WO2016027883A1 - Feuille pour formation de membrane protectrice, et procédé de fabrication de puce semi-conductrice avec membrane protectrice - Google Patents

Feuille pour formation de membrane protectrice, et procédé de fabrication de puce semi-conductrice avec membrane protectrice Download PDF

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Publication number
WO2016027883A1
WO2016027883A1 PCT/JP2015/073503 JP2015073503W WO2016027883A1 WO 2016027883 A1 WO2016027883 A1 WO 2016027883A1 JP 2015073503 W JP2015073503 W JP 2015073503W WO 2016027883 A1 WO2016027883 A1 WO 2016027883A1
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WIPO (PCT)
Prior art keywords
protective film
forming
film
sheet
workpiece
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PCT/JP2015/073503
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English (en)
Japanese (ja)
Inventor
山本　大輔
尚哉 佐伯
裕之 米山
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リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to SG11201701272UA priority Critical patent/SG11201701272UA/en
Priority to JP2016544263A priority patent/JP6589209B2/ja
Priority to CN201580044561.4A priority patent/CN106660332B/zh
Priority to KR1020177004494A priority patent/KR102376017B1/ko
Priority to MYPI2017700515A priority patent/MY186759A/en
Publication of WO2016027883A1 publication Critical patent/WO2016027883A1/fr
Priority to PH12017500285A priority patent/PH12017500285A1/en

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    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/50—Working by transmitting the laser beam through or within the workpiece
    • B23K26/53—Working by transmitting the laser beam through or within the workpiece for modifying or reforming the material inside the workpiece, e.g. for producing break initiation cracks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body

Definitions

  • the present invention relates to a protective film-forming sheet capable of forming a protective film on a workpiece such as a semiconductor wafer or a workpiece (for example, a semiconductor chip) obtained by processing the workpiece.
  • a protective film-forming sheet capable of forming a protective film on a workpiece such as a semiconductor wafer or a workpiece (for example, a semiconductor chip) obtained by processing the workpiece.
  • semiconductor devices have been manufactured by a mounting method called a face-down method.
  • a mounting method called a face-down method.
  • the circuit surface side of the semiconductor chip is bonded to a chip mounting portion such as a lead frame. Therefore, the back surface side of the semiconductor chip on which no circuit is formed is exposed.
  • Patent Documents 1 and 2 disclose a protective film forming / dicing integrated sheet (that is, a protective film) in which a protective film forming layer (that is, a protective film forming film) capable of forming the protective film is formed on an adhesive sheet. Forming sheet).
  • the protective film forming / dicing integrated sheet the protective film forming film is cured by heat treatment to form the protective film. That is, according to the protective film forming / dicing integrated sheet, both the dicing of the semiconductor wafer and the protective film formation on the semiconductor chip can be performed, and the semiconductor chip with the protective film can be obtained.
  • a laminated adhesive sheet (that is, a laminate in which two adhesive sheets comprising a base material and an adhesive layer are laminated) is attached to an extremely thin semiconductor wafer, and the laminated adhesive sheet is laminated from the laminated adhesive sheet side.
  • Stealth dicing to divide the semiconductor wafer along the dicing line and produce semiconductor chips by expanding the adhesive sheet after irradiating the semiconductor wafer with laser light and forming the modified part inside the semiconductor wafer The law is disclosed.
  • the member positioned between the adhesive sheet and the semiconductor wafer is also divided in the same manner as the semiconductor wafer.
  • a protective film formation film may be cooled.
  • the protective film in stealth dicing, when a member positioned between a pressure sensitive adhesive sheet and a workpiece such as a semiconductor wafer is a protective film formed from a protective film forming film, the protective film is suitable when the pressure sensitive adhesive sheet is expanded. It aims at providing the sheet
  • segmented into. Another object of the present invention is to provide a method for producing a workpiece such as a semiconductor chip with a protective film using the protective film-forming sheet.
  • a protective film-forming sheet comprising a first support sheet and a protective film-forming film laminated on the first surface side of the first support sheet, wherein the protective film-forming film is cured
  • the protective film made of a conductive material and formed by curing the protective film-forming film has a breaking strain at 50 ° C. of 20% or less and a peak temperature T1 of loss tangent within a range of 25 ° C. to 60 ° C.
  • a protective film forming sheet comprising a first support sheet and a protective film-forming film laminated on the first surface side of the first support sheet, wherein the protective film-forming film is cured
  • the protective film made of a conductive material and formed by curing the protective film-forming film has a breaking strain at 50 ° C. of 20% or less and a peak temperature T1 of loss tangent within a range of 25 ° C. to 60 ° C.
  • the said protective film is a sheet
  • the said protective film is a sheet
  • the protective film forming sheet includes the second support sheet laminated on the surface of the protective film forming film opposite to the surface facing the first support sheet. 4) The protective film-forming sheet according to any one of 4).
  • the first support sheet provided in the protective film forming sheet is stretched in a state where the protective film is held within a range of 40 ° C.
  • Laminating step of obtaining a third laminate comprising: a second curing step of obtaining the protective film by curing the protective film-forming film provided in the third laminated body; a third substrate; The third pressure-sensitive adhesive layer side surface of the processing sheet provided with a third pressure-sensitive adhesive layer laminated on one surface side of the third base material, and the third curing step.
  • a protective film-forming sheet comprising a first support sheet and a protective film-forming film laminated on the first surface side of the first support sheet,
  • the protective film-forming film is made of a curable material,
  • the protective film-forming film has the following characteristics: When the protective film-forming film is cured to form a protective film, the breaking strain at 50 ° C. is 20% or less and the loss tangent peak temperature T1 is 25 ° C. to 60 ° C.
  • the protective film-forming sheet according to [1], wherein the protective film-forming film further has the following characteristics:
  • the storage elastic modulus at 25 ° C. of the protective film is 3.0 ⁇ 10 9 Pa or more.
  • a surface opposite to the surface facing the first support sheet in the protective film-forming film provided in the protective film-forming sheet described in any one of [1] to [5] A sticking step of obtaining a first laminate including the protective film forming sheet and the work by sticking the exposed face to one face of the work;
  • the first support sheet is extended in a state where the temperature T2 of the protective film in the first laminated body that has undergone the first curing step is maintained within a range of 40 ° C.
  • dividing the protective film By dividing the protective film, a plurality of chips with the protective film formed by dividing the laminate of the workpiece and the protective film so that a cut surface is generated in the thickness direction is provided on one side of the first support sheet.
  • the modified layer forming a modified layer in the workpiece interior.
  • Irradiate The method of manufacturing a protective layer with a chip containing the modified layer forming step, forming a modified layer in the workpiece interior.
  • the protective film forming sheet of the present invention even if the protective film formed from the protective film forming film is a member located between the adhesive sheet and a workpiece such as a semiconductor wafer, the adhesive sheet in stealth dicing.
  • the protective film can be appropriately divided when the is expanded. Therefore, it is possible to stably manufacture a semiconductor chip with a protective film.
  • FIG. 1 is a cross-sectional view of a protective film forming sheet according to an embodiment of the present invention.
  • the protective film forming sheet 3 according to the present embodiment includes a first support sheet 4 and one surface of the first support sheet 4 (a “first surface” to be described later;
  • the jig pressure-sensitive adhesive layer 5 is a layer for bonding the protective film forming sheet 3 to a jig such as a ring frame.
  • the protective film forming sheet 3 includes a release sheet 6 on the protective film forming film 1 and the jig pressure-sensitive adhesive layer 5 (that is, opposite to the first support sheet 4). ing.
