WO2020100434A1 - Adhesive tape and method for producing semiconductor package - Google Patents

Adhesive tape and method for producing semiconductor package Download PDF

Info

Publication number
WO2020100434A1
WO2020100434A1 PCT/JP2019/037160 JP2019037160W WO2020100434A1 WO 2020100434 A1 WO2020100434 A1 WO 2020100434A1 JP 2019037160 W JP2019037160 W JP 2019037160W WO 2020100434 A1 WO2020100434 A1 WO 2020100434A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive tape
adhesive layer
lead frame
semiconductor package
linking agent
Prior art date
Application number
PCT/JP2019/037160
Other languages
French (fr)
Japanese (ja)
Inventor
憲明 阿部
佐藤　信之
透 太刀川
Original Assignee
株式会社有沢製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社有沢製作所 filed Critical 株式会社有沢製作所
Priority to JP2020556665A priority Critical patent/JP7168681B2/en
Publication of WO2020100434A1 publication Critical patent/WO2020100434A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings

Definitions

  • the present invention relates to an adhesive tape for use in a semiconductor package manufacturing method, and a semiconductor package manufacturing method.
  • Patent Document 1 discloses “a base material layer made of a polyimide material and an adhesive having a storage elastic modulus at 200 ° C. of 1.0 ⁇ 10 5 Pa or more and an acrylic material having a thickness of 1 to 20 ⁇ m.
  • a heat-resistant adhesive tape characterized in that it is composed of at least a layer and is attached to the back surface of the lead frame.
  • Patent Document 2 discloses an "adhesive tape comprising a base material layer and an adhesive layer laminated on the base material layer, wherein the adhesive layer contains (meth) acrylic acid and It is formed by a pressure-sensitive adhesive containing a polymer containing a structural unit derived from a monomer component other than (meth) acrylic acid and an epoxy crosslinking agent, and the (meth) acrylic acid is based on 100 parts by weight of the monomer component.
  • Non-Patent Document 1 describes the effect of plasma on acrylic resins. Specifically, it is described that the bond is selectively cleaved at a site adjacent to the benzene ring contained in the acrylic resin by exposure to plasma.
  • Patent Document 2 describes that the plasma resistance of the adhesive tape is improved by increasing the degree of crosslinking of the polymer contained in the adhesive layer. However, if the degree of crosslinking of the polymer is increased, it becomes difficult to secure the adhesive force of the adhesive tape under high temperature conditions necessary to prevent mold flash.
  • the present invention provides an adhesive tape that can be peeled off cleanly from a lead frame without leaving a part of the adhesive layer and can prevent mold flash, and a method of manufacturing a semiconductor package using the same.
  • the purpose is to
  • the present invention includes the following embodiments.
  • the adhesive layer contains a non-aromatic acrylic polymer cross-linked by a metal chelate cross-linking agent, Adhesive tape for use in a method of manufacturing a semiconductor package.
  • Adhesive tape for use in a method of manufacturing a semiconductor package.
  • the metal chelate crosslinking agent is an aluminum chelate crosslinking agent.
  • a pressure-sensitive adhesive tape for use in a method for manufacturing a semiconductor package comprising a base material and an adhesive layer arranged on the base material,
  • the following formula: [(AB) / A] x 100 (In the formula, A is the contact angle of water with respect to the adhesive layer before plasma treatment, B is the contact angle of water with respect to the adhesive layer after plasma treatment) And the change rate (%) of the contact angle of water with respect to the adhesive layer before and after the plasma treatment is 10% or less,
  • the pressure-sensitive adhesive tape, wherein the peeling force of the pressure-sensitive adhesive tape from the copper foil is 100 mN / 25 mm or more at 150 ° C.
  • a method for manufacturing a semiconductor package comprising:
  • the adhesive tape which can be peeled off from a lead frame neatly, without leaving a part of adhesive layer, and can prevent mold flash, and the manufacturing method of a semiconductor package using this. Can be provided.
  • the first embodiment of the present invention comprises a non-aromatic acrylic polymer comprising a substrate and an adhesive layer disposed on the substrate, wherein the adhesive layer is cross-linked by a metal chelate cross-linking agent.
  • An adhesive tape for use in a method of manufacturing a semiconductor package including: Specifically, the adhesive tape is used to prevent mold flash.
  • a non-aromatic acrylic polymer and a metal chelate cross-linking agent By using a non-aromatic acrylic polymer and a metal chelate cross-linking agent, excellent plasma resistance and high adhesion under high temperature conditions can be obtained. As a result, the adhesive tape can be cleanly peeled from the lead frame without leaving a part of the adhesive layer, and mold flash can be prevented.
  • the base material in the present embodiment is not particularly limited as long as it is a heat resistant base material that can withstand the temperature conditions in the manufacturing process of the semiconductor package.
  • the heat resistant substrate is preferably a substrate that can withstand a temperature of 150 ° C., 170 ° C., 200 ° C., 250 ° C., or 300 ° C., for example.
  • Specific examples of the base material include polyimide, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyetherimide, polysulfone, polyphenylene sulfide, polyether ether ketone, polyarylate, and aramid.
  • the thickness of the substrate is not particularly limited, but may be, for example, 5 to 50 ⁇ m, 10 to 40 ⁇ m, 20 to 30 ⁇ m, or the like.
  • the adhesive layer in the present embodiment contains a non-aromatic acrylic polymer cross-linked by a metal chelate cross-linking agent.
  • a non-aromatic acrylic polymer cross-linked by a metal chelate cross-linking agent.
  • plasma resistance is improved.
  • the present inventors presume as follows.
  • the adhesive layer contains an aromatic acrylic polymer
  • the plasma treatment intensively cuts the bonds around the aromatic ring.
  • the degree of modification of the surface of the adhesive layer becomes strong, and the plasma resistance is significantly reduced.
  • the adhesive layer in the present embodiment contains the non-aromatic acrylic polymer, the above-mentioned intensive cutting does not occur even if the plasma treatment is performed.
  • the degree of modification of the surface of the adhesive layer due to the plasma treatment is weakened, and good plasma resistance can be secured.
  • the non-aromatic acrylic polymer cross-linked by the metal chelate cross-linking agent may be only one kind or a combination of two or more kinds. When two or more kinds are combined, at least one kind of non-aromatic acrylic polymer must contain 1 to 20% by weight of a structural unit derived from acrylic acid, based on the total amount of the non-aromatic acrylic polymer. Is preferred. Since a polymer usually has a molecular weight distribution, a combination of a plurality of polymer molecules constituting the molecular weight distribution is regarded as one type.
  • the metal chelate crosslinking agent may be only one kind or a combination of two or more kinds.
  • the adhesive layer may contain further components as long as the effects of the present invention are not impaired. Further components include, for example, plasticizers, pigments, dyes, antistatic agents, fillers and the like.
  • the thickness of the adhesive layer after drying is preferably 2 to 12 ⁇ m, more preferably 4 to 10 ⁇ m, and further preferably 6 to 8 ⁇ m.
  • the non-aromatic acrylic polymer in the present embodiment means a polymer having a structural unit (hereinafter referred to as “acrylic unit”) derived from (meth) acrylic acid and / or a derivative thereof and having no aromatic ring.
  • (meth) acrylic acid means acrylic acid and / or methacrylic acid.
  • examples of the (meth) acrylic acid derivative include (meth) acrylic acid ester.
  • Specific derivatives of (meth) acrylic acid include, for example, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid.
  • the non-aromatic acrylic polymer needs to have a functional group for bonding with the metal chelate crosslinking agent.
  • the functional group is preferably a carboxyl group.
  • the constituent unit having a functional group is preferably contained in an amount of 1 to 20% by weight based on the total amount of the non-aromatic acrylic polymer.
  • the non-aromatic acrylic polymer may have an additional structural unit in addition to the acrylic unit.
  • the further structural unit include structural units derived from acrylonitrile, vinyl acetate, vinyl chloride, butadiene, isoprene and the like.
  • the amount of acrylic units constituting the non-aromatic acrylic polymer is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight based on the non-aromatic acrylic polymer. It is more than weight%.
  • the upper limit of the amount of acrylic units is not particularly limited, but may be, for example, 100% by weight or 95% by weight.
  • the weight average molecular weight of the non-aromatic acrylic polymer is preferably 300,000 to 1,500,000, and more preferably 500,000 to 1,000,000, from the viewpoint of achieving both workability and adhesive residue.
  • the amount of the non-aromatic acrylic polymer is preferably 85 to 99% by weight, more preferably 90 to 98% by weight, further preferably 93 to 97% by weight, based on the adhesive layer. :
  • the metal chelate cross-linking agent in this embodiment means a cross-linking agent having a metal ion and a ligand. Since the metal chelate cross-linking agent is an ionic bond-forming cross-linking agent, it has a lower elastic modulus at 175 ° C. than the covalent-bonding cross-linking agent. As a result, the adhesive layer has a high adhesive force under high temperature conditions, and mold flash can be effectively suppressed. Further, the metal chelate crosslinking agent preferably has a ligand having a boiling point of 200 ° C. or lower.
  • the ligand is volatilized by drying, and the metal chelate crosslinking agent can irreversibly crosslink with the non-aromatic acrylic polymer.
  • the lower limit of the boiling point of the ligand is not particularly limited, but may be, for example, 60 ° C, 70 ° C, 80 ° C or the like.
  • metal chelate cross-linking agent having a ligand having a boiling point of 200 ° C. or less examples include an aluminum chelate cross-linking agent, a titanium chelate cross-linking agent, a zirconium chelate cross-linking agent, and the like.
  • Examples of the aluminum chelate cross-linking agent include aluminum tris (acetylacetonate), aluminum bisethylacetoacetate monoacetylacetonate, and aluminum tris (ethylacetoacetate).
  • Examples of the titanium chelate cross-linking agent include titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis (ethylacetoacetate), titanium di-2-ethylhexoxybis (2-ethyl). -3-hydroxyhexoxide), titanium lactate ammonium salt, titanium lactate, titanium diisopropoxybis (triethanolaminate), titanium aminoethylaminoethanolate, and the like.
  • zirconium chelate cross-linking agent examples include zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium dibutoxybis (ethylacetoacetate), zirconium lactate ammonium salt and the like.
  • the metal chelate cross-linking agent is preferably an aluminum chelate cross-linking agent, and more preferably aluminum tris (acetylacetonate).
  • the amount of the metal chelate cross-linking agent is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, further preferably 3 to 7% by weight, based on the adhesive layer.
  • the adhesive tape according to the present embodiment may include a release film on the adhesive layer.
  • the adhesive tape according to this embodiment can be manufactured by a known method. For example, a step of mixing a non-aromatic acrylic polymer, a metal chelate crosslinking agent, and a solvent (mixing step), a step of applying the mixture to a substrate (application step), a step of drying the applied mixture (drying step) ),
  • the adhesive tape can be manufactured by the method including.
  • Examples of the solvent used in the mixing step include a ketone solvent (acetylacetone, methylethylketone, acetone, etc.), an alcohol solvent (methanol, ethanol, propanol, butanol, etc.), an ether solvent (tetrahydrofuran, etc.), a nitrile solvent (acetonitrile, etc.), an amide. Solvents (N, N-dimethylformamide etc.) and the like can be mentioned.
