypropylmethylmethoxysilane, manufactured by Toray Dow Corning Co., Ltd.).

  About Examples 1-5 and Comparative Examples 1-3, evaluation of virgin material reliability, evaluation of deterioration material reliability, and evaluation of reliability after sheet-like adhesive deterioration were performed, respectively. Tables 2 and 3 show evaluation of virgin material reliability, evaluation of deteriorated material reliability, and evaluation of reliability after sheet adhesive deterioration.

<Virgin material reliability evaluation>
For the evaluation of the reliability of the virgin material, the sheet-like adhesives according to Examples 1 to 5 and the sheet-like adhesives according to Comparative Examples 1 to 3 produced according to the above-described method for producing a sheet-like adhesive using a virgin compound material. Using, a dummy element in which an aluminum wiring is formed on a silicon chip is die-bonded on an FR4 substrate plated with silver via a sheet-like adhesive, under conditions of 175 ° C., 70 kgf / cm 2 and a molding time of 120 seconds. Twenty 1.0 mm-thick BGA packages were molded and post-cured at 180 ° C. for 4 hours, and used as evaluation packages. The reliability of the virgin material is evaluated by immersing the obtained package in a solder bath adjusted to 260 ° C. for 10 seconds, and then using an ultrasonic survey device (Hyper, manufactured by Hitachi Construction Machinery Co., Ltd.). The presence or absence of package cracks was evaluated. The number of defective packages in Table 2 and Table 3 indicates the number of cracked packages in 20 evaluation packages, and the ratio of defective packages is the number of defective packages in 20 evaluation packages. The ratio (%) is shown.

<Evaluation of degraded material reliability>
Evaluation of reliability of deteriorated materials is based on Examples 1 to 5 manufactured according to the above-described method for manufacturing a sheet-like adhesive using a compounded material that has been processed for 168 hours in advance at 30 ° C. and 85% RH. Using the sheet-like adhesive and the sheet-like adhesives according to Comparative Examples 1 to 3, evaluation was performed in the same manner as the above-described evaluation of virgin material reliability.

<Evaluation of reliability after deterioration of sheet adhesive>
Evaluation of reliability after deterioration of sheet-like adhesive was carried out according to the above-described method for producing sheet-like adhesive using a virgin compound material, and sheets according to Examples 1 to 5 and Comparative Examples 1 to 3 Evaluation was performed in the same manner as the above-described evaluation of the virgin material reliability, using the sheet-like adhesive after being treated for 168 hours under the conditions of 30 ° C. and 85% RH.

As shown in Table 2, the package using the sheet-like adhesive according to Examples 1 to 5 uses a chelate-modified epoxy resin, and chelate modification with respect to 100% by mass of the cured resin component (epoxy resin and phenol resin). Since the blending ratio of the epoxy resin is 10% by mass or more , there is no package crack in any of the virgin material reliability evaluation, the deterioration material reliability evaluation, and the sheet-like adhesive deterioration evaluation. It became a result.

The package using the sheet-like adhesive according to Example 3 contains a silane coupling agent, but the blending ratio of the silane coupling agent to 100 parts by mass of the cured resin component is 0.1 parts by mass. In the evaluation of the reliability of the deteriorated material and the evaluation of the reliability after deterioration of the sheet adhesive, there was no influence due to the deterioration of the silane coupling agent, and a good result was obtained.

  As shown in Table 3, since the package using the sheet-like adhesive according to Comparative Example 1 does not use the chelate-modified epoxy resin, the adhesive force (adhesion force) of the sheet-like adhesive 12 is reduced, In the evaluation of the reliability of the virgin material, a crack was generated in 35% of the packages. Further, in the evaluation of the reliability of the deteriorated material and the evaluation of the reliability after deterioration of the sheet-like adhesive, cracks were generated in 35% package and 40% package, respectively. That is, since the package using the sheet-like adhesive according to Comparative Example 1 does not use the chelate-modified epoxy resin, the adhesive force (adhesion force) of the sheet-like adhesive 12 is reduced, and the virgin material reliability is reduced. The result was inferior to the reliability of the deteriorated material and the reliability after deterioration of the sheet adhesive.