  • the release sheet 6 is a sheet that is peeled and removed when the protective film forming sheet 3 is used, and is not an essential component in the protective film forming sheet 3. That is, one side surface of the protective film-forming sheet according to one embodiment of the present invention includes a first support sheet 4 and a protective film-forming film 1 laminated on one surface side of the first support sheet 4.
  • the protective film-forming sheet 3 holds the workpiece by being attached to the workpiece when the workpiece is processed, and a protective film is applied to the workpiece or a workpiece obtained by processing the workpiece. Used to form.
  • This protective film is composed of a cured protective film-forming film 1.
  • the protective film forming sheet 3 according to the present embodiment is used to hold a semiconductor wafer during dicing processing of a semiconductor wafer as a workpiece and to form a protective film on a semiconductor chip obtained by dicing. It is not limited to this.
  • the protective film forming sheet 3 according to the present embodiment is usually formed into a long shape, wound into a roll, and used in a roll-to-roll manner.
  • the first support sheet 4 according to the protective film-forming sheet 3 according to an embodiment of the present invention includes a base 41 and one surface side of the base 41 (that is, the protective film-forming film 1 side; 1 and the adhesive layer 42 laminated on the upper side).
  • first surface the surface of the first support sheet 4 on which the protective film forming film 1 is laminated
  • second surface the opposite surface (the lower surface in FIG. 1)
  • first support sheet 4 the pressure-sensitive adhesive layer 42 is laminated on the first surface side of the first support sheet 4
  • the base material 41 is laminated on the second surface side of the first support sheet 4. ing.
  • the base material 41 according to the protective film-forming sheet 3 according to an embodiment of the present invention is not particularly limited as long as it is a base material normally used as a base material of an adhesive sheet used for stealth dicing.
  • the base material 41 may have a single layer structure or a laminated structure.
  • the protective film-forming film 1 is a film that forms a protective film by heating, and the substrate 41 is also heated when the protective film-forming film 1 for forming the protective film is heated, No. 41 is required to be a base material that can be appropriately used even after this heating (for example, it can be appropriately expanded).
  • the melting point of the base material 41 is preferably 90 to 180 ° C., particularly preferably 100 to 160 ° C., and further preferably 110 to 150 ° C.
  • the storage elastic modulus of the substrate 41 at 130 ° C. is preferably 1 to 100 MPa.
  • the storage elastic modulus at 130 ° C. is in the above range, it is possible to reduce the possibility that a problem occurs when the first support sheet 4 is expanded while ensuring the heat resistance of the base material 41.
  • the storage elastic modulus of the base material 41 at 130 ° C. is more preferably 2 to 80 MPa. It is particularly preferably 5 to 50 MPa.
  • the measuring method of the said storage elastic modulus is as showing to the test example mentioned later.
  • the method of adjusting the storage elastic modulus in 130 degreeC of the base material 41 generally it can adjust mainly with the storage elastic modulus of the resin material to be used.
  • the storage elastic modulus tends to increase when the molecular weight is high, and the storage elastic modulus tends to increase due to cross-linking or narrow molecular weight distribution. Based on this tendency, it can be adjusted to an arbitrary storage elastic modulus.
  • the light transmittance at a wavelength of 1064 nm after the substrate 41 is heated is preferably 40% or more and 100% or less, and is preferably 50% or more and 99.9%. More preferably, it is 60% or more and 99.5% or less. Since the light transmittance at a wavelength of 1064 nm after the heating of the base material 41 is in the above range, the work can be divided by stealth dicing.
  • the light transmittance at a wavelength of 532 nm after the substrate 41 is heated is preferably 0.1% or more and 40% or less. It is more preferably 3% or more and 35% or less, and particularly preferably 0.5% or more and 30% or less. Since the light transmittance at a wavelength of 532 nm after heating the substrate 41 is in the above range, the laser printability is excellent.
  • the resin film constituting the substrate 41 include polyethylene films such as low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, and high density polyethylene (HDPE) film, polypropylene film, and ethylene-propylene.
  • polyethylene films such as low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, and high density polyethylene (HDPE) film, polypropylene film, and ethylene-propylene.
  • Polyolefin films such as copolymer film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, norbornene resin film; ethylene-vinyl acetate copolymer film, ethylene- (meth) acrylic acid copolymer Polymer films, ethylene copolymer films such as ethylene- (meth) acrylate copolymer films; polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films Lum, polyethylene terephthalate film, a polyester film such as polyethylene terephthalate and polybutylene terephthalate film; polyurethane film; polyimide film; polystyrene films; polycarbonate films; fluororesin films and the like.
  • modified films such as these crosslinked films and ionomer films are also used.
  • a laminated film in which a plurality of the above films are laminated may be used.
  • (meth) acrylic acid in the present specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.
  • polyolefin film is preferable, polyethylene film, polypropylene film and ethylene-propylene copolymer film are more preferable, and ethylene-propylene copolymer film is particularly preferable.
  • these resin films the above-described physical properties are easily satisfied.
  • the above-described physical properties are satisfied by adjusting the copolymerization ratio of the ethylene monomer and the propylene monomer. easy.
  • these resin films are preferable also from a viewpoint of workpiece sticking property or chip peelability.
  • the resin film may be subjected to a surface treatment by an oxidation method, an unevenness method, or a primer treatment on one or both sides as desired for the purpose of improving the adhesion with the pressure-sensitive adhesive layer 42 laminated on the surface.
  • an oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, and ultraviolet irradiation treatment.
  • the unevenness method include a sand blast method and a thermal spraying method.
  • the base material 41 may contain various additives such as a colorant, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler in the resin film.
  • the thickness of the substrate 41 is not particularly limited as long as it can function properly in each step in which the protective film forming sheet 3 is used, but is preferably 20 ⁇ m to 450 ⁇ m, more preferably 25 ⁇ m to 400 ⁇ m. 50 ⁇ m to 350 ⁇ m is particularly preferable.
  • the “thickness” means a value represented by an average of thicknesses measured with a contact-type thickness meter at any five locations.
  • the pressure-sensitive adhesive layer 42 provided in the first support sheet 4 according to the protective film-forming sheet 3 according to an embodiment of the present invention may be composed of an energy ray non-curable pressure-sensitive adhesive, or energy rays. You may be comprised from a curable adhesive.
  • the energy ray non-curable adhesive those having desired adhesive strength and removability are preferable, for example, acrylic adhesive, rubber adhesive, silicone adhesive, urethane adhesive, polyester adhesive.
  • Polyvinyl ether-based pressure-sensitive adhesives can be used. Among these, an acrylic pressure-sensitive adhesive having high adhesion to the protective film-forming film 1 is preferable.
  • the adhesive strength of the energy ray-curable adhesive is reduced by irradiation with energy rays. Therefore, if an energy ray-curable pressure-sensitive adhesive is used, when the work or workpiece and the first support sheet 4 are desired to be separated, they can be easily separated by irradiating energy rays.
  • energy rays ultraviolet rays, electron beams, etc. are usually used. Irradiation of energy rays varies depending on the kind of energy rays, for example, in the case of ultraviolet rays, preferably 50 ⁇ 1000mJ / cm 2 in quantity, more preferably 100 ⁇ 500mJ / cm 2. In the case of an electron beam, about 10 to 1000 krad is preferable.
  • the pressure-sensitive adhesive layer 42 in the protective film forming sheet 3 is preferably cured.
  • a material obtained by curing an energy ray-curable pressure-sensitive adhesive usually has a high elastic modulus and high surface smoothness. Therefore, the protective film-forming film 1 in contact with a cured portion made of such a material is cured to form a protective film.
  • the surface of the protective film in contact with the cured portion of the pressure-sensitive adhesive layer 42 has high smoothness (gloss), and is excellent in appearance as a protective film for the chip. Further, when laser printing is performed on a protective film having high surface smoothness, the visibility of the printing is improved.