  • Examples of the coating method in the coating step include die coater coating, bar coater coating, air knife coater coating, gravure coater coating, reverse roll coater coating, lip coater coating and the like.
  • the adhesive tape according to this embodiment may further have the features of the adhesive tape according to the following second embodiment.
  • a second embodiment of the present invention is an adhesive tape for use in a method for manufacturing a semiconductor package, which comprises a base material and an adhesive layer disposed on the base material, and has the following formula: [(AB) / A] x 100 (In the formula, A is a contact angle of water with respect to the adhesive layer before plasma treatment, B is the contact angle of water with respect to the adhesive layer after plasma treatment) And the change rate (%) of the contact angle of water with respect to the adhesive layer before and after the plasma treatment is 10% or less,
  • the adhesive tape has a peeling force of 100 mN / 25 mm or more at 150 ° C. from the copper foil. Specifically, the adhesive tape is used to prevent mold flash.
  • the contact angle of water to the adhesive layer is reduced by the plasma treatment, the adhesive strength of the adhesive layer increases and it becomes impossible to cleanly remove the adhesive tape from the lead frame.
  • the change rate (%) of the contact angle of water before and after the plasma treatment is 10% or less, an increase in the adhesive force can be suppressed and the adhesive tape can be peeled off neatly at room temperature. Further, by setting the peeling force of the adhesive tape to 100 mN / 25 mm or more at 150 ° C., mold flash can be prevented.
  • the rate of change (%) in the contact angle of water with respect to the adhesive layer before and after plasma treatment is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.
  • the lower limit of the rate of change (%) is not particularly limited, but may be 0%, 1% or the like, for example.
  • the contact angle before and after the plasma treatment can be measured by the method described in the examples below, and the rate of change can be calculated based on the measured contact angle.
  • the peeling force of the adhesive tape at 25 ° C can be measured by the method described in the following examples.
  • the lower limit of the peeling force of the adhesive tape at 25 ° C. is not particularly limited, but may be 100 mN / 25 mm, 200 mN / 25 mm or the like, for example.
  • 100 mN / 25 mm or more is preferable, and 150 mN / 25 mm or more is more preferable.
  • the peeling force of the adhesive tape at 150 ° C can be measured by the method described in the following examples.
  • the upper limit of the peeling force of the adhesive tape at 150 ° C. is not particularly limited, but may be, for example, 500 mN / 25 mm, 1000 mN / 25 mm or the like.
  • the elastic modulus of the adhesive tape is 175 ° C., preferably 5 ⁇ 10 5 to 20 ⁇ 10 5 in order to secure mold flash resistance and to sufficiently connect the semiconductor chip and the surface of the lead frame with a bonding wire. Pa, more preferably 5 ⁇ 10 5 to 10 ⁇ 10 5 Pa.
  • the elastic modulus of the adhesive tape can be measured by the method described in the examples below.
  • the adhesive tape according to this embodiment may further have the features of the adhesive tape according to the first embodiment.
  • the third embodiment of the present invention relates to a method of manufacturing a semiconductor package including a sticking step, a fixing step, a plasma processing step, a connecting step, a sealing step, and a peeling step.
  • a sticking step a sticking step
  • a fixing step a fixing step
  • a plasma processing step a plasma processing step
  • a connecting step a sealing step
  • a peeling step a peeling step
  • the sticking step in this embodiment is a step of sticking the adhesive tape according to the first embodiment or the second embodiment to the back surface of the lead frame.
  • the attaching step can be performed by a known method.
  • the fixing step in this embodiment is a step of fixing the semiconductor chip to the die pad on the surface of the lead frame to which the adhesive tape is attached.
  • the fixing step can be performed by a known method.
  • the plasma treatment step in this embodiment is a step of treating the semiconductor chip and the surface of the lead frame with plasma.
  • the plasma treatment step can be performed by a known method.
  • plasma treatment can be performed under an atmosphere of an inert gas (argon, nitrogen, etc.) under the conditions of 50 to 300 W (preferably 100 to 150 W) and 5 to 60 seconds (preferably 10 to 30 seconds). .
  • an inert gas argon, nitrogen, etc.
  • connection step in this embodiment is a step of connecting the semiconductor chip, which has been treated with plasma, and the surface of the lead frame with a bonding wire.
  • the connecting step can be performed by a known method.
  • the sealing step in this embodiment is a step of sealing the bonding wire, the semiconductor chip, and the surface of the lead frame with resin.
  • the sealing step can be performed by a known method.
  • the sealing step can be performed at 110 to 200 ° C, preferably 130 to 180 ° C.
  • the peeling step in this embodiment is a step of peeling the adhesive tape from the back surface of the lead frame whose surface is sealed with resin.
  • the peeling step can be performed by a known method.
  • the manufacturing method When the lead frame has a plurality of die pads on the surface, and a plurality of semiconductor chips are fixed to the plurality of die pads, the manufacturing method according to the present embodiment, the adhesive tape is peeled off, the surface is sealed with resin. The method may further include a cutting step of cutting the formed lead frame into individual semiconductor packages.
  • ⁇ Polymer> The following polymers were used in the Examples and Comparative Examples.
  • Acrylic polymer A In a reaction vessel, butyl acrylate (BA) (92 parts by weight), acrylic acid (AA) (8 parts by weight), ethyl acetate (100 parts by weight), and azobisisobutyronitrile (AIBN) (0.3 parts by weight). Part) and stirred at 70 ° C. After 60 minutes from the start of the reaction, a part of the reaction solution was taken out every 30 minutes, the reaction was stopped with deionized water, the mixture was extracted with methyl ethyl ketone, and the extracted solution was analyzed by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the reaction vessel was cooled to stop the reaction when the weight average molecular weight of the reaction product reached 700,000 or more.
  • the resulting mixture was washed with deionized water and dried to obtain an acrylic polymer A.
  • the weight average molecular weight of the acrylic polymer A was 750,000, and the acid value as determined by titration with an aqueous potassium hydroxide solution was 810 mgKOH / g.
  • the reaction vessel was cooled to stop the reaction when the weight average molecular weight of the reaction product reached 500,000 or more.
  • the resulting mixture was washed with deionized water and dried to obtain an acrylic polymer B.
  • the weight average molecular weight of the acrylic polymer B was 540,000.
  • the reaction vessel was cooled and the reaction was stopped when the weight average molecular weight of the reaction product reached 100,000 or more.
  • the resulting mixture was washed with deionized water and dried to obtain an acrylic polymer C.
  • the weight average molecular weight of the acrylic polymer C was 120,000, and the acid value by titration with an aqueous potassium hydroxide solution was 670 mgKOH / g.
  • ⁇ Crosslinking agent> The following cross-linking agents were used in the examples and comparative examples.
  • Aluminum chelate cross-linking agent [aluminum tris (acetylacetonate), trade name: Organix AL-3100 (manufactured by Matsumoto Fine Chemical Co., Ltd.)]
  • Titanium chelate cross-linking agent [titanium diisopropoxybis (acetylacetonate), trade name: Organix TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.)]
  • Zirconium chelate crosslinking agent [zirconium tetraacetylacetonate, trade name: Organix ZC-700 (manufactured by Matsumoto Fine Chemical Co., Ltd.)]
  • Phenol novolac type epoxy resin cross-linking agent [trade name: EPICLON N730A (manufactured by DIC Corporation)]
  • Alicyclic epoxy resin crosslinking agent A [trade name
  • Example 1 ⁇ Production of adhesive tape> Acrylic polymer A (100 parts by weight), aluminum chelate crosslinking agent (4 parts by weight), acetylacetone (10 parts by weight), and methyl ethyl ketone (60 parts by weight) were stirred at room temperature to obtain a composition 1.
  • the composition 1 was applied to a polyimide film (thickness: 25 ⁇ m) using a die coater so that the thickness after drying was 7 ⁇ m, and dried at 150 ° C. for 5 minutes to obtain an adhesive tape.
  • the release surface of the release film that had been subjected to the release treatment was attached to the adhesive layer of the adhesive tape by laminating and heated at 105 ° C. for 24 hours to obtain an adhesive tape with a release film.
  • the pressure-sensitive adhesive tape with a release film was divided into two, a first pressure-sensitive adhesive tape and a second pressure-sensitive adhesive tape, the release film was removed, and the charge was sufficiently removed.
  • Plasma treatment was performed only on the second adhesive tape under an argon atmosphere (flow rate of 50 cc) and 120 W for 20 seconds.
  • the first adhesive tape and the second adhesive tape were fixed to a pedestal of a contact angle meter [Product name: CA-X (manufactured by Kyowa Interface Science Co., Ltd.)] with the adhesive layer facing up in an atmosphere of 23 ° C.
  • the contact angle when pure water was dropped on was measured. The measurement was performed 10 times, and the average value was calculated.
  • Rate of change of contact angle of water [(contact angle of water on first adhesive tape-contact angle of water on second adhesive tape after plasma treatment) / contact angle of water on first adhesive tape] ⁇ 100
  • the adhesive tape was roll-laminated (30 ° C., 0.4 MPa, 1 m / min) on the glossy side of the rolled copper foil (thickness 35 ⁇ m), and then a 25 mm width test piece was prepared.
  • the peel strength was evaluated according to the following criteria. The results are shown in Table 1.
  • Peeling force is less than 500 mN / 25 mm ⁇ : Peeling force is 500 mN / 25 mm or more and less than 1200 mN / 25 mm ⁇ : Peeling force is 1200 mN / 25 mm or more and less than 1300 mN / 25 mm ⁇ : Peeling force is 1300 mN / 25 mm or more
  • Peeling force is 150 mN / 25 mm or more
  • Peeling force is 100 mN / 25 mm or more, less than 150 mN / 25 mm
  • Peeling force is 50 mN / 25 mm or more, less than 100 mN / 25 mm
  • Peeling force is less than 50 mN / 25 mm
  • the pressure-sensitive adhesive composition is applied to a release film so as to have a thickness after drying of 100 ⁇ m, dried and then heated at 105 ° C. for 24 hours to remove the release film.
  • Got The storage elastic modulus (E ′) of 23 ° C. to 200 ° C. of the obtained single film was measured at a temperature rising rate of 10 ° C./min and 1 Hz with a dynamic mechanical analysis (DMA) device. .. Among these, the value at 175 ° C. was evaluated according to the following criteria. The results are shown in Table 1.
  • Storage elastic modulus at 175 ° C. is 5 ⁇ 10 5 Pa or more and less than 10 ⁇ 10 5 Pa ⁇ : Storage elastic modulus at 175 ° C. is 10 ⁇ 10 5 Pa or more and less than 20 ⁇ 10 5 Pa ⁇ : Storage elastic modulus at 175 ° C. Is 20 ⁇ 10 5 Pa or more and less than 30 ⁇ 10 5 Pa ⁇ : Storage elastic modulus at 175 ° C. is 30 ⁇ 10 5 Pa or more
  • Examples 2 to 4 and Comparative Examples 1 to 7 A pressure-sensitive adhesive tape with a release film was produced in the same manner as in Example 1 using the polymers and cross-linking agents shown in Tables 1 and 2, and the rate of change in water contact angle was calculated. Moreover, the peeling force and the elastic modulus were measured. The results are shown in Tables 1 and 2.
  • the adhesive tapes of Examples 1 to 4 have plasma resistance, and therefore can be peeled off cleanly from the lead frame without leaving a part of the adhesive layer. Moreover, since the adhesive tapes of Examples 1 to 4 have excellent adhesive strength under high temperature conditions, mold flash can be suppressed.

