WO2017188231A1 - Film pour former un revêtement protecteur et feuille composite pour former un revêtement protecteur - Google Patents

Film pour former un revêtement protecteur et feuille composite pour former un revêtement protecteur Download PDF

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Publication number
WO2017188231A1
WO2017188231A1 PCT/JP2017/016335 JP2017016335W WO2017188231A1 WO 2017188231 A1 WO2017188231 A1 WO 2017188231A1 JP 2017016335 W JP2017016335 W JP 2017016335W WO 2017188231 A1 WO2017188231 A1 WO 2017188231A1
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WO
WIPO (PCT)
Prior art keywords
protective film
forming
film
meth
sensitive adhesive
Prior art date
Application number
PCT/JP2017/016335
Other languages
English (en)
Japanese (ja)
Inventor
山本　大輔
洋一 稲男
Original Assignee
リンテック株式会社
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 リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020187030754A priority Critical patent/KR102407322B1/ko
Priority to CN201780025032.9A priority patent/CN109071845A/zh
Priority to JP2018514615A priority patent/JP6971977B2/ja
Publication of WO2017188231A1 publication Critical patent/WO2017188231A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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 potential barriers, e.g. a 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
    • H01L21/67—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
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers

Definitions

  • the present invention relates to a protective film-forming film and a protective film-forming composite sheet.
  • a semiconductor device using a mounting method called a so-called face-down method has been manufactured.
  • a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. For this reason, the back surface opposite to the circuit surface of the semiconductor chip may be exposed.
  • a resin film containing an organic material is formed as a protective film on the exposed back surface of the semiconductor chip, and may be taken into the semiconductor device as a semiconductor chip with a protective film.
  • the protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing process or packaging.
  • a protective film-forming composite sheet comprising a protective film-forming film for forming a protective film on a support sheet is used.
  • the protective film-forming film can form a protective film by curing, and the support sheet can also be used as a dicing sheet.
  • the dicing sheet can be integrated.
  • a protective film-forming composite sheet for example, a sheet provided with a thermosetting protective film-forming film that forms a protective film by being cured by heating has been mainly used so far.
  • a protective film-forming composite sheet is pasted to the back surface (surface opposite to the electrode-forming surface) of the semiconductor wafer with a thermosetting protective film-forming film, and then the protective film-forming film is heated.
  • the semiconductor wafer is divided together with the protective film by dicing to form a semiconductor chip. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is stuck.
  • hardening and dicing of the film for protective film formation may be performed in the reverse order.
  • thermosetting protective film-forming film since the heat curing of the thermosetting protective film-forming film usually takes a long time of about several hours, shortening of the curing time is desired.
  • a protective film-forming film that can be cured by irradiation with energy rays such as ultraviolet rays has been studied.
  • an energy ray curable protective film (see Patent Document 1) formed on a release film, and an energy ray curable chip protective film that can form a protective film having high hardness and excellent adhesion to a semiconductor chip (Patent Document) 2).
  • the semiconductor chip with the protective film after pick-up is packed in an embossed carrier tape 102 as shown in FIG. 7 for use in the next process, and the embossed carrier tape 102 is stored, transported, or wound around a reel. May be traded.
  • the circuit surface side of the semiconductor chip is usually directed to the bottom of the pocket 102a of the embossed carrier tape 102, and the protective film side is directed to the pocket.
  • the opening is closed and packed by sticking a cover tape 103 which is stored toward the opening of 102a and forms a lid of the embossed carrier tape 102.
  • the embossed carrier tape 102 packed with the semiconductor chip 101 with the protective film is set on the mounter together with the reel, and the semiconductor chip 