  • the energy ray-curable pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 42 may be mainly composed of a polymer having energy ray-curing property; a polymer having no energy ray-curing property and many energy ray-curing properties.
  • the pressure-sensitive adhesive may be mainly composed of a mixture with at least one component selected from the group consisting of functional monomers and oligomers.
  • the “main component” as used herein means that it is contained in an amount of 60% by mass or more based on the total mass of the energy ray-curable pressure-sensitive adhesive.
  • the polymer having energy ray curability is a (meth) acrylic acid ester (co) polymer (A) in which a functional group having energy ray curability (that is, energy ray curable group) is introduced into the side chain (hereinafter referred to as “ It is preferably an energy beam curable polymer (A) ”.
  • This energy ray curable polymer (A) includes a (meth) acrylic copolymer (a1) having a functional group-containing monomer unit, and an unsaturated group-containing compound (a2) having a substituent bonded to the functional group. It is preferable that it is a polymer obtained by making it react.
  • the acrylic copolymer (a1) comprises at least a structural unit derived from a functional group-containing monomer and a structural unit derived from a (meth) acrylate monomer or a derivative thereof.
  • the functional group-containing monomer in the structural unit derived from the functional group-containing monomer includes a monomer having a polymerizable double bond and a functional group such as a hydroxyl group, an amino group, a substituted amino group, and an epoxy group in the molecule. preferable.
  • the functional group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
  • Examples of the (meth) acrylic acid ester monomer include alkyl (meth) acrylates having an alkyl group having 1 to 20 carbon atoms, cycloalkyl (meth) acrylates having an alkyl group having 3 to 11 carbon atoms, and benzyl (meth) acrylate. Etc. are used.
  • alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms are preferred, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate.
  • the structural unit derived from the functional group-containing monomer is usually 3 to 100% by mass, preferably 5 to 40% by mass, based on the total mass of the acrylic copolymer (a1).
  • a structural unit derived from a (meth) acrylic acid ester monomer or a derivative thereof is usually contained in an amount of 0 to 97% by mass, preferably 60 to 95% by mass. That is, the acrylic copolymer (a1) contains 3 to 100% by mass of structural units derived from the functional group-containing monomer with respect to the total mass of the acrylic copolymer (a1).
  • a structural unit derived from a meth) acrylate monomer or a derivative thereof is usually contained in a proportion of 0 to 97% by mass; a structural unit derived from the functional group-containing monomer is contained in a proportion of 5 to 40% by mass. It is more preferable that the structural unit derived from the (meth) acrylic acid ester monomer or a derivative thereof is usually contained in a proportion of 60 to 95% by mass. In addition, the total mass of the structural unit derived from the functional group-containing monomer and the structural unit derived from the (meth) acrylic acid ester monomer or derivative thereof does not exceed 100% by mass.
  • the acrylic copolymer (a1) can be obtained by copolymerizing a functional group-containing monomer as described above with a (meth) acrylic acid ester monomer or a derivative thereof in a conventional manner. Dimethylacrylamide, vinyl formate, vinyl acetate, styrene and the like may be copolymerized.
  • the substituent of the unsaturated group-containing compound (a2) can be appropriately selected according to the type of functional group of the functional group-containing monomer unit of the acrylic copolymer (a1).
  • the substituent is preferably an isocyanate group or an epoxy group
  • the substituent is an amino group, a carboxyl group or an aziridinyl group. preferable.
  • the unsaturated group-containing compound (a2) contains 1 to 5, preferably 1 to 2, energy beam polymerizable carbon-carbon double bonds per molecule.
  • Specific examples of such unsaturated group-containing compound (a2) include, for example, 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- ( Bisacryloyloxymethyl) ethyl isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; diisocyanate compound or polyisocyanate compound, polyol compound, and hydroxyethyl (meth) Acryloyl monoisocyanate compound obtained by reaction with acrylate; glycidyl (meth) acrylate; (meth) acrylic acid, 2- (1
  • the unsaturated group-containing compound (a2) is usually used in a proportion of 10 to 100 equivalents, preferably 20 to 95 equivalents, per 100 equivalents of the functional group-containing monomer of the acrylic copolymer (a1).
  • the reaction temperature, pressure, solvent, time, presence of catalyst, catalyst can be selected as appropriate.
  • the functional group present in the acrylic copolymer (a1) reacts with the substituent in the unsaturated group-containing compound (a2), so that the unsaturated group is contained in the acrylic copolymer (a1). It introduce
  • the weight average molecular weight of the energy beam curable polymer (A) thus obtained is preferably 10,000 or more, more preferably 150,000 to 1,500,000, particularly preferably 200,000 to 1,000,000.
  • the weight average molecular weight (Mw) in this specification is the value of polystyrene conversion measured by the gel permeation chromatography method (GPC method).
  • the energy beam curable pressure sensitive adhesive is mainly composed of a polymer having energy beam curable properties
  • the energy beam curable pressure sensitive adhesive is at least selected from the group consisting of energy beam curable monomers and oligomers.
  • One component (B) may be further contained.
  • At least one component (B) selected from the group consisting of energy ray-curable monomers and oligomers for example, an ester of a polyhydric alcohol and (meth) acrylic acid can be used.
  • Examples of at least one component (B) selected from the group consisting of such energy ray-curable monomers and oligomers include monofunctional acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane
  • Polyfunctional oligoesters such as diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate; polyester oligo (meth) acrylate Rate, and polyurethane oligo (meth) acrylate.
  • At least one component (B) selected from the group consisting of energy beam curable monomers and / or oligomers it is selected from the group consisting of energy beam curable monomers and oligomers in the energy beam curable adhesive.
  • the content of at least one component (B) is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the energy ray-curable pressure-sensitive adhesive.
  • photopolymerization initiator (C) examples include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, 2,4-diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, ⁇ -chloranthraquinone, (2,4 6-trimethylbenzyldiphenyl) phosphine oxide, 2-benzothiazole-N, N-diethyldithiocarbamate, oligo ⁇ 2-hydroxy-2-methy 1- [4-trimethyl
  • the photopolymerization initiator (C) is an energy ray curable copolymer (A) (in the case of blending at least one component (B) selected from the group consisting of energy ray curable monomers and oligomers).
  • A energy ray curable copolymer
  • B component selected from the group consisting of energy ray curable monomers and oligomers
  • the amount is preferably 0.1 to 10 parts by mass, particularly 0.5 to 6 parts by mass.
  • the energy ray curable pressure-sensitive adhesive other components may be appropriately blended in addition to the above components.
  • other components include a polymer component or oligomer component (D) that does not have energy beam curability, and a crosslinking agent (E).
  • a polymer component or oligomer component (D) that does not have energy beam curability and a crosslinking agent (E).
  • one aspect of the energy beam curable pressure-sensitive adhesive is at least one component (B) selected from the group consisting of an energy beam curable copolymer (A) and, optionally, an energy beam curable monomer and oligomer.
  • Examples of the polymer component or oligomer component (D) having no energy ray curability include polyacrylates, polyesters, polyurethanes, polycarbonates, polyolefins, etc., and polymers having a weight average molecular weight (Mw) of 3,000 to 2.5 million. Or an oligomer is preferable.
  • crosslinking agent (E) a polyfunctional compound having reactivity with the functional group of the energy beam curable copolymer (A) or the like can be used.
  • polyfunctional compounds include isocyanate compounds, epoxy compounds, amine compounds, melamine compounds, aziridine compounds, hydrazine compounds, aldehyde compounds, oxazoline compounds, metal alkoxide compounds, metal chelate compounds, metal salts, ammonium salts. And reactive phenol resins.
  • the blending amount of these other components is not particularly limited, and is appropriately determined in the range of 0 to 40 parts by mass with respect to 100 parts by mass of the energy beam curable copolymer (A).