Abstract

The present invention addresses the problem of providing an adhesive tape that can be detached cleanly from a lead frame without leaving behind a portion of an adhesive layer and that can prevent mold flash, and a method for producing a semiconductor package in which the adhesive tape is used. This problem can be solved by an adhesive tape for use in a method for producing a semiconductor package, the adhesive tape including a substrate and an adhesive layer disposed on the substrate, and the adhesive layer including a non-aromatic acrylic polymer cross-linked by a metal chelate cross-linking agent.

Description

粘着テープ、及び半導体パッケージの製造方法Adhesive tape and method for manufacturing semiconductor package
　本発明は、半導体パッケージの製造方法において使用するための粘着テープ、及び半導体パッケージの製造方法に関する。 The present invention relates to an adhesive tape for use in a semiconductor package manufacturing method, and a semiconductor package manufacturing method.
　ＱＦＮ（Ｑｕａｄ　Ｆｌａｔ　Ｎｏ　Ｌｅａｄ）、ＳＯＮ（Ｓｍａｌｌ　Ｏｕｔｌｉｎｅ　Ｎｏ　Ｌｅａｄ）等の半導体パッケージは、半導体チップが固定されたリードフレームの表面を樹脂で封止することによって製造されている。しかしながら、封止の際に、樹脂が、リードフレームの開口部を通って裏面に漏れ出て、半導体パッケージの端子を被覆するという問題（いわゆる、モールドフラッシュ）が生じることがある。この問題に対し、特許文献１は、「ポリイミド材料からなる基材層と、２００℃における貯蔵弾性率が１．０×１０５Ｐａ以上であるアクリル系材料からなる厚さ１～２０μｍの粘着剤層とから少なくとも構成されていることを特徴とする耐熱性粘着テープ」をリードフレームの裏面に貼り付ける方法を記載している。 Semiconductor packages such as QFN (Quad Flat No Lead) and SON (Small Outline No Lead) are manufactured by sealing the surface of a lead frame to which a semiconductor chip is fixed with resin. However, during sealing, the resin may leak to the back surface through the opening of the lead frame and cover the terminals of the semiconductor package (so-called mold flash). In order to solve this problem, Patent Document 1 discloses “a base material layer made of a polyimide material and an adhesive having a storage elastic modulus at 200 ° C. of 1.0 × 10 5 Pa or more and an acrylic material having a thickness of 1 to 20 μm. A heat-resistant adhesive tape characterized in that it is composed of at least a layer and is attached to the back surface of the lead frame.
　しかしながら、粘着テープは、半導体パッケージの製造過程において実施されるプラズマ処理によって変性し、リードフレームから完全に剥離できず、その一部が残存してしまうという問題が生じることがある。この問題に対し、特許文献２は、「基材層と該基材層上に積層された粘着剤層とを備えた粘着テープであって、前記粘着剤層は、（メタ）アクリル酸と該（メタ）アクリル酸以外のモノマー成分とに由来する構造単位を含むポリマー及びエポキシ系架橋剤を含む粘着剤によって形成されており、前記（メタ）アクリル酸は、前記モノマー成分１００重量部に対して５重量部以上含有され、前記エポキシ系架橋剤は、前記（メタ）アクリル酸に対して０．４当量以上に対応する重量部数で含有されていることを特徴とする樹脂封止型半導体装置の製造における樹脂封止用耐熱性粘着テープ」を使用することを記載している。 However, the adhesive tape may be modified by the plasma treatment carried out in the manufacturing process of the semiconductor package, may not be completely peeled off from the lead frame, and a part of it may remain. In order to solve this problem, Patent Document 2 discloses an "adhesive tape comprising a base material layer and an adhesive layer laminated on the base material layer, wherein the adhesive layer contains (meth) acrylic acid and It is formed by a pressure-sensitive adhesive containing a polymer containing a structural unit derived from a monomer component other than (meth) acrylic acid and an epoxy crosslinking agent, and the (meth) acrylic acid is based on 100 parts by weight of the monomer component. 5 parts by weight or more, and the epoxy-based cross-linking agent is contained in a number of parts by weight corresponding to 0.4 equivalent or more with respect to the (meth) acrylic acid. The use of "heat resistant adhesive tape for resin encapsulation in production" is described.
　なお、非特許文献１は、プラズマが与えるアクリル系樹脂への影響について記載している。具体的には、プラズマへの暴露によって、アクリル系樹脂に含まれるベンゼン環に隣接する部位で選択的に結合が開裂することが記載されている。 Note that Non-Patent Document 1 describes the effect of plasma on acrylic resins. Specifically, it is described that the bond is selectively cleaved at a site adjacent to the benzene ring contained in the acrylic resin by exposure to plasma.
特開２００４－０１４９３０号公報JP, 2004-014930, A 特開２０１１－１２４４９５号公報JP, 2011-124495, A
　特許文献２には、粘着剤層に含まれるポリマーの架橋度を高めることによって、粘着テープのプラズマ耐性が向上することが記載されている。しかしながら、ポリマーの架橋度を高めると、モールドフラッシュを防止するために必要な、高温条件下における粘着テープの粘着力を確保することが困難になるとの問題が生じる。 Patent Document 2 describes that the plasma resistance of the adhesive tape is improved by increasing the degree of crosslinking of the polymer contained in the adhesive layer. However, if the degree of crosslinking of the polymer is increased, it becomes difficult to secure the adhesive force of the adhesive tape under high temperature conditions necessary to prevent mold flash.
　本発明は、粘着層の一部を残すことなく、リードフレームからきれいに剥離することができ、かつ、モールドフラッシュを防止することができる粘着テープ、及びこれを用いた半導体パッケージの製造方法を提供することを目的とする。 The present invention provides an adhesive tape that can be peeled off cleanly from a lead frame without leaving a part of the adhesive layer and can prevent mold flash, and a method of manufacturing a semiconductor package using the same. The purpose is to
　本発明者等が鋭意検討した結果、非芳香族アクリル系重合体及び金属キレート架橋剤を使用して、粘着テープの粘着層を形成することにより、優れたプラズマ耐性が得られること、及び高温条件下において高い粘着力が得られることを見出した。優れたプラズマ耐性を有することによって、プラズマ処理による粘着層の変性が抑制され、常温条件下において、粘着テープをリードフレームからきれいに剥離することができる。また、高温条件下において高い粘着力を有することによって、モールドフラッシュを防止することができる。 As a result of diligent studies by the present inventors, by using a non-aromatic acrylic polymer and a metal chelate cross-linking agent to form an adhesive layer of an adhesive tape, excellent plasma resistance can be obtained, and high temperature conditions It was found that a high adhesive strength can be obtained below. Due to having excellent plasma resistance, modification of the adhesive layer due to plasma treatment is suppressed, and the adhesive tape can be neatly peeled from the lead frame under normal temperature conditions. Further, by having a high adhesive force under high temperature conditions, mold flash can be prevented.
　本発明は以下の実施形態を含む。
［１］
　基材と、前記基材上に配置された粘着層と、を含み、
　前記粘着層が、金属キレート架橋剤によって架橋されている非芳香族アクリル系重合体を含む、
　半導体パッケージの製造方法において使用するための粘着テープ。
［２］
　前記金属キレート架橋剤が、２００℃以下の沸点を有する配位子を含む、［１］に記載の粘着テープ。
［３］
　前記金属キレート架橋剤が、アルミニウムキレート架橋剤である、［１］又は［２］に記載の粘着テープ。
［４］
　基材と、前記基材上に配置された粘着層と、を含む、半導体パッケージの製造方法において使用するための粘着テープであって、
　下記式：
［（Ａ－Ｂ）／Ａ］×１００
（式中、
　Ａは、プラズマ処理前の前記粘着層に対する水の接触角であり、
　Ｂは、プラズマ処理後の前記粘着層に対する水の接触角である）
で表される、プラズマ処理の前後における前記粘着層に対する水の接触角の変化率（％）が１０％以下であり、
　銅箔からの前記粘着テープの剥離力が、１５０℃で１００ｍＮ／２５ｍｍ以上である、前記粘着テープ。
［５］
　リードフレームの裏面に、［１］～［４］のいずれかに記載の粘着テープを貼り付ける貼付工程；
　前記粘着テープが貼り付けられたリードフレームの表面のダイパッドに半導体チップを固定する固定工程；
　前記半導体チップと前記リードフレームの表面とをプラズマで処理するプラズマ処理工程；
　プラズマで処理された、前記半導体チップと前記リードフレームの表面とをボンディングワイヤーで接続する接続工程；
　前記ボンディングワイヤーと前記半導体チップと前記リードフレームの表面とを樹脂で封止する封止工程；及び
　前記樹脂で表面が封止されたリードフレームの裏面から前記粘着テープを剥離する剥離工程；
を含む、半導体パッケージの製造方法。 The present invention includes the following embodiments.
[1]
A substrate and an adhesive layer arranged on the substrate,
The adhesive layer contains a non-aromatic acrylic polymer cross-linked by a metal chelate cross-linking agent,
Adhesive tape for use in a method of manufacturing a semiconductor package.
[2]
The pressure-sensitive adhesive tape according to [1], wherein the metal chelate crosslinking agent contains a ligand having a boiling point of 200 ° C. or lower.
[3]
The pressure-sensitive adhesive tape according to [1] or [2], wherein the metal chelate crosslinking agent is an aluminum chelate crosslinking agent.
[4]
A pressure-sensitive adhesive tape for use in a method for manufacturing a semiconductor package, comprising a base material and an adhesive layer arranged on the base material,
The following formula:
[(AB) / A] x 100
(In the formula,
A is the contact angle of water with respect to the adhesive layer before plasma treatment,
B is the contact angle of water with respect to the adhesive layer after plasma treatment)
And the change rate (%) of the contact angle of water with respect to the adhesive layer before and after the plasma treatment is 10% or less,
The pressure-sensitive adhesive tape, wherein the peeling force of the pressure-sensitive adhesive tape from the copper foil is 100 mN / 25 mm or more at 150 ° C.
[5]
An attaching step of attaching the adhesive tape according to any one of [1] to [4] to the back surface of the lead frame;
A fixing step of fixing the semiconductor chip to the die pad on the surface of the lead frame to which the adhesive tape is attached;
A plasma treatment step of treating the semiconductor chip and the surface of the lead frame with plasma;
A connecting step of connecting the semiconductor chip and the surface of the lead frame treated with plasma with a bonding wire;
A sealing step of sealing the bonding wire, the semiconductor chip, and the surface of the lead frame with a resin; and a peeling step of peeling the adhesive tape from the back surface of the lead frame whose surface is sealed with the resin.