  The package using the sheet-like adhesive according to Comparative Example 2 uses a chelate-modified epoxy resin, but 5 outside the above range of 10% by mass or more that defines the chelate-modified epoxy resin component in the cured resin component. Since it was mass%, the adhesive force (adhesion force) of the sheet-like adhesive 12 was lowered, and in the evaluation of the virgin material reliability, 30% of the packages were cracked. Also, in the evaluation of the reliability of the deteriorated material and the evaluation of the reliability after deterioration of the sheet-like adhesive, cracks were generated in the 25% package and the 30% package, respectively. That is, the package using the sheet-like adhesive according to Comparative Example 2 uses a chelate-modified epoxy resin, but is outside the above range of 10% by mass or more that defines the chelate-modified epoxy resin component in the cured resin component. Therefore, the adhesive strength (adhesive strength) of the sheet-like adhesive 12 is lowered, resulting in inferior virgin material reliability, deteriorated material reliability, and reliability after deterioration of the sheet-like adhesive. . In addition, since chelate-modified epoxy resin is used, deterioration of the compounded material due to the storage time of the compounded material and deterioration of the sheeted adhesive due to bleed-out due to the storage time of the produced sheet-like adhesive Therefore, the reliability of the deteriorated material and the reliability after deterioration of the sheet adhesive did not decrease compared to the reliability of the virgin material.

  The package using the sheet-like adhesive according to Comparative Example 3 uses a chelate-modified epoxy resin, but since the blending ratio of the silane coupling agent is large and 0.3 parts by mass, the virgin material reliability is improved. In the evaluation, no package crack occurred. However, the adhesive strength (adhesive force) of the sheet-like adhesive 12 is reduced due to material deterioration and bleed-out of the silane coupling agent, and in the evaluation of the deterioration material reliability and the reliability after deterioration of the sheet-like adhesive, Cracks occurred in 30% package and 20% package, resulting in inferior degradation material reliability and reliability after sheet adhesive degradation.

  In addition, the mixing ratio of the acrylic resin copolymer of Example 1 was set to 280 parts by weight and 120 parts by weight, respectively, and a sheet-like adhesive was prepared in the same manner as in Example 1, and evaluation and deterioration of virgin material reliability were performed. Evaluation of material reliability and reliability after sheet-like adhesive deterioration were performed. When the blending ratio of the acrylic resin copolymer is as large as 280 parts by weight, the adhesive strength is lowered, and therefore the number of defective packages is one in the evaluation of the virgin material reliability. In addition, when the blending ratio of the acrylic resin copolymer is as small as 120 parts by weight, the amount of cure shrinkage increases, and therefore the number of defective packages was two in the evaluation of the virgin material reliability. However, in both cases, since a predetermined amount of chelate-modified epoxy is used instead of the silane coupling agent, there has been no increase in defective packages due to aging due to material deterioration or deterioration of the sheet-like adhesive.

  From the results shown in Tables 2 and 3, the adhesive strength of the sheet-like adhesive 12 can be improved by including 10 mass% or more of the chelate-modified epoxy resin in the cured resin component. Moreover, even if the adhesive film 20 is produced using the compounded material (sheet adhesive composition) of the sheet adhesive 12 stored in a harsh environment, the adhesive strength of the sheet adhesive 12 is reduced. And storage of the compounded material is easy. Moreover, even after the produced adhesive film 20 is stored in a harsh environment, the adhesive strength of the sheet-like adhesive 12 does not decrease, and the produced adhesive film 20 can be easily stored. That is, the adhesive strength of the sheet-like adhesive 12 is excellent, the compounded material can be easily stored, and the adhesive film 20 with high production efficiency can be produced. The produced adhesive film 20 can be easily stored. In addition, since the wafer processing tape 10 is produced using the adhesive film 20 according to the above-described embodiment, the production efficiency is excellent in the adhesive strength of the sheet-like adhesive 12 and easy storage of the compounded material. The wafer processing tape 10 having a high height can be produced, and the produced wafer processing tape 10 can be easily stored.

10: Wafer processing tape 11: Release film 12: Sheet adhesive 13: Adhesive film 13a: Base film 13b: Adhesive layer 20: Adhesive film

Claims (2)

As a cured resin component, including a cured resin that cures with heat and high energy rays and an epoxy curing agent that cures the epoxy,
Part or all of the cured resin is a chelate-modified epoxy resin,
Wherein the chelating modified epoxy resin is seen containing more than 10 wt% the cured resin component,
Including 100 to 270 parts by mass of acrylic resin copolymer with respect to 100 parts by mass of the cured resin component,
If it contains a coupling agent, the sheet-like adhesive for wafer processing or die bonding process, wherein said coupling agent 0.1 parts by weight or less free Mukoto to the curable resin component 100 parts by mass. The sheet-like adhesive for wafer processing or die bonding process according to claim 1 is laminated on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film on the pressure-sensitive adhesive film in which the pressure-sensitive adhesive layer is laminated on the base film. Wafer processing tape characterized by being made .

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