  • the energy ray curable pressure-sensitive adhesive is mainly composed of a mixture of a polymer component not having energy ray curable properties and at least one selected from the group consisting of energy ray curable polyfunctional monomers and oligomers. This will be described below.
  • the polymer component having no energy beam curability for example, the same components as those of the acrylic copolymer (a1) described above can be used.
  • the content of the polymer component having no energy beam curability in the energy beam curable resin composition is preferably 20 to 99.9% by mass with respect to the total mass of the energy beam curable resin composition. In particular, it is preferably 30 to 80% by mass.
  • the at least one component selected from the group consisting of energy ray-curable polyfunctional monomers and oligomers the same components as the aforementioned component (B) are selected.
  • the blending ratio of the polymer component not having energy ray curability to at least one component selected from the group consisting of energy ray curable polyfunctional monomers and oligomers is 100 parts by mass of the polymer component not having energy ray curability.
  • at least one component selected from the group consisting of a polyfunctional monomer and an oligomer is preferably 10 to 150 parts by mass, and more preferably 25 to 100 parts by mass.
  • the photopolymerization initiator (C) and the crosslinking agent (E) can be appropriately blended as described above. That is, one aspect of the energy ray curable pressure-sensitive adhesive is a polymer component that does not have energy ray curable, at least one component selected from the group consisting of energy ray curable polyfunctional monomers and oligomers, and, if desired, And at least one component selected from the group consisting of a photopolymerization initiator (C) and a crosslinking agent (E).
  • the thickness of the pressure-sensitive adhesive layer 42 is not particularly limited as long as it can function properly in each step in which the protective film forming sheet 3 is used. Specifically, the thickness is preferably 1 ⁇ m to 50 ⁇ m, more preferably 2 ⁇ m to 30 ⁇ m, and particularly preferably 3 ⁇ m to 20 ⁇ m.
  • the protective film forming film 1 is a film for forming a protective film on a workpiece or a workpiece obtained by processing the workpiece.
  • This protective film is composed of a cured protective film-forming film 1.
  • the workpiece include a semiconductor wafer, and examples of the workpiece obtained by processing the workpiece include a semiconductor chip.
  • the present invention is not limited to these.
  • the protective film is formed on the back side of the semiconductor wafer (the side on which no electrodes such as bumps are formed).
  • the protective film-forming film 1 may be a single-layer film or a multi-layer film. However, the protective-film-forming film 1 is a single layer in terms of ease of light transmittance control and manufacturing cost. Is preferred.
  • the protective film-forming film 1 is preferably made of a curable material, and a specific example of such a material is an uncured curable adhesive.
  • a workpiece such as a semiconductor wafer
  • the protective film forming film 1 is cured, thereby firmly bonding the protective film formed of the cured protective film forming film 1 to the workpiece.
  • a durable protective film can be formed on the chip or the like. That is, one side surface of the protective film forming sheet according to one embodiment of the present invention includes a protective film forming film made of an uncured curable material.
  • the protective film-forming film 1 preferably has adhesiveness at room temperature or exhibits adhesiveness by heating. Thereby, when superposing
  • the curable adhesive constituting the protective film-forming film 1 having the above characteristics contains a curable component and a binder polymer component.
  • a curable component a thermosetting component, an energy ray curable component, or a mixture thereof can be used, but it is particularly preferable to use a thermosetting component. That is, the protective film forming film 1 is preferably composed of a thermosetting adhesive.
  • thermosetting component examples include epoxy resins, phenol resins, melamine resins, urea resins, polyester resins, urethane resins, acrylic resins, polyimide resins, benzoxazine resins, and mixtures thereof.
  • an epoxy resin, a phenol resin, and a mixture thereof are preferably used.
  • Epoxy resin has the property of forming a three-dimensional network and forming a strong film when heated.
  • an epoxy resin conventionally known various epoxy resins are used, but those having a molecular weight (formula) of about 300 to 2000 are preferable, and those having a molecular weight of 300 to 500 are more preferable.
  • the epoxy equivalent of the epoxy resin is preferably 50 to 5000 g / eq.
  • epoxy resins include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolac; glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; Glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid; glycidyl type or alkyl glycidyl type epoxy resins in which active hydrogen bonded to nitrogen atom such as aniline isocyanurate is substituted with glycidyl group; 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3 - Epoxy) as cyclohexane -m- dioxane, carbon in the
  • bisphenol-based glycidyl type epoxy resins o-cresol novolac type epoxy resins and phenol novolac type epoxy resins are preferably used. These epoxy resins may be used alone or in combination of two or more.
  • thermally activated latent epoxy resin 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.
  • the heat activated latent epoxy resin curing agent is activated by a method in which active species (anions and cations) are generated by a chemical reaction by heating; the epoxy resin is stably dispersed in the epoxy resin at around room temperature and is heated at a high temperature.
  • thermally active latent epoxy resin curing agent examples include various onium salts, dibasic acid dihydrazide compounds, dicyandiamide, amine adduct curing agents, high melting point active hydrogen compounds such as imidazole compounds, and the like. These thermally activated latent epoxy resin curing agents can be used singly or in combination of two or more.
  • the heat-activatable latent epoxy resin curing agent as described above is preferably 0.1 to 20 parts by weight, particularly preferably 0.2 to 10 parts by weight, and still more preferably 0.8 to 100 parts by weight of the epoxy resin. It is used at a ratio of 3 to 5 parts by weight.
  • phenolic resin condensates of phenols such as alkylphenols, polyhydric phenols, naphthols, and aldehydes are used without particular limitation.
  • 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 modified products thereof Etc. are used.
  • the phenolic hydroxyl group contained in these phenolic resins can easily undergo an addition reaction with the epoxy group of the above epoxy resin by heating to form a cured product having high impact resistance. For this reason, you may use together an epoxy resin and a phenol-type resin.
  • Examples of the energy ray curable component include components listed as at least one component selected from the group consisting of an energy ray curable polymer in the pressure-sensitive adhesive layer 42 and energy ray curable monomers and oligomers.
  • the binder polymer component can give an appropriate tack to the protective film forming film 1 and improve the operability of the protective film forming sheet 3.
  • the weight average molecular weight of the binder polymer is usually in the range of 50,000 to 2,000,000, preferably 100,000 to 1,500,000, particularly preferably 200,000 to 1,000,000. When the weight average molecular weight is too low, the film formation of the protective film-forming film 1 becomes insufficient, and when it is too high, the compatibility with other components is deteriorated, and as a result, uniform film formation is prevented.
  • a binder polymer for example, an acrylic polymer, a polyester resin, a phenoxy resin, a urethane resin, a silicone resin, a rubber polymer, and the like are used, and an acrylic polymer is particularly preferably used.
  • the acrylic polymer examples include a (meth) acrylic acid ester copolymer composed of a (meth) acrylic acid ester monomer and a structural unit derived from a (meth) acrylic acid derivative.
  • the (meth) acrylic acid ester monomer is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms, specifically, methyl (meth) acrylate, (meth) Examples include ethyl acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.
  • (meth) acrylic acid derivatives include (meth) acrylic acid, glycidyl (meth) acrylate, and hydroxyethyl (meth) acrylate.
  • the weight average molecular weight of the polymer is preferably 100,000 or more, particularly preferably 150,000 to 1,000,000.
  • the glass transition temperature of the acrylic polymer is usually 20 ° C. or lower, preferably about ⁇ 70 ° C. to 0 ° C., and has adhesiveness at room temperature (23 ° C.).
  • the blending ratio of the thermosetting component and the binder polymer component is the blending amount of the thermosetting component, preferably 50-1500 parts by weight, more preferably 70-1000 parts by weight, when the binder polymer component is 100 parts by weight. Particularly preferred is 80 to 800 parts by weight.