A method for manufacturing a semiconductor package, comprising:
　本発明によれば、粘着層の一部を残すことなく、リードフレームからきれいに剥離することができ、かつ、モールドフラッシュを防止することができる粘着テープ、及びこれを用いた半導体パッケージの製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the adhesive tape which can be peeled off from a lead frame neatly, without leaving a part of adhesive layer, and can prevent mold flash, and the manufacturing method of a semiconductor package using this. Can be provided.
＜粘着テープ＞
　本発明の第１実施形態は、基材と、前記基材上に配置された粘着層と、を含み、前記粘着層が、金属キレート架橋剤によって架橋されている非芳香族アクリル系重合体を含む、半導体パッケージの製造方法において使用するための粘着テープに関する。具体的には、粘着テープは、モールドフラッシュを防止するために使用される。非芳香族アクリル系重合体及び金属キレート架橋剤を使用することによって、優れたプラズマ耐性、及び高温条件下における高い粘着力が得られる。これにより、粘着テープを、粘着層の一部を残すことなく、リードフレームからきれいに剥離することができると共に、モールドフラッシュを防止することができる。 <Adhesive tape>
The first embodiment of the present invention comprises a non-aromatic acrylic polymer comprising a substrate and an adhesive layer disposed on the substrate, wherein the adhesive layer is cross-linked by a metal chelate cross-linking agent. An adhesive tape for use in a method of manufacturing a semiconductor package, including: Specifically, the adhesive tape is used to prevent mold flash. By using a non-aromatic acrylic polymer and a metal chelate cross-linking agent, excellent plasma resistance and high adhesion under high temperature conditions can be obtained. As a result, the adhesive tape can be cleanly peeled from the lead frame without leaving a part of the adhesive layer, and mold flash can be prevented.
　本実施形態における基材は、半導体パッケージの製造過程における温度条件に耐えられる耐熱性基材であれば特に限定されない。耐熱性基材は、例えば、１５０℃、１７０℃、２００℃、２５０℃、又は３００℃の温度に耐えられる基材であることが好ましい。具体的な基材としては、例えば、ポリイミド、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエーテルサルフォン、ポリエーテルイミド、ポリサルフォン、ポリフェニレンサルファイド、ポリエーテルエーテルケトン、ポリアリレート、アラミド等が挙げられる。基材の厚さは、特に限定されないが、例えば、５～５０μｍ、１０～４０μｍ、２０～３０μｍ等としてもよい。 The base material in the present embodiment is not particularly limited as long as it is a heat resistant base material that can withstand the temperature conditions in the manufacturing process of the semiconductor package. The heat resistant substrate is preferably a substrate that can withstand a temperature of 150 ° C., 170 ° C., 200 ° C., 250 ° C., or 300 ° C., for example. Specific examples of the base material include polyimide, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyetherimide, polysulfone, polyphenylene sulfide, polyether ether ketone, polyarylate, and aramid. The thickness of the substrate is not particularly limited, but may be, for example, 5 to 50 μm, 10 to 40 μm, 20 to 30 μm, or the like.
　本実施形態における粘着層は、金属キレート架橋剤によって架橋されている非芳香族アクリル系重合体を含む。粘着層は、非芳香族アクリル系重合体を含むことにより、プラズマ耐性が向上する。詳しいメカニズムは定かではないが、本発明者は以下のように推測する。粘着層が芳香族アクリル系重合体を含む場合、プラズマ処理によって、芳香環周辺の結合が集中的に切断される。その結果、粘着層表面の変性度合いが強くなり、プラズマ耐性が大幅に低下する。これに対し、本実施形態における粘着層は、非芳香族アクリル系重合体を含むため、プラズマ処理を行っても、上述した集中的な切断は発生しない。その結果、プラズマ処理による粘着層表面の変性度合いは弱くなり、良好なプラズマ耐性を確保することができる。 The adhesive layer in the present embodiment contains a non-aromatic acrylic polymer cross-linked by a metal chelate cross-linking agent. By including the non-aromatic acrylic polymer in the adhesive layer, plasma resistance is improved. Although the detailed mechanism is not clear, the present inventors presume as follows. When the adhesive layer contains an aromatic acrylic polymer, the plasma treatment intensively cuts the bonds around the aromatic ring. As a result, the degree of modification of the surface of the adhesive layer becomes strong, and the plasma resistance is significantly reduced. On the other hand, since the adhesive layer in the present embodiment contains the non-aromatic acrylic polymer, the above-mentioned intensive cutting does not occur even if the plasma treatment is performed. As a result, the degree of modification of the surface of the adhesive layer due to the plasma treatment is weakened, and good plasma resistance can be secured.
　金属キレート架橋剤によって架橋される非芳香族アクリル系重合体は、１種類のみであってもよいし、２種類以上の組み合わせであってもよい。２種類以上を組み合わせる場合、少なくとも１種類の非芳香族アクリル系重合体は、アクリル酸に由来する構成単位を、非芳香族アクリル系重合体の全体量に対して、１～２０重量％含むことが好ましい。なお、重合体は通常、分子量分布を有するため、当該分子量分布を構成する複数の重合体分子の組み合わせを１つの種類と見なす。金属キレート架橋剤は、１種類のみであってもよいし、２種類以上の組み合わせであってもよい。粘着層は、本発明の効果を損なわない範囲で、更なる成分を含んでいてもよい。更なる成分としては、例えば、可塑剤、顔料、染料、帯電防止剤、充填剤等が挙げられる。 The non-aromatic acrylic polymer cross-linked by the metal chelate cross-linking agent may be only one kind or a combination of two or more kinds. When two or more kinds are combined, at least one kind of non-aromatic acrylic polymer must contain 1 to 20% by weight of a structural unit derived from acrylic acid, based on the total amount of the non-aromatic acrylic polymer. Is preferred. Since a polymer usually has a molecular weight distribution, a combination of a plurality of polymer molecules constituting the molecular weight distribution is regarded as one type. The metal chelate crosslinking agent may be only one kind or a combination of two or more kinds. The adhesive layer may contain further components as long as the effects of the present invention are not impaired. Further components include, for example, plasticizers, pigments, dyes, antistatic agents, fillers and the like.
　粘着層の乾燥後の厚さは、好ましくは２～１２μｍであり、より好ましくは４～１０μｍであり、更に好ましくは６～８μｍである。 The thickness of the adhesive layer after drying is preferably 2 to 12 μm, more preferably 4 to 10 μm, and further preferably 6 to 8 μm.
　本実施形態における非芳香族アクリル系重合体は、（メタ）アクリル酸及び／又はその誘導体に由来する構成単位（以下「アクリル単位」という。）を有し、芳香環を有しない重合体を意味する。本明細書において、（メタ）アクリル酸は、アクリル酸及び／又はメタクリル酸を意味する。（メタ）アクリル酸の誘導体としては、例えば、（メタ）アクリル酸エステル等が挙げられる。具体的な（メタ）アクリル酸の誘導体としては、例えば、（メタ）アクリル酸ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル等が挙げられる。これらの中でも、常温タックを適度に確保する観点から、アクリル酸ブチル、アクリル酸２－エチルヘキシルが好ましい。また、非芳香族アクリル系重合体は、金属キレート架橋剤と結合するための官能基を有する必要がある。官能基としては、カルボキシル基が好ましい。また、官能基を有する構成単位は、非芳香族アクリル系重合体の全体量に対して１～２０重量％含まれることが好ましい。 The non-aromatic acrylic polymer in the present embodiment means a polymer having a structural unit (hereinafter referred to as “acrylic unit”) derived from (meth) acrylic acid and / or a derivative thereof and having no aromatic ring. To do. In the present specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid. Examples of the (meth) acrylic acid derivative include (meth) acrylic acid ester. Specific derivatives of (meth) acrylic acid include, for example, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include isoamyl, n-hexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, and dodecyl (meth) acrylate. Among these, butyl acrylate and 2-ethylhexyl acrylate are preferable from the viewpoint of ensuring a proper room temperature tack. Further, the non-aromatic acrylic polymer needs to have a functional group for bonding with the metal chelate crosslinking agent. The functional group is preferably a carboxyl group. Further, the constituent unit having a functional group is preferably contained in an amount of 1 to 20% by weight based on the total amount of the non-aromatic acrylic polymer.
　非芳香族アクリル系重合体は、アクリル単位に加えて、更なる構成単位を有していてもよい。更なる構成単位としては、例えば、アクリロニトリル、酢酸ビニル、塩化ビニル、ブタジエン、イソプレン等に由来する構成単位が挙げられる。 The non-aromatic acrylic polymer may have an additional structural unit in addition to the acrylic unit. Examples of the further structural unit include structural units derived from acrylonitrile, vinyl acetate, vinyl chloride, butadiene, isoprene and the like.
　非芳香族アクリル系重合体を構成するアクリル単位の量は、非芳香族アクリル系重合体に対して、好ましくは７０重量％以上であり、より好ましくは８０重量％以上であり、更に好ましくは９０重量％以上である。アクリル単位の量の上限は、特に制限されないが、例えば、１００重量％、９５重量％等としてもよい。 The amount of acrylic units constituting the non-aromatic acrylic polymer is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight based on the non-aromatic acrylic polymer. It is more than weight%. The upper limit of the amount of acrylic units is not particularly limited, but may be, for example, 100% by weight or 95% by weight.
　非芳香族アクリル系重合体の重量平均分子量は、作業性と糊残り性を両立させる観点から、好ましくは３０万～１５０万であり、より好ましくは５０万～１００万である。 The weight average molecular weight of the non-aromatic acrylic polymer is preferably 300,000 to 1,500,000, and more preferably 500,000 to 1,000,000, from the viewpoint of achieving both workability and adhesive residue.
　非芳香族アクリル系重合体の量は、粘着層に対して、好ましくは８５～９９重量％であり、より好ましくは９０～９８重量％であり、更に好ましくは９３～９７重量％である。　　　 The amount of the non-aromatic acrylic polymer is preferably 85 to 99% by weight, more preferably 90 to 98% by weight, further preferably 93 to 97% by weight, based on the adhesive layer. ：
　本実施形態における金属キレート架橋剤は、金属イオンと配位子を有する架橋剤を意味する。金属キレート架橋剤は、イオン結合性の架橋剤であることから、共有結合性の架橋剤に比べ、１７５℃における弾性率が低い。これにより、粘着層は高温条件下において高い粘着力を有し、モールドフラッシュを効果的に抑制することができる。また、金属キレート架橋剤は、沸点が２００℃以下の配位子を有することが好ましい。これにより、粘着層を形成する工程で、乾燥により配位子が揮発し、金属キレート架橋剤は、不可逆的に非芳香族アクリル系重合体と架橋することができる。配位子の沸点の下限は特に限定されないが、例えば、６０℃、７０℃、８０℃等であってもよい。 The metal chelate cross-linking agent in this embodiment means a cross-linking agent having a metal ion and a ligand. Since the metal chelate cross-linking agent is an ionic bond-forming cross-linking agent, it has a lower elastic modulus at 175 ° C. than the covalent-bonding cross-linking agent. As a result, the adhesive layer has a high adhesive force under high temperature conditions, and mold flash can be effectively suppressed. Further, the metal chelate crosslinking agent preferably has a ligand having a boiling point of 200 ° C. or lower. Thereby, in the step of forming the adhesive layer, the ligand is volatilized by drying, and the metal chelate crosslinking agent can irreversibly crosslink with the non-aromatic acrylic polymer. The lower limit of the boiling point of the ligand is not particularly limited, but may be, for example, 60 ° C, 70 ° C, 80 ° C or the like.
　沸点が２００℃以下の配位子を有する金属キレート架橋剤としては、例えば、アルミニウムキレート架橋剤、チタンキレート架橋剤、ジルコニウムキレート架橋剤等が挙げられる。 Examples of the metal chelate cross-linking agent having a ligand having a boiling point of 200 ° C. or less include an aluminum chelate cross-linking agent, a titanium chelate cross-linking agent, a zirconium chelate cross-linking agent, and the like.
　アルミニウムキレート架橋剤としては、例えば、アルミニウムトリス（アセチルアセトネート）、アルミニウムビスエチルアセトアセテートモノアセチルアセトネート、アルミニウムトリス（エチルアセトアセテート）等が挙げられる。
　チタンキレート架橋剤としては、例えば、チタンジイソプロポキシビス（アセチルアセトネート）、チタンテトラアセチルアセトネート、チタンジイソプロポキシビス（エチルアセトアセテート）、チタニウムジ－２－エチルヘキソキシビス（２－エチル－３－ヒドロキシヘキソキシド）、チタンラクテートアンモニウム塩、チタンラクテート、チタンジイソプロポキシビス（トリエタノールアミネート）、チタンアミノエチルアミノエタノレート等が挙げられる。
　ジルコニウムキレート架橋剤としては、例えば、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムジブトキシビス（エチルアセトアセテート）、ジルコニウムラクテートアンモニウム塩等が挙げられる。
　特に限定するものではないが、ポットライフ（シェルフライフ）の観点から、金属キレート架橋剤は、アルミニウムキレート架橋剤であることが好ましく、アルミニウムトリス（アセチルアセトネート）であることがより好ましい。 Examples of the aluminum chelate cross-linking agent include aluminum tris (acetylacetonate), aluminum bisethylacetoacetate monoacetylacetonate, and aluminum tris (ethylacetoacetate).
Examples of the titanium chelate cross-linking agent include titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis (ethylacetoacetate), titanium di-2-ethylhexoxybis (2-ethyl). -3-hydroxyhexoxide), titanium lactate ammonium salt, titanium lactate, titanium diisopropoxybis (triethanolaminate), titanium aminoethylaminoethanolate, and the like.
Examples of the zirconium chelate cross-linking agent include zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium dibutoxybis (ethylacetoacetate), zirconium lactate ammonium salt and the like.
Although not particularly limited, from the viewpoint of pot life (shelf life), the metal chelate cross-linking agent is preferably an aluminum chelate cross-linking agent, and more preferably aluminum tris (acetylacetonate).
　金属キレート架橋剤の量は、粘着層に対して、好ましくは１～１５重量％であり、より好ましくは２～１０重量％であり、更に好ましくは３～７重量％である。 The amount of the metal chelate cross-linking agent is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, further preferably 3 to 7% by weight, based on the adhesive layer.
　本実施形態に係る粘着テープは、粘着層上に離型フィルムを含んでいてもよい。 The adhesive tape according to the present embodiment may include a release film on the adhesive layer.
　本実施形態に係る粘着テープは、公知の方法で製造することができる。例えば、非芳香族アクリル系重合体、金属キレート架橋剤、及び溶媒を混合する工程（混合工程）、混合物を基材に塗布する工程（塗布工程）、塗布された混合物を乾燥する工程（乾燥工程）、を含む方法によって、粘着テープを製造することができる。 The adhesive tape according to this embodiment can be manufactured by a known method. For example, a step of mixing a non-aromatic acrylic polymer, a metal chelate crosslinking agent, and a solvent (mixing step), a step of applying the mixture to a substrate (application step), a step of drying the applied mixture (drying step) ), The adhesive tape can be manufactured by the method including.
　混合工程で使用する溶媒としては、例えば、ケトン溶媒（アセチルアセトン、メチルエチルケトン、アセトン等）、アルコール溶媒（メタノール、エタノール、プロパノール、ブタノール等）、エーテル溶媒（テトラヒドロフラン等）、ニトリル溶媒（アセトニトリル等）、アミド溶媒（Ｎ，Ｎ－ジメチルホルムアミド等）等が挙げられる。 Examples of the solvent used in the mixing step include a ketone solvent (acetylacetone, methylethylketone, acetone, etc.), an alcohol solvent (methanol, ethanol, propanol, butanol, etc.), an ether solvent (tetrahydrofuran, etc.), a nitrile solvent (acetonitrile, etc.), an amide. Solvents (N, N-dimethylformamide etc.) and the like can be mentioned.
　塗布工程における塗布の方法としては、例えば、ダイコーター塗工、バーコーター塗工、エアナイフコーター塗工、グラビアコーター塗工、リバースロールコーター塗工、リップコーター塗工等が挙げられる。 Examples of the coating method in the coating step include die coater coating, bar coater coating, air knife coater coating, gravure coater coating, reverse roll coater coating, lip coater coating and the like.
　本実施形態に係る粘着テープは、以下の第２実施形態に係る粘着テープの特徴を更に有していてもよい。 The adhesive tape according to this embodiment may further have the features of the adhesive tape according to the following second embodiment.
　本発明の第２実施形態は、基材と、前記基材上に配置された粘着層と、を含む、半導体パッケージの製造方法において使用するための粘着テープであって、下記式：
［（Ａ－Ｂ）／Ａ］×１００
（式中、
　Ａは、プラズマ処理前の前記粘着層に対する水の接触角であり、
　Ｂは、プラズマ処理後の前記粘着層に対する水の接触角である）
で表される、プラズマ処理の前後における前記粘着層に対する水の接触角の変化率（％）が１０％以下であり、
　銅箔からの前記粘着テープの剥離力が、１５０℃で１００ｍＮ／２５ｍｍ以上である、前記粘着テープに関する。具体的には、粘着テープは、モールドフラッシュを防止するために使用される。 A second embodiment of the present invention is an adhesive tape for use in a method for manufacturing a semiconductor package, which comprises a base material and an adhesive layer disposed on the base material, and has the following formula:
[(AB) / A] x 100
(In the formula,
A is a contact angle of water with respect to the adhesive layer before plasma treatment,
B is the contact angle of water with respect to the adhesive layer after plasma treatment)
And the change rate (%) of the contact angle of water with respect to the adhesive layer before and after the plasma treatment is 10% or less,
The adhesive tape has a peeling force of 100 mN / 25 mm or more at 150 ° C. from the copper foil. Specifically, the adhesive tape is used to prevent mold flash.
　プラズマ処理によって、粘着層に対する水の接触角が小さくなると、粘着層の粘着力が上昇し、粘着テープをリードフレームからきれいに剥離することができなくなる。一方、プラズマ処理の前後における水の接触角の変化率（％）を１０％以下とすることによって、粘着力の上昇を抑制し、常温条件下において、粘着テープをきれいに剥離することができる。また、粘着テープの剥離力を、１５０℃で１００ｍＮ／２５ｍｍ以上とすることによって、モールドフラッシュを防止することができる。 When the contact angle of water to the adhesive layer is reduced by the plasma treatment, the adhesive strength of the adhesive layer increases and it becomes impossible to cleanly remove the adhesive tape from the lead frame. On the other hand, by setting the change rate (%) of the contact angle of water before and after the plasma treatment to be 10% or less, an increase in the adhesive force can be suppressed and the adhesive tape can be peeled off neatly at room temperature. Further, by setting the peeling force of the adhesive tape to 100 mN / 25 mm or more at 150 ° C., mold flash can be prevented.
　プラズマ処理の前後における粘着層に対する水の接触角の変化率（％）は、好ましくは１０％以下であり、より好ましくは５％以下であり、更に好ましくは３％以下である。前記変化率（％）の下限は、特に制限されないが、例えば、０％、１％等としてもよい。プラズマ処理の前後における接触角は、以下の実施例に記載の方法により測定することができ、測定した接触角に基づいて変化率を計算することができる。 The rate of change (%) in the contact angle of water with respect to the adhesive layer before and after plasma treatment is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less. The lower limit of the rate of change (%) is not particularly limited, but may be 0%, 1% or the like, for example. The contact angle before and after the plasma treatment can be measured by the method described in the examples below, and the rate of change can be calculated based on the measured contact angle.
　常温条件下における粘着テープの剥離力は、粘着テープをリードフレームからきれいに剥離するために、低いほど好ましい。具体的には、２５℃条件下で１２００ｍＮ／２５ｍｍ未満が好ましく、５００ｍＮ／２５ｍｍ未満がより好ましい。２５℃での粘着テープの剥離力は、以下の実施例に記載の方法により測定することができる。２５℃での粘着テープの剥離力の下限は特に限定されないが、例えば、１００ｍＮ／２５ｍｍ、２００ｍＮ／２５ｍｍ等であってもよい。 The lower the peel strength of the adhesive tape under normal temperature conditions, the better the peel strength of the adhesive tape from the lead frame. Specifically, it is preferably less than 1200 mN / 25 mm and more preferably less than 500 mN / 25 mm under the condition of 25 ° C. The peeling force of the adhesive tape at 25 ° C can be measured by the method described in the following examples. The lower limit of the peeling force of the adhesive tape at 25 ° C. is not particularly limited, but may be 100 mN / 25 mm, 200 mN / 25 mm or the like, for example.