  • the protective film-forming film 1 may further contain at least one component selected from the group consisting of a colorant and a filler.
  • the colorant for example, known colorants such as inorganic pigments, organic pigments, organic dyes and the like can be used.
  • the colorant is an organic colorant. It is preferable to contain.
  • the colorant is a colorant composed of a pigment. Preferably there is.
  • the filler examples include silica such as crystalline silica, fused silica, and synthetic silica, and inorganic filler such as alumina and glass balloon.
  • silica is preferable, synthetic silica is more preferable, and synthetic silica of the type in which ⁇ -ray sources that cause malfunction of the semiconductor device are removed as much as possible is optimal.
  • the shape of the filler include a spherical shape, a needle shape, and an indefinite shape, and a spherical shape is preferable, and a true spherical shape is particularly preferable.
  • the content of at least one component selected from the group consisting of a colorant and a filler is preferably 5 to 75% by mass with respect to the total mass of the protective film-forming film.
  • the average particle size of the filler is preferably 0.005 to 20 ⁇ m.
  • the protective film forming film 1 may contain a coupling agent.
  • a coupling agent By containing the coupling agent, after the protective film forming film 1 is cured, the adhesiveness and adhesion between the protective film and the workpiece can be improved without impairing the heat resistance of the protective film. Water resistance (moisture heat resistance) can also be improved.
  • a silane coupling agent is preferable because of its versatility and cost merit.
  • silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (methacryloxy).
  • ⁇ -glycidoxypropyltrimethoxysilane is preferred. These can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the coupling agent is 0.1 when the total mass part of the binder polymer component and the curable component is 100 parts by mass. ⁇ 5 parts by mass are preferred.
  • the protective film-forming film 1 may contain a crosslinking agent such as an organic polyvalent isocyanate compound, an organic polyvalent imine compound, and an organometallic chelate compound in order to adjust the cohesive force before curing.
  • the protective film-forming film 1 may contain an antistatic agent in order to suppress static electricity and improve the reliability of the chip.
  • the protective film-forming film 1 may contain a flame retardant such as a phosphoric acid compound, a bromine compound, or a phosphorus compound in order to enhance the flame retardant performance of the protective film and improve the reliability as a package.
  • one side surface of the protective film-forming film 1 includes at least one component selected from the group consisting of a curable component, a binder polymer component, and, if desired, a colorant and a filler, a coupling agent, a crosslinking agent, a charging agent. And at least one component selected from the group consisting of an inhibitor and a flame retardant.
  • the thickness of the protective film-forming film 1 is preferably 3 ⁇ m to 300 ⁇ m, more preferably 5 ⁇ m to 200 ⁇ m, and more preferably 7 ⁇ m to 100 ⁇ m in order to effectively exhibit the function as a protective film. Particularly preferred.
  • the protective film has a breaking strain at 50 ° C. of 0.1% or more and 20% or less.
  • the breaking strain is 20% or less, when the first support sheet 4 is expanded (expanded) under the conditions described later, the protective film provided in the first support sheet 4 can be appropriately divided. It becomes possible.
  • the breaking strain at 50 ° C. exceeds 20%, the protective film is likely to be divided inappropriately. Specifically, the phenomenon in which the material forming the protective film in the divided portion is partly thread-like and does not split (this book In the specification, it is also referred to as “stringing phenomenon”). From the viewpoint of more stably achieving appropriate division of the protective film, the breaking strain at 50 ° C.
  • the “breaking strain at 50 ° C.” of the protective film can be measured by a method described in a test example described later.
  • the protective film has a loss tangent peak temperature T1 in the range of 25 ° C to 60 ° C.
  • the condition described later specifically, the temperature T2 of the protective film when the first support sheet 4 is extended in the first dividing step is 40 ° C.
  • the protective film provided in the first support sheet 4 can be appropriately divided.
  • the temperature T1 is excessively low, the protective film becomes soft, and the breaking strain at 50 ° C. of the protective film tends to exceed 20%.
  • the temperature T2 is preferably equal to or higher than the peak temperature T1 of the loss tangent.
  • the “peak temperature of loss tangent” of the protective film can be measured by the method described in a test example described later.
  • the protective film preferably has a storage elastic modulus at 25 ° C. of 3.0 ⁇ 10 9 Pa or more and 5.0 ⁇ 10 11 or less, and is 5.0 ⁇ 10 9 Pa or more and 1.0 ⁇ 10 11 or less. More preferably.
  • the storage elastic modulus at 25 ° C. of the protective film is 3.0 ⁇ 10 9 Pa or more, when the semiconductor chip with the protective film is separated from the first support sheet 4, the problem that the protective film gets stuck is less likely to occur. .
  • the protective film preferably has a loss tangent at 25 ° C. of 0.01 or more and 0.4 or less.
  • the loss tangent of the protective film at 25 ° C. is more preferably 0.03 or more and 0.3 or less, and particularly preferably 0.05 or more and 0.2 or less.
  • the “storage elastic modulus at 25 ° C.” and “loss tangent at 25 ° C.” of the protective film can be measured by the methods described in the test examples described later.
  • the protective film preferably has a light transmittance at a wavelength of 1064 nm of 40% or more and 100% or less. Since the light transmittance at a wavelength of 1064 nm of the protective film is 40% or more, the laser light for stealth dicing can efficiently reach the workpiece such as a semiconductor wafer. From the viewpoint of more stably realizing efficient arrival of the laser beam to the semiconductor wafer, the light transmittance at a wavelength of 1064 nm of the protective film is preferably 50% or more and 99.9% or less, and 60% or more. 99.5% or less is more preferable.
  • the protective film preferably has a breaking stress at 50 ° C. of 1.0 ⁇ 10 3 Pa or more and 2.0 ⁇ 10 7 Pa or less.
  • the breaking stress is 2.0 ⁇ 10 7 Pa or less
  • the breaking stress at 50 ° C. is 2.0 ⁇ 10 7 Pa or less
  • the “breaking stress at 50 ° C.” of the protective film can be measured by a method described in a test example described later.
  • one side surface of the protective film-forming sheet of the present invention has the protective film-forming film
  • the protective film-forming film is a protective film-forming sheet having the following characteristics:
  • the breaking strain at 50 ° C. is 0.1% or more and 20% or less, and the loss tangent peak temperature T1 is in the range of 25 ° C. to 60 ° C.
  • the protective film-forming film may further have at least one of the following characteristics: Storage elastic modulus at 25 ° C. is 3.0 ⁇ 10 9 Pa or more and 5.0 ⁇ 10 11 or less; Loss tangent at 25 ° C. is 0.01 or more and 0.4 or less;
  • the light transmittance at a wavelength of 1064 nm is 40% or more and 100% or less;
  • the breaking stress at 50 ° C. is 1.0 ⁇ 10 3 Pa or more and 2.0 ⁇ 10 7 Pa or less.
  • the “characteristic” means a chemical or physicochemical characteristic of the protective film-forming film.
  • Adhesive layer for jigs Adhesives constituting the adhesive layer 5 for jigs are preferably adhesives having a desired adhesive strength and removability, such as acrylic adhesives, rubber adhesives, and silicone adhesives.
  • An adhesive, a urethane-based adhesive, a polyester-based adhesive, a polyvinyl ether-based adhesive, or the like can be used.
  • an acrylic pressure-sensitive adhesive that has high adhesion to a jig such as a ring frame and can effectively prevent the protective film forming sheet 3 from being peeled off from the ring frame or the like in a dicing process or the like is preferable.
  • the base material as a core material may intervene in the middle of the thickness direction of the adhesive layer 5 for jigs.