　高温条件下における粘着テープの剥離力は、モールドフラッシュ耐性を確保する観点から、高いほど好ましい。具体的には、１５０℃条件下で１００ｍＮ／２５ｍｍ以上が好ましく、１５０ｍＮ／２５ｍｍ以上がより好ましい。１５０℃での粘着テープの剥離力は、以下の実施例に記載の方法により測定することができる。１５０℃での粘着テープの剥離力の上限は特に限定されないが、例えば、５００ｍＮ／２５ｍｍ、１０００ｍＮ／２５ｍｍ等であってもよい。 The higher the peeling force of the adhesive tape under high temperature conditions, the better from the viewpoint of ensuring mold flash resistance. Specifically, at 150 ° C., 100 mN / 25 mm or more is preferable, and 150 mN / 25 mm or more is more preferable. The peeling force of the adhesive tape at 150 ° C can be measured by the method described in the following examples. The upper limit of the peeling force of the adhesive tape at 150 ° C. is not particularly limited, but may be, for example, 500 mN / 25 mm, 1000 mN / 25 mm or the like.
　粘着テープの弾性率は、モールドフラッシュ耐性を確保し、且つ、半導体チップとリードフレームの表面とをボンディングワイヤーで十分に接続するために、１７５℃で、好ましくは５×１０５～２０×１０５Ｐａであり、より好ましくは５×１０５～１０×１０５Ｐａである。粘着テープの弾性率は、以下の実施例に記載の方法により測定することができる。 The elastic modulus of the adhesive tape is 175 ° C., preferably 5 × 10 5 to 20 × 10 5 in order to secure mold flash resistance and to sufficiently connect the semiconductor chip and the surface of the lead frame with a bonding wire. Pa, more preferably 5 × 10 5 to 10 × 10 5 Pa. The elastic modulus of the adhesive tape can be measured by the method described in the examples below.
　本実施形態に係る粘着テープは、第１実施形態に係る粘着テープの特徴を更に有していてもよい。 The adhesive tape according to this embodiment may further have the features of the adhesive tape according to the first embodiment.
＜半導体パッケージの製造方法＞
　本発明の第３実施形態は、貼付工程、固定工程、プラズマ処理工程、接続工程、封止工程、及び剥離工程を含む、半導体パッケージの製造方法に関する。以下、各工程について説明する。 <Semiconductor package manufacturing method>
The third embodiment of the present invention relates to a method of manufacturing a semiconductor package including a sticking step, a fixing step, a plasma processing step, a connecting step, a sealing step, and a peeling step. Hereinafter, each step will be described.
　本実施形態における貼付工程は、リードフレームの裏面に、第１実施形態又は第２実施形態に係る粘着テープを貼り付ける工程である。貼付工程は、公知の方法で行うことができる。 The sticking step in this embodiment is a step of sticking the adhesive tape according to the first embodiment or the second embodiment to the back surface of the lead frame. The attaching step can be performed by a known method.
　本実施形態における固定工程は、粘着テープが貼り付けられたリードフレームの表面のダイパッドに半導体チップを固定する工程である。固定工程は、公知の方法で行うことができる。 The fixing step in this embodiment is a step of fixing the semiconductor chip to the die pad on the surface of the lead frame to which the adhesive tape is attached. The fixing step can be performed by a known method.
　本実施形態におけるプラズマ処理工程は、半導体チップとリードフレームの表面とをプラズマで処理する工程である。プラズマ処理工程は、公知の方法で行うことができる。例えば、不活性ガス（アルゴン、窒素等）の雰囲気下で、５０～３００Ｗ（好ましくは１００～１５０Ｗ）、５～６０秒間（好ましくは１０～３０秒間）の条件で、プラズマ処理を行うことができる。 The plasma treatment step in this embodiment is a step of treating the semiconductor chip and the surface of the lead frame with plasma. The plasma treatment step can be performed by a known method. For example, plasma treatment can be performed under an atmosphere of an inert gas (argon, nitrogen, etc.) under the conditions of 50 to 300 W (preferably 100 to 150 W) and 5 to 60 seconds (preferably 10 to 30 seconds). .
　本実施形態における接続工程は、プラズマで処理された、半導体チップとリードフレームの表面とをボンディングワイヤーで接続する工程である。接続工程は、公知の方法で行うことができる。 The connection step in this embodiment is a step of connecting the semiconductor chip, which has been treated with plasma, and the surface of the lead frame with a bonding wire. The connecting step can be performed by a known method.
　本実施形態における封止工程は、ボンディングワイヤーと半導体チップとリードフレームの表面とを樹脂で封止する工程である。封止工程は、公知の方法で行うことができる。例えば、１１０～２００℃、好ましくは１３０～１８０℃で、封止工程を行うことができる。 The sealing step in this embodiment is a step of sealing the bonding wire, the semiconductor chip, and the surface of the lead frame with resin. The sealing step can be performed by a known method. For example, the sealing step can be performed at 110 to 200 ° C, preferably 130 to 180 ° C.
　本実施形態における剥離工程は、樹脂で表面が封止されたリードフレームの裏面から粘着テープを剥離する工程である。剥離工程は、公知の方法で行うことができる。 The peeling step in this embodiment is a step of peeling the adhesive tape from the back surface of the lead frame whose surface is sealed with resin. The peeling step can be performed by a known method.
　リードフレームが表面に複数のダイパッドを有し、当該複数のダイパッドに複数の半導体チップを固定する場合には、本実施形態に係る製造方法は、粘着テープが剥離された、樹脂で表面が封止されたリードフレームを、個々の半導体パッケージに切断する切断工程を更に含んでいてもよい。 When the lead frame has a plurality of die pads on the surface, and a plurality of semiconductor chips are fixed to the plurality of die pads, the manufacturing method according to the present embodiment, the adhesive tape is peeled off, the surface is sealed with resin. The method may further include a cutting step of cutting the formed lead frame into individual semiconductor packages.
　以下、実施例及び比較例を用いて本発明をより詳細に説明するが、本発明の技術的範囲はこれに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the technical scope of the present invention is not limited thereto.
＜重合体＞
　実施例及び比較例では、以下の重合体を使用した。
（１）アクリル系重合体Ａ
　反応容器に、アクリル酸ブチル（ＢＡ）（９２重量部）、アクリル酸（ＡＡ）（８重量部）、酢酸エチル（１００重量部）、及びアゾビスイソブチロニトリル（ＡＩＢＮ）（０．３重量部）を加え、７０℃で撹拌した。反応開始６０分後から３０分ごとに反応溶液の一部を取り出し、脱イオン水で反応を停止させ、メチルエチルケトンにより抽出し、抽出溶液をゲル浸透クロマトグラフィー（ＧＰＣ）で分析した。ＧＰＣ分析から、反応物の重量平均分子量が７０万以上となった段階で反応容器を冷却し、反応を停止させた。得られた混合物を脱イオン水により水洗し、乾燥することでアクリル系重合体Ａを得た。アクリル系重合体Ａの重量平均分子量は７５万であり、水酸化カリウム水溶液での滴定による酸価は８１０ｍｇＫＯＨ/ｇであった。 <Polymer>
The following polymers were used in the Examples and Comparative Examples.
(1) Acrylic polymer A
In a reaction vessel, butyl acrylate (BA) (92 parts by weight), acrylic acid (AA) (8 parts by weight), ethyl acetate (100 parts by weight), and azobisisobutyronitrile (AIBN) (0.3 parts by weight). Part) and stirred at 70 ° C. After 60 minutes from the start of the reaction, a part of the reaction solution was taken out every 30 minutes, the reaction was stopped with deionized water, the mixture was extracted with methyl ethyl ketone, and the extracted solution was analyzed by gel permeation chromatography (GPC). From the GPC analysis, the reaction vessel was cooled to stop the reaction when the weight average molecular weight of the reaction product reached 700,000 or more. The resulting mixture was washed with deionized water and dried to obtain an acrylic polymer A. The weight average molecular weight of the acrylic polymer A was 750,000, and the acid value as determined by titration with an aqueous potassium hydroxide solution was 810 mgKOH / g.
（２）アクリル系重合体Ｂ
　反応容器に、アクリル酸ブチル（ＢＡ）（８２重量部）、アクリロニトリル（ＡＮ）（１２重量部）、アクリル酸２－ヒドロキシエチル（２ＨＥＡ）（５重量部）、アクリル酸（ＡＡ）（１重量部）、酢酸エチル（１００重量部）、及びアゾビスイソブチロニトリル（ＡＩＢＮ）（０．３重量部）を加え、７０℃で撹拌した。反応開始６０分後から３０分ごとに反応溶液の一部を取り出し、脱イオン水で反応を停止させ、メチルエチルケトンにより抽出し、抽出溶液をゲル浸透クロマトグラフィー（ＧＰＣ）で分析した。ＧＰＣ分析から、反応物の重量平均分子量が５０万以上となった段階で反応容器を冷却し、反応を停止させた。得られた混合物を脱イオン水により水洗し、乾燥することでアクリル系重合体Ｂを得た。アクリル系重合体Ｂの重量平均分子量は５４万であった。 (2) Acrylic polymer B
In a reaction vessel, butyl acrylate (BA) (82 parts by weight), acrylonitrile (AN) (12 parts by weight), 2-hydroxyethyl acrylate (2HEA) (5 parts by weight), acrylic acid (AA) (1 part by weight) ), Ethyl acetate (100 parts by weight), and azobisisobutyronitrile (AIBN) (0.3 parts by weight) were added, and the mixture was stirred at 70 ° C. After 60 minutes from the start of the reaction, a part of the reaction solution was taken out every 30 minutes, the reaction was stopped with deionized water, the mixture was extracted with methyl ethyl ketone, and the extracted solution was analyzed by gel permeation chromatography (GPC). From the GPC analysis, the reaction vessel was cooled to stop the reaction when the weight average molecular weight of the reaction product reached 500,000 or more. The resulting mixture was washed with deionized water and dried to obtain an acrylic polymer B. The weight average molecular weight of the acrylic polymer B was 540,000.
（３）アクリル系重合体Ｃ
　反応容器に、アクリル酸ブチル（ＢＡ）（７２重量部）、スチレン（ＳＴ）（２０重量部）、アクリル酸（ＡＡ）（８重量部）、酢酸エチル（１００重量部）、及びアゾビスイソブチロニトリル（ＡＩＢＮ）（０．３重量部）を加え、７０℃で撹拌した。反応開始６０分後から３０分ごとに反応溶液の一部を取り出し、脱イオン水で反応を停止させ、メチルエチルケトンにより抽出し、抽出溶液をゲル浸透クロマトグラフィー（ＧＰＣ）で分析した。ＧＰＣ分析から、反応物の重量平均分子量が１０万以上となった段階で反応容器を冷却し、反応を停止させた。得られた混合物を脱イオン水により水洗し、乾燥することでアクリル系重合体Ｃを得た。アクリル系重合体Ｃの重量平均分子量は１２万であり、水酸化カリウム水溶液での滴定による酸価は６７０ｍｇＫＯＨ/ｇであった。 (3) Acrylic polymer C
In a reaction vessel, butyl acrylate (BA) (72 parts by weight), styrene (ST) (20 parts by weight), acrylic acid (AA) (8 parts by weight), ethyl acetate (100 parts by weight), and azobisisobutyrate. Ronitrile (AIBN) (0.3 parts by weight) was added, and the mixture was stirred at 70 ° C. After 60 minutes from the start of the reaction, a part of the reaction solution was taken out every 30 minutes, the reaction was stopped with deionized water, the mixture was extracted with methyl ethyl ketone, and the extracted solution was analyzed by gel permeation chromatography (GPC). From the GPC analysis, the reaction vessel was cooled and the reaction was stopped when the weight average molecular weight of the reaction product reached 100,000 or more. The resulting mixture was washed with deionized water and dried to obtain an acrylic polymer C. The weight average molecular weight of the acrylic polymer C was 120,000, and the acid value by titration with an aqueous potassium hydroxide solution was 670 mgKOH / g.