  • the thickness of the jig pressure-sensitive adhesive layer 5 is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m, from the viewpoint of adhesion to a jig such as a ring frame.
  • Release sheet The release sheet 6 according to the protective film-forming sheet 3 according to an embodiment of the present invention includes the protective film-forming film 1 and the jig adhesive layer 5 until the protective film-forming sheet 3 is used. Protect.
  • the configuration of the release sheet 6 is arbitrary, and a sheet obtained by peeling a plastic film with a release agent or the like is exemplified.
  • the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; and polyolefin films such as polypropylene and polyethylene.
  • a silicone release agent, a fluorine release agent, a long-chain alkyl release agent, or the like can be used, and among these, a silicone release agent that can provide stable performance at low cost is preferable.
  • the thickness of the release sheet 6 is not particularly limited, but is usually about 20 ⁇ m to 250 ⁇ m.
  • the protective film forming sheet 3 is preferably a laminate including the protective film forming film 1 (also referred to as “laminate I” in this specification) and the first support sheet 4. Are separately produced, and then the protective film-forming film 1 and the first support sheet 4 are prepared using the laminate I and the laminate II.
  • the present invention is not limited to this.
  • the protective film forming film 1 is formed on the release surface of the first release sheet.
  • a coating agent for a protective film-forming film containing a curable adhesive constituting the protective film-forming film 1 and, if desired, further a solvent is prepared, and a roll coater, a knife coater, a roll knife coater, an air knife
  • the coating agent is applied to the release surface of the first release sheet by a coating machine such as a coater, die coater, bar coater, gravure coater, curtain coater, and the like, and dried to form the protective film forming film 1 as the first release sheet. Formed on the release surface.
  • a laminate (laminate I) in which the protective film-forming film 1 is sandwiched between two release sheets by laminating the release surface of the second release sheet on the exposed surface of the protective film-forming film 1 and press-bonding it. obtain.
  • the protective film-forming film 1 (and the second release sheet) may be formed in a desired shape, for example, a circle. In this case, what is necessary is just to remove suitably the protective film formation film 1 and the excess part of the 2nd peeling sheet which arose by the half cut.
  • an adhesive for the adhesive layer containing the adhesive constituting the adhesive layer 42 and optionally further a solvent is applied to the release surface of the third release sheet. It is made to dry and the adhesive layer 42 is formed in the peeling surface of a 3rd peeling sheet. Then, the base material 41 is crimped
  • the pressure-sensitive adhesive layer 42 when the pressure-sensitive adhesive layer 42 is made of an energy ray-curable pressure-sensitive adhesive, the pressure-sensitive adhesive layer 42 may be irradiated with energy rays at this stage to cure the pressure-sensitive adhesive layer 42 or to protect it.
  • the pressure-sensitive adhesive layer 42 may be cured by irradiating energy rays after laminating the film-forming film 1.
  • the adhesive layer 42 when hardening the adhesive layer 42 after laminating
  • energy rays ultraviolet rays, electron beams, etc. are usually used. Irradiation of energy rays varies depending on the kind of energy rays, for example, in the case of ultraviolet rays, preferably 50 ⁇ 1000mJ / cm 2 in quantity, more preferably 100 ⁇ 500mJ / cm 2. In the case of an electron beam, about 10 to 1000 krad is preferable.
  • the second release sheet in laminate I is peeled off, and the third release sheet in laminate II is peeled off and exposed in laminate I.
  • the protective film forming film 1 and the pressure-sensitive adhesive layer 42 of the first support sheet 4 exposed in the laminate II are overlapped and pressure-bonded.
  • the first support sheet 4 may be half-cut as desired to have a desired shape, for example, a circle having a larger diameter than the protective film-forming film 1. In this case, an excess portion of the first support sheet 4 generated by the half cut may be removed as appropriate.
  • a protective film-forming sheet 3 comprising the film-forming film 1 and a first release sheet laminated on the surface opposite to the surface facing the first support sheet 4 in the protective film-forming film 1 is obtained.
  • the jig pressure-sensitive adhesive layer 5 is formed on the peripheral edge of the surface opposite to the surface facing the first support sheet 4 in the protective film forming film 1. .
  • the jig pressure-sensitive adhesive layer 5 can also be applied and formed in the same manner as the pressure-sensitive adhesive layer 42.
  • the exposed surface is attached to one surface of the semiconductor wafer 7 as a work, specifically, the surface (back surface) opposite to the circuit forming surface, and the protective film forming sheet 3 is attached. And a workpiece 1 are obtained (FIG. 3).
  • the first laminated body 10 shown in FIG. 3 further includes a jig pressure-sensitive adhesive layer 5 and a ring frame 8.
  • the jig adhesive layer 5 is an element of the protective film forming sheet 3, and the protective film forming film 1 of the protective film forming sheet 3 is attached to the semiconductor wafer 7 in the first attaching step.
  • the jig adhesive layer 5 of the protective film forming sheet 3 may be attached to the ring frame 8.
  • one side surface of the first sticking step is a surface opposite to the surface facing the first support sheet in the protective film forming film provided in the protective film forming sheet according to one embodiment of the present invention. And affixing the exposed surface to one surface of the workpiece to obtain a first laminate including the protective film forming sheet and the workpiece.
  • the heating time and heating temperature vary depending on the material constituting the film, it is preferable to heat at 90 to 170 ° C. for 0.5 to 5 hours, for example.
  • seat 3 for protective film formation of the 1st laminated body 10 obtained by the 1st sticking process is equipped is hardened, and a protective film is obtained.
  • the curing conditions for obtaining the protective film are appropriately set based on the material constituting the protective film forming film 1.
  • the protective film forming film 1 is a thermosetting adhesive
  • the protective film forming film 1 may be heated at a predetermined temperature for an appropriate time.
  • the protective film formation film 1 is not a thermosetting adhesive, it heat-processes separately. That is, one side surface of the first curing step includes obtaining a protective film by curing the protective film forming film in the first laminate.
  • one aspect of the first dividing step is that the temperature T2 of the protective film in the first laminated body that has undergone the first curing step is kept in a range of 40 ° C. to 70 ° C.
  • the method for extending the first support sheet 4 is not limited. As shown in FIG. 4, the ring-shaped member R is pressed against the surface of the first support sheet 4 opposite to the surface facing the ring frame 8, and the ring frame 8 and the ring-shaped member R are pressed.
  • the first support sheet 4 may be extended by changing the relative position in the vertical direction. That is, the stress generated in the support sheet 4 by the extension includes a vector amount in a horizontal direction or a direction parallel to the back surface of the semiconductor wafer 7.
  • the protective film forming film 1 is generally composed of a curable material that is a material capable of forming a protective film by curing, and a typical example thereof is an uncured curable adhesive. .
  • a curable material that is a material capable of forming a protective film by curing, and a typical example thereof is an uncured curable adhesive.
  • Such a material has a large amount of deformation (breaking strain) until it breaks when a tensile force is applied, and may not be divided even when the first support sheet 4 is stretched (expanded). Therefore, when the first support sheet 4 is expanded, the protective film-forming film 1 is cooled to about 0 ° C. to ⁇ 20 ° C. (specifically, it may be achieved by cooling the first laminate 10).
  • the breaking strain of the protective film-forming film 1 is reduced.
  • a relatively expensive cooling facility is required for cooling compared to heating, and the energy required for cooling is greater than the energy required for heating. For this reason, cooling the protective film-forming film 1, generally cooling the first laminated body 10, brings about an initial investment and an increase in running cost in the method for manufacturing a chip with a protective film.
  • the first support sheet 4 is positioned between the first support sheet 4 and the semiconductor wafer 7 when the first support sheet 4 is expanded.