＜架橋剤＞
　実施例及び比較例では、以下の架橋剤を使用した。
（１）アルミニウムキレート架橋剤［アルミニウムトリス（アセチルアセトネート）、商品名：オルガチックスＡＬ－３１００（マツモトファインケミカル株式会社製）］
（２）チタンキレート架橋剤［チタンジイソプロポキシビス（アセチルアセトネート）、商品名：オルガチックスＴＣ－１００（マツモトファインケミカル株式会社製）］
（３）ジルコニウムキレート架橋剤［ジルコニウムテトラアセチルアセトネート、商品名：オルガチックスＺＣ－７００（マツモトファインケミカル株式会社製）］
（４）フェノールノボラック型エポキシ樹脂架橋剤［商品名：ＥＰＩＣＬＯＮ　Ｎ７３０Ａ（ＤＩＣ株式会社製）］
（５）脂環式エポキシ樹脂架橋剤Ａ［商品名：ＥＨＰＥ３１５０（株式会社ダイセル製）］
（６）脂環式エポキシ樹脂架橋剤Ｂ［商品名：Ｔｅｔｒａｄ－Ｃ（三菱ガス化学株式会社製）］
（７）イミダゾール系触媒［商品名：キュアゾールＣ１１Ｚ（四国化成工業株式会社製）］
（８）イソシアネート型架橋剤［商品名：デュラネートＳＢＮ－７０Ｄ（旭化成株式会社製）］ <Crosslinking agent>
The following cross-linking agents were used in the examples and comparative examples.
(1) Aluminum chelate cross-linking agent [aluminum tris (acetylacetonate), trade name: Organix AL-3100 (manufactured by Matsumoto Fine Chemical Co., Ltd.)]
(2) Titanium chelate cross-linking agent [titanium diisopropoxybis (acetylacetonate), trade name: Organix TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.)]
(3) Zirconium chelate crosslinking agent [zirconium tetraacetylacetonate, trade name: Organix ZC-700 (manufactured by Matsumoto Fine Chemical Co., Ltd.)]
(4) Phenol novolac type epoxy resin cross-linking agent [trade name: EPICLON N730A (manufactured by DIC Corporation)]
(5) Alicyclic epoxy resin crosslinking agent A [trade name: EHPE3150 (manufactured by Daicel Corporation)]
(6) Alicyclic epoxy resin cross-linking agent B [trade name: Tetrad-C (manufactured by Mitsubishi Gas Chemical Co., Inc.)]
(7) Imidazole-based catalyst [trade name: Curezol C11Z (manufactured by Shikoku Chemicals Co., Ltd.)]
(8) Isocyanate type cross-linking agent [Brand name: Duranate SBN-70D (manufactured by Asahi Kasei Corporation)]
［実施例１］
＜粘着テープの製造＞
　アクリル系重合体Ａ（１００重量部）、アルミニウムキレート架橋剤（４重量部）、アセチルアセトン（１０重量部）、及びメチルエチルケトン（６０重量部）を室温で撹拌して、組成物１を得た。組成物１を、乾燥後の厚さが７μｍになるように、ポリイミドフィルム（厚さ２５μｍ）にダイコーターを用いて塗布し、１５０℃で５分乾燥し、粘着テープを得た。粘着テープの粘着層に、離型処理を施した離型フィルムの離型面を、ラミネートにより貼り合わせ、１０５℃で２４時間加熱し、離型フィルム付き粘着テープを得た。 [Example 1]
<Production of adhesive tape>
Acrylic polymer A (100 parts by weight), aluminum chelate crosslinking agent (4 parts by weight), acetylacetone (10 parts by weight), and methyl ethyl ketone (60 parts by weight) were stirred at room temperature to obtain a composition 1. The composition 1 was applied to a polyimide film (thickness: 25 μm) using a die coater so that the thickness after drying was 7 μm, and dried at 150 ° C. for 5 minutes to obtain an adhesive tape. The release surface of the release film that had been subjected to the release treatment was attached to the adhesive layer of the adhesive tape by laminating and heated at 105 ° C. for 24 hours to obtain an adhesive tape with a release film.
＜水の接触角の変化率＞
　離型フィルム付き粘着テープを、第１粘着テープ及び第２粘着テープの２つに分割し、離型フィルムを除去し、十分に除電した。アルゴン雰囲気下（流速５０ｃｃ）、１２０Ｗ、２０秒間の条件で、第２粘着テープにのみプラズマ処理を行った。第１粘着テープ及び第２粘着テープを、２３℃雰囲気下、接触角計［製品名：ＣＡ－Ｘ（協和界面科学株式会社製）］の台座に、粘着層を上にして固定し、粘着層に純水を滴下したときの接触角を測定した。測定は１０回行い、その平均値を算出した。接触角の平均値と下記式から、水の接触角の変化率を算出した。
水の接触角の変化率（％）＝［（第１粘着テープに対する水の接触角－プラズマ処理後の第２粘着テープに対する水の接触角）／第１粘着テープに対する水の接触角］×１００ <Change rate of contact angle of water>
The pressure-sensitive adhesive tape with a release film was divided into two, a first pressure-sensitive adhesive tape and a second pressure-sensitive adhesive tape, the release film was removed, and the charge was sufficiently removed. Plasma treatment was performed only on the second adhesive tape under an argon atmosphere (flow rate of 50 cc) and 120 W for 20 seconds. The first adhesive tape and the second adhesive tape were fixed to a pedestal of a contact angle meter [Product name: CA-X (manufactured by Kyowa Interface Science Co., Ltd.)] with the adhesive layer facing up in an atmosphere of 23 ° C. The contact angle when pure water was dropped on was measured. The measurement was performed 10 times, and the average value was calculated. The change rate of the contact angle of water was calculated from the average value of the contact angle and the following formula.
Rate of change of contact angle of water (%) = [(contact angle of water on first adhesive tape-contact angle of water on second adhesive tape after plasma treatment) / contact angle of water on first adhesive tape] × 100
　この水の接触角の変化率を下記の基準で評価した。結果を表１に示す。
　◎：水の接触角の変化率が５％以下
　○：水の接触角の変化率が５％より大きく、１０％以下
　△：水の接触角の変化率が１０％より大きく、１５％以下
　×：水の接触角の変化率が１５％より大きい The rate of change of the contact angle of this water was evaluated according to the following criteria. The results are shown in Table 1.
⊚: Change rate of contact angle of water is 5% or less ◯: Change rate of contact angle of water is more than 5% and 10% or less Δ: Change rate of contact angle of water is more than 10% and 15% or less × : Water contact angle change rate is greater than 15%
＜剥離力の測定＞
　粘着テープを、圧延銅箔（厚さ３５μｍ）の光沢面側に、ロールラミネート（３０℃、０．４ＭＰａ、１ｍ／ｍｉｎ）した後、２５ｍｍ幅の試験片を作成した。作製した試験片の圧延銅箔面とステンレス板とを両面テープで貼り合わせ、粘着テープを１８０°方向に２００ｍｍ／ｍｉｎの速度で引き剥がした際の剥離力を、２５℃及び１５０℃の雰囲気下で測定した。この剥離力を下記の基準で評価した。結果を表１に示す。 <Measurement of peeling force>
The adhesive tape was roll-laminated (30 ° C., 0.4 MPa, 1 m / min) on the glossy side of the rolled copper foil (thickness 35 μm), and then a 25 mm width test piece was prepared. The peeling force when the rolled copper foil surface of the produced test piece and the stainless steel plate were bonded together with a double-sided tape and the adhesive tape was peeled off at a speed of 200 mm / min in the 180 ° direction under an atmosphere of 25 ° C and 150 ° C. It was measured at. The peel strength was evaluated according to the following criteria. The results are shown in Table 1.
[２５℃雰囲気下の剥離力]
　◎：剥離力が５００ｍＮ／２５ｍｍ未満
　○：剥離力が５００ｍＮ／２５ｍｍ以上、１２００ｍＮ／２５ｍｍ未満
　△：剥離力が１２００ｍＮ／２５ｍｍ以上、１３００ｍＮ／２５ｍｍ未満
　×：剥離力が１３００ｍＮ／２５ｍｍ以上 [Peeling force under 25 ° C atmosphere]
⊚: Peeling force is less than 500 mN / 25 mm ◯: Peeling force is 500 mN / 25 mm or more and less than 1200 mN / 25 mm Δ: Peeling force is 1200 mN / 25 mm or more and less than 1300 mN / 25 mm ×: Peeling force is 1300 mN / 25 mm or more
[１５０℃雰囲気下の剥離力]
　◎：剥離力が１５０ｍＮ／２５ｍｍ以上
　○：剥離力が１００ｍＮ／２５ｍｍ以上、１５０ｍＮ／２５ｍｍ未満
　△：剥離力が５０ｍＮ／２５ｍｍ以上、１００ｍＮ／２５ｍｍ未満
　×：剥離力が５０ｍＮ／２５ｍｍ未満 [Peeling force under 150 ° C atmosphere]
◎: Peeling force is 150 mN / 25 mm or more ◯: Peeling force is 100 mN / 25 mm or more, less than 150 mN / 25 mm △: Peeling force is 50 mN / 25 mm or more, less than 100 mN / 25 mm ×: Peeling force is less than 50 mN / 25 mm
＜弾性率の測定＞
　粘着剤組成物を、乾燥後の厚さが１００μｍになるように離型フィルム上に塗布し、乾燥した後に１０５℃で２４時間加熱し、離型フィルムを除去することで、粘着剤の単膜を得た。得られた単膜について、動的粘弾性測定（ＤＭＡ：Ｄｙｎａｍｉｃ　Ｍｅｃｈａｎｉｃａｌ　Ａｎａｌｙｓｉｓ)装置にて昇温速度１０℃／ｍｉｎ、１Ｈｚの条件で２３℃～２００℃の貯蔵弾性率(Ｅ’)を測定した。このうち、１７５℃における値を下記の基準で評価した。結果を表１に示す。 <Measurement of elastic modulus>
The pressure-sensitive adhesive composition is applied to a release film so as to have a thickness after drying of 100 μm, dried and then heated at 105 ° C. for 24 hours to remove the release film. Got The storage elastic modulus (E ′) of 23 ° C. to 200 ° C. of the obtained single film was measured at a temperature rising rate of 10 ° C./min and 1 Hz with a dynamic mechanical analysis (DMA) device. .. Among these, the value at 175 ° C. was evaluated according to the following criteria. The results are shown in Table 1.
　◎：１７５℃における貯蔵弾性率が５×１０５Ｐａ以上１０×１０５Ｐａ未満
　○：１７５℃における貯蔵弾性率が１０×１０５Ｐａ以上２０×１０５Ｐａ未満
　△：１７５℃における貯蔵弾性率が２０×１０５Ｐａ以上３０×１０５Ｐａ未満
　×：１７５℃における貯蔵弾性率が３０×１０５Ｐａ以上 ◎: Storage elastic modulus at 175 ° C. is 5 × 10 5 Pa or more and less than 10 × 10 5 Pa ○: Storage elastic modulus at 175 ° C. is 10 × 10 5 Pa or more and less than 20 × 10 5 Pa Δ: Storage elastic modulus at 175 ° C. Is 20 × 10 5 Pa or more and less than 30 × 10 5 Pa ×: Storage elastic modulus at 175 ° C. is 30 × 10 5 Pa or more
［実施例２～４及び比較例１～７］
　表１及び表２に示す重合体及び架橋剤を使用して、実施例１と同様に離型フィルム付き粘着テープを製造し、水の接触角の変化率を算出した。また、剥離力、及び弾性率を測定した。結果は表１及び表２に示す。 [Examples 2 to 4 and Comparative Examples 1 to 7]
A pressure-sensitive adhesive tape with a release film was produced in the same manner as in Example 1 using the polymers and cross-linking agents shown in Tables 1 and 2, and the rate of change in water contact angle was calculated. Moreover, the peeling force and the elastic modulus were measured. The results are shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　表１及び表２の結果のとおり、実施例１～４の粘着テープは、プラズマ耐性を有しているため、粘着層の一部を残すことなく、リードフレームからきれいに剥離することができる。また、実施例１～４の粘着テープは、高温条件下で優れた粘着力を有しているため、モールドフラッシュを抑制することができる。
 