  • the member is a protective film. Since the protective film is obtained by curing the protective film-forming film 1, its breaking strain is lower than that of the protective film-forming film 1. Therefore, the division failure due to the breaking strain is unlikely to occur. However, since the protective film is a cured material, the breaking stress may be increased, and there is a possibility that division failure may occur due to the height of the breaking stress. Therefore, in the method for manufacturing a chip with a protective film according to an embodiment of the present invention, when the first support sheet 4 is expanded, the temperature T2 of the protective film is maintained in the range of 40 ° C. to 70 ° C. It is said.
  • the possibility of the defective division of the protective film is reduced. If the temperature T2 of the protective film is increased to about 40 ° C., the reduction of the breaking stress becomes clear as compared with the room temperature (23 ° C.) state, and the effect (reduction of defective partitioning) derived from the heat expansion can be stably enjoyed. It becomes possible to do.
  • the temperature T2 of the protective film during expansion of the first support sheet 4 is more than 70 ° C.
  • an increase in the breaking strain of the protective film a change in mechanical properties of the first support sheet 4 (decrease in Young's modulus,
  • There is an increased possibility of inconveniences such as work defects caused by softening and the like specifically examples include a decrease in the amount of expand and fusion of the first support sheet 4 to the table). Therefore, by setting the temperature T2 of the protective film at the time of expanding the first support sheet 4 to 70 ° C. or less, the possibility that a problem occurs in the production of the chip with the protective film can be stably reduced.
  • the temperature T2 of the protective film during the expansion of the first support sheet 4 may be preferably 42 ° C. or more and 65 ° C. or less, It may be more preferable to set it as 43 degreeC or more and 60 degrees C or less, and it may be especially preferable to set it as 45 degreeC or more and 55 degrees C or less.
  • each of the plurality of protective film-provided chips 9 included in the second stacked body 20 obtained by performing the first division step is changed to the first pickup step.
  • the individual chip 9 with protective film is obtained as a workpiece.
  • This separation method is not limited.
  • a push-up pin P and a vacuum suction collet C may be used.
  • tip 9 with a protective film can be obtained. That is, according to one aspect of the first pickup process, the chip with the protective film is processed by separating each of the plurality of chips with the protective film included in the second laminate from the first support sheet. Including getting as.
  • Modified layer forming step Before the first dividing step is started, the laser beam in the infrared region (for example, 1064 nm) is irradiated so as to be focused on the focal point set inside the semiconductor wafer 7 (work). Then, a modified layer forming step for forming a modified layer inside the semiconductor wafer 7 is performed. In the first dividing step, the first support sheet to be bonded to the semiconductor wafer 7 that has undergone the modified layer forming step is stretched to divide the semiconductor wafer 7 along the planned dividing line. That is, one side of the modified layer forming step is to irradiate the laser beam in the infrared region so as to be focused on the focal point set inside the workpiece before the first dividing step is started. Forming a modified layer inside the workpiece.
  • the laser beam in the infrared region for example, 1064 nm
  • a modified layer forming step for forming a modified layer inside the semiconductor wafer 7 is performed.
  • FIG. 6 shows a protective film forming sheet according to another embodiment of the present invention. It is sectional drawing.
  • the protective film forming sheet 3 ⁇ / b> A according to this embodiment includes a first support sheet 4 in which an adhesive layer 42 is laminated on one surface of a base material 41, and a first support sheet.
  • a release sheet 6 is provided.
  • the protective film-forming film 1 in the embodiment is formed to be substantially the same as or slightly larger than the work in the surface direction, and smaller than the first support sheet 4 in the surface direction.
  • the part of the pressure-sensitive adhesive layer 42 where the protective film forming film 1 is not laminated can be attached to a jig such as a ring frame.
  • each member of the protective film forming sheet 3A is the same as the material and thickness of each member of the protective film forming sheet 3 described above.
  • the pressure-sensitive adhesive layer 42 is made of an energy ray-curable pressure-sensitive adhesive
  • the portion in contact with the protective film forming film 1 in the pressure-sensitive adhesive layer 42 cures the energy ray-curable pressure-sensitive adhesive, and the other portions are energy. It is preferable not to cure the linear curable adhesive.
  • the adhesive layer 5 for jigs of the protective film forming sheet 3 described above is provided on the peripheral edge of the adhesive layer 42 of the first support sheet 4 of the protective film forming sheet 3A on the side opposite to the base 41.
  • a similar pressure-sensitive adhesive layer for jigs may be provided separately.
  • seat 3B for protective film formation which concerns on one of other embodiment of this invention is equipped It may be made of a base material (only) without an adhesive layer.
  • the surface on the protective film forming film side of the substrate corresponds to the first surface of the first support sheet.
  • the peripheral portion of the surface opposite to the surface facing the substrate (first support sheet) in the protective film forming film is for the jig shown in FIG. It is preferable that the same adhesive layer for jigs as the adhesive layer 5 is provided.
  • the first support sheet is a release sheet
  • the first support sheet provided in the protective film-forming sheet according to one of the other embodiments of the present invention may be a release sheet having a release surface. Good.
  • the release surface corresponds to the first surface of the first support sheet.
  • the specific configuration of the release sheet is not limited.
  • the protective film-forming sheet according to one of the other embodiments of the present invention is a surface opposite to the surface facing the first support sheet of the protective film-forming film. You may provide the 2nd support sheet laminated
  • the second support sheet is a release sheet, and may be arranged so that the release surface faces the protective film-forming film.
  • the protective film-forming film 1 is formed from the first support sheet 4 in the first pickup process, specifically, it is a part of the chip 7 with the protective film.
  • the divided body of the protective film is separated.
  • the protective film-forming film is peeled from the first support sheet and then cured to form a protective film.
  • An example of such a manufacturing method is as follows.
  • the surface opposite to the surface facing the first support sheet in the protective film forming film 1 provided in the protective film forming sheet according to the embodiment of the present invention is exposed, and the exposed surface is a semiconductor wafer.
  • the work 7 and the protective film forming film 1 are attached to one surface of the work 7 and the like, and the first support sheet of the protective film forming sheet is peeled from the protective film forming film 1.
  • a laminating step for obtaining a third laminate 11 comprising; A second curing step of obtaining a protective film by curing the protective film-forming film 1 provided in the third laminate 11; The third pressure-sensitive adhesive layer side 131 of the processing sheet 13 provided with the third base material 11 and the third pressure-sensitive adhesive layer 131 laminated on one surface side of the third base material 132. By attaching the surface and the surface on the protective film side of the third laminate 11 that has undergone the second curing step, the processing sheet 13 and the third laminate 11 are provided. 2nd sticking process of obtaining the laminated body 12 of 4; In a state where the temperature T3 of the protective film included in the fourth stacked body 12 is maintained within a range of 40 ° C.
  • the processing sheet 13 included in the fourth stacked body 12 is extended, By dividing the protective film together with the work 7, a plurality of chips 9 with a protective film formed by dividing the laminate of the work 7 and the protective film so as to generate a cut surface in the thickness direction is provided.
  • a second dividing step of obtaining a fifth laminated body 14 disposed on one surface of the sheet 13 for use; and each of the plurality of protective film-provided chips 9 provided in the fifth laminated body 14 for the processing A second pick-up step that separates from the sheet 13 and obtains a chip 9 with a protective film as a workpiece, and further, the focal point set inside the workpiece 7 before the second dividing step is started. Focused Uni irradiated with laser light in the infrared region, including a modified layer forming step of forming a modified layer inside the workpiece 7.
  • the 3rd base material 132 with which processing sheet 13 is provided should just have the same characteristic as base material 41 with which support sheet 4 is provided.
  • seat 13 for processing is provided should just have the characteristic similar to the adhesive layer 42 with which the support sheet 4 is provided.
  • segmentation process is more than said temperature T1.
  • another layer may be interposed between the base material 41 and the pressure-sensitive adhesive layer 42 in the first support sheet 4. Further, another layer may be laminated on the first surface of the first support sheet 4 made of the base material 41.
  • a layer for adjusting the adhesion between the substrate 41 and the pressure-sensitive adhesive layer 42 such as a primer layer, and the adhesion between the support sheet 4 and the protective film forming film 1 are prepared.
  • Example 1 The following components are mixed at a blending ratio shown in Table 1 (in terms of solid content) and diluted with methyl ethyl ketone so that the solid content concentration is 50% by mass with respect to the total mass of the coating agent for protective film forming film. Thus, a coating agent for a protective film-forming film was prepared.
  • Binder polymer (meth) acrylic ester copolymer obtained by copolymerizing 10 parts by weight of n-butyl acrylate, 70 parts by weight of methyl acrylate, 5 parts by weight of glycidyl methacrylate and 15 parts by weight of 2-hydroxyethyl acrylate Combined (weight average molecular weight: 400,000, glass transition temperature: -1 ° C)
  • A-2 Binder polymer: (meth) acrylic acid ester copolymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 400,000, glass transition temperature: -6 °C)
  • the aforementioned coating agent for a protective film-forming film is finally obtained.
  • the protective film-forming film is laminated with the release surface of a release sheet (SP-PET251130, manufactured by Lintec Co., Ltd.) on which one side of the PET film is formed with a silicone release agent layer.
  • Example 2 For the protective film-forming film in which the types and blending amounts of the components constituting the protective film-forming film are the compositions shown in the column of Example 2 in Table 1 and diluted with methyl ethyl ketone so that the solid content concentration becomes 50% A protective film-forming sheet was produced in the same manner as in Example 1 except that the coating agent was adjusted.
  • a dicing tape was attached to the ring frame.
  • a laser (wavelength: 1064 nm) focused inside the wafer was irradiated through the dicing tape and the protective film using a laser irradiation apparatus. At this time, irradiation was performed while scanning along a planned cutting line set so that a 5 mm ⁇ 5 mm chip body was formed.
  • an expander (DISCO, DDS2300)
  • a dicing tape was attached to a wafer with a protective film at a speed of 100 mm / second and an expand amount of 10 mm in an environment of 50 ° C.
  • the chip with protective film was picked up by pulling up the extruded chip with protective film with a vacuum suction collet.
  • A the trace of the pin pressed against the protective film is not found good
  • B the case where “possible”
  • C the case where “possible”
  • the results are shown in Table 2.
  • the protective film according to Comparative Example 2 was not properly divided in Test Example 2, the protective film according to Examples 1 and 2 and Comparative Example 1 (the evaluation target was a part of the split). Only this 4th laminated body provided with a protective film performed this evaluation.
  • the protective film-forming sheet of the example provided with a protective film having a breaking strain at 50 ° C. of 20% or less and a loss tangent peak temperature T1 in the range of 25 ° C. to 60 ° C.
  • the strength of the protective film was also excellent.
  • the protective film-forming sheet according to the present invention can be suitably used in the case where it includes a step of dividing the protective film while heating, it is extremely important industrially.
  • SYMBOLS 1 Protective film formation film 3, 3A, 3B ... Protective film formation sheet 4 ... Support sheet 41 ... Base material 42 ... Adhesive layer 5 ... Jig adhesive layer 6 ... Release sheet 7 ... Semiconductor wafer 8 ... Ring frame DESCRIPTION OF SYMBOLS 9 ... Chip 10 with a protective film ... 1st laminated body 11 ... 2nd laminated body 12 ... 3rd laminated body 13 ... Sheet

Abstract

L'invention concerne une feuille pour formation de membrane protectrice (3) qui est équipée : d'une première feuille de support (4); et d'un film de formation de membrane protectrice (1) stratifié du côté d'une première face de cette première feuille de support (4). Ce film de formation de membrane protectrice (1) est constitué d'un matériau durcissable. Lorsque ce film de formation de membrane protectrice (1) constitue une membrane protectrice telle que le durcissement du film de formation de membrane protectrice (1) constitue une caractéristique de la feuille pour formation de membrane protectrice (3), alors l'effort de rupture à 50°C de cette membrane protectrice est inférieure ou égale à 20%, et la température pic (T1) de son facteur de pertes diélectriques est comprise entre 25 et 60°C.
PCT/JP2015/073503 2014-08-22 2015-08-21 Feuille pour formation de membrane protectrice, et procédé de fabrication de puce semi-conductrice avec membrane protectrice WO2016027883A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
SG11201701272UA SG11201701272UA (en) 2014-08-22 2015-08-21 Protective coating-forming sheet and method for manufacturing semiconductor chip provided with protective coating
JP2016544263A JP6589209B2 (ja) 2014-08-22 2015-08-21 保護膜形成用シートおよび保護膜付き半導体チップの製造方法
CN201580044561.4A CN106660332B (zh) 2014-08-22 2015-08-21 保护膜形成用片以及带有保护膜的半导体芯片的制造方法
KR1020177004494A KR102376017B1 (ko) 2014-08-22 2015-08-21 보호막 형성용 시트 및 보호막이 형성된 반도체 칩의 제조 방법
MYPI2017700515A MY186759A (en) 2014-08-22 2015-08-21 Protective coating-forming sheet and method for manufacturing semiconductor chip provided with protective coating
PH12017500285A PH12017500285A1 (en) 2014-08-22 2017-02-16 Protective coating-forming sheet and method for manufacturing semiconductor chip provided with protective coating

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014169267 2014-08-22
JP2014-169267 2014-08-22
JP2014-169266 2014-08-22
JP2014169266 2014-08-22

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PCT/JP2015/073503 WO2016027883A1 (fr) 2014-08-22 2015-08-21 Feuille pour formation de membrane protectrice, et procédé de fabrication de puce semi-conductrice avec membrane protectrice

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KR (2) KR102376017B1 (fr)
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MY (2) MY182846A (fr)
PH (2) PH12017500284A1 (fr)
SG (2) SG11201701272UA (fr)
TW (4) TWI668290B (fr)
WO (2) WO2016027888A1 (fr)

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KR102577856B1 (ko) * 2016-04-28 2023-09-12 린텍 가부시키가이샤 보호막 형성용 필름 및 보호막 형성용 복합 시트
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KR20200138145A (ko) * 2018-03-30 2020-12-09 린텍 가부시키가이샤 지지 시트 및 보호막 형성용 복합 시트
JP7453879B2 (ja) 2020-08-12 2024-03-21 リンテック株式会社 保護膜形成用シートロールおよび保護膜形成用シートロールの製造方法

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SG11201701272UA (en) 2017-04-27
KR102376017B1 (ko) 2022-03-17
SG11201701270QA (en) 2017-03-30
KR102368140B1 (ko) 2022-02-25
JP6589209B2 (ja) 2019-10-16
CN106660333A (zh) 2017-05-10
PH12017500285B1 (en) 2017-06-28
CN106660332A (zh) 2017-05-10
MY186759A (en) 2021-08-18
KR20170044652A (ko) 2017-04-25
TW201614023A (en) 2016-04-16
CN106660333B (zh) 2018-11-06
TW201614024A (en) 2016-04-16
PH12017500284B1 (en) 2017-07-03
PH12017500284A1 (en) 2017-07-03
TW201938728A (zh) 2019-10-01
KR20170044108A (ko) 2017-04-24
TW201940622A (zh) 2019-10-16
TWI712670B (zh) 2020-12-11
CN106660332B (zh) 2020-08-07
JPWO2016027883A1 (ja) 2017-06-01
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