 
  As can be seen from the results of Tables 1 and 2, the adhesive tapes of Examples 1 to 4 have plasma resistance, and therefore can be peeled off cleanly from the lead frame without leaving a part of the adhesive layer. Moreover, since the adhesive tapes of Examples 1 to 4 have excellent adhesive strength under high temperature conditions, mold flash can be suppressed.


Claims (5)

  1. 　基材と、前記基材上に配置された粘着層と、を含み、
    　前記粘着層が、金属キレート架橋剤によって架橋されている非芳香族アクリル系重合体を含む、
    　半導体パッケージの製造方法において使用するための粘着テープ。     A substrate and an adhesive layer arranged on the substrate,
    The adhesive layer contains a non-aromatic acrylic polymer cross-linked by a metal chelate cross-linking agent,
    Adhesive tape for use in a method of manufacturing a semiconductor package.
  2. 　前記金属キレート架橋剤が、２００℃以下の沸点を有する配位子を含む、請求項１に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1, wherein the metal chelate crosslinking agent contains a ligand having a boiling point of 200 ° C or lower.
  3. 　前記金属キレート架橋剤が、アルミニウムキレート架橋剤である、請求項１又は２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1 or 2, wherein the metal chelate cross-linking agent is an aluminum chelate cross-linking agent.
  4. 　基材と、前記基材上に配置された粘着層と、を含む、半導体パッケージの製造方法において使用するための粘着テープであって、
    　下記式：
    ［（Ａ－Ｂ）／Ａ］×１００
    （式中、
    　Ａは、プラズマ処理前の前記粘着層に対する水の接触角であり、
    　Ｂは、プラズマ処理後の前記粘着層に対する水の接触角である）
    で表される、プラズマ処理の前後における前記粘着層に対する水の接触角の変化率（％）が１０％以下であり、
    　銅箔からの前記粘着テープの剥離力が、１５０℃で１００ｍＮ／２５ｍｍ以上である、前記粘着テープ。     A pressure-sensitive adhesive tape for use in a method for manufacturing a semiconductor package, comprising a base material and an adhesive layer arranged on the base material,
    The following formula:
    [(AB) / A] x 100
    (In the formula,
    A is the contact angle of water with respect to the adhesive layer before plasma treatment,
    B is the contact angle of water with respect to the adhesive layer after plasma treatment)
    And the change rate (%) of the contact angle of water with respect to the adhesive layer before and after the plasma treatment is 10% or less,
    The pressure-sensitive adhesive tape, wherein the peeling force of the pressure-sensitive adhesive tape from the copper foil is 100 mN / 25 mm or more at 150 ° C.
  5. 　リードフレームの裏面に、請求項１～４のいずれかに記載の粘着テープを貼り付ける貼付工程；
    　前記粘着テープが貼り付けられたリードフレームの表面のダイパッドに半導体チップを固定する固定工程；
    　前記半導体チップと前記リードフレームの表面とをプラズマで処理するプラズマ処理工程；
    　プラズマで処理された、前記半導体チップと前記リードフレームの表面とをボンディングワイヤーで接続する接続工程；
    　前記ボンディングワイヤーと前記半導体チップと前記リードフレームの表面とを樹脂で封止する封止工程；及び
    　前記樹脂で表面が封止されたリードフレームの裏面から前記粘着テープを剥離する剥離工程；
    を含む、半導体パッケージの製造方法。
     
          An attaching step of attaching the adhesive tape according to any one of claims 1 to 4 to the back surface of the lead frame;
    A fixing step of fixing the semiconductor chip to the die pad on the surface of the lead frame to which the adhesive tape is attached;
    A plasma treatment step of treating the semiconductor chip and the surface of the lead frame with plasma;
    A connecting step of connecting the semiconductor chip and the surface of the lead frame treated with plasma with a bonding wire;
    A sealing step of sealing the bonding wire, the semiconductor chip, and the surface of the lead frame with a resin; and a peeling step of peeling the adhesive tape from the back surface of the lead frame whose surface is sealed with the resin.
    A method for manufacturing a semiconductor package, comprising:

PCT/JP2019/037160 2018-11-16 2019-09-24 Adhesive tape and method for producing semiconductor package WO2020100434A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020556665A JP7168681B2 (en) 2018-11-16 2019-09-24 Adhesive tape and method for manufacturing semiconductor package

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-215590 2018-11-16
JP2018215590 2018-11-16

Publications (1)

Publication Number Publication Date
WO2020100434A1 true WO2020100434A1 (en) 2020-05-22

Family

ID=70730695

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/037160 WO2020100434A1 (en) 2018-11-16 2019-09-24 Adhesive tape and method for producing semiconductor package

Country Status (3)

Country Link
JP (1) JP7168681B2 (en)
TW (1) TW202035620A (en)
WO (1) WO2020100434A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022208325A1 (en) * 2021-03-29 2022-10-06 3M Innovative Properties Company Adhesive tape

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002338910A (en) * 2001-05-16 2002-11-27 Tomoegawa Paper Co Ltd Pressure-sensitive adhesive sheet for manufacturing semiconductor device
JP2006169480A (en) * 2004-12-20 2006-06-29 Lintec Corp Heat resistant adhesive tape used for semiconductor
WO2012018142A1 (en) * 2010-08-04 2012-02-09 リンテック株式会社 Adhesive for crystalline metal oxide conducting film and adhesive sheet for crystalline metal oxide conducting film using the same
JP2012059846A (en) * 2010-09-07 2012-03-22 Kawamura Sangyo Kk Adhesive film for semiconductor production
JP2012201846A (en) * 2011-03-28 2012-10-22 Furukawa Electric Co Ltd:The Pressure-sensitive adhesive tape for semiconductor wafer processing
JP2016216597A (en) * 2015-05-20 2016-12-22 ニッタ株式会社 Temperature-sensitive adhesive composition
JP2019156940A (en) * 2018-03-12 2019-09-19 リンテック株式会社 Temperature-sensitive adhesive sheet and laminate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5271316B2 (en) * 2010-07-12 2013-08-21 川崎重工業株式会社 Gear train lubricator

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002338910A (en) * 2001-05-16 2002-11-27 Tomoegawa Paper Co Ltd Pressure-sensitive adhesive sheet for manufacturing semiconductor device
JP2006169480A (en) * 2004-12-20 2006-06-29 Lintec Corp Heat resistant adhesive tape used for semiconductor
WO2012018142A1 (en) * 2010-08-04 2012-02-09 リンテック株式会社 Adhesive for crystalline metal oxide conducting film and adhesive sheet for crystalline metal oxide conducting film using the same
JP2012059846A (en) * 2010-09-07 2012-03-22 Kawamura Sangyo Kk Adhesive film for semiconductor production
JP2012201846A (en) * 2011-03-28 2012-10-22 Furukawa Electric Co Ltd:The Pressure-sensitive adhesive tape for semiconductor wafer processing
JP2016216597A (en) * 2015-05-20 2016-12-22 ニッタ株式会社 Temperature-sensitive adhesive composition
JP2019156940A (en) * 2018-03-12 2019-09-19 リンテック株式会社 Temperature-sensitive adhesive sheet and laminate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022208325A1 (en) * 2021-03-29 2022-10-06 3M Innovative Properties Company Adhesive tape

Also Published As

Publication number Publication date
TW202035620A (en) 2020-10-01
JPWO2020100434A1 (en) 2021-11-18
JP7168681B2 (en) 2022-11-09

Similar Documents

Publication Publication Date Title
JP4360446B1 (en) Semiconductor device manufacturing method and semiconductor device
JP7143845B2 (en) Temporary protective film for semiconductor encapsulation molding
JP6268329B2 (en) Adhesive composition and adhesive sheet
TW201940622A (en) Sheet for forming protective film and method of manufacturing tip having protective film
TW201222651A (en) Dicing-diebonding film and method for fabricating semiconductor device
TW200946631A (en) Dicing die bond film
JP4466397B2 (en) Adhesive film for semiconductor and semiconductor device using the same
KR20060056362A (en) Heat resistant masking tape
WO2016017789A1 (en) Adhesive sheet
JP6299315B2 (en) Wafer processing tape
JP2007059787A (en) Adhesive film for semiconductor and semiconductor device using it
KR101208082B1 (en) Adhesive tape for semiconductor process and manufacturing method thereof
JP2008179820A (en) Adhesive film for semiconductor and semiconductor device using this
KR20170103749A (en) Resin film-forming sheet, resin film-forming composite sheet, and silicon wafer regeneration method
JP7168681B2 (en) Adhesive tape and method for manufacturing semiconductor package
JP7151782B2 (en) Temporary protective film for manufacturing semiconductor device, reel body, and method for manufacturing semiconductor device
TWI759029B (en) Adhesive tape
TWI827551B (en) Adhesive film for semiconductor device manufacturing, semiconductor device and manufacturing method thereof
TW202330830A (en) Thermosetting adhesive composition, multilayer film, bonded body and method for producing same
KR20230141527A (en) Protective film forming film, composite sheet for forming protective film, method of manufacturing semiconductor device, and use of protective film forming film
TW202334354A (en) Pressure-sensitive adhesive composition to be used in pressure-sensitive adhesive tape for semiconductor processing and pressure-sensitive adhesive tape using the pressure-sensitive adhesive composition
KR20140085714A (en) Adhesive tape for electronic component
TW202016251A (en) Adhesion agent composition, adhesive film, and method for producing connecting body

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19885062

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020556665

Country of ref document: JP

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 19885062

Country of ref document: EP

Kind code of ref document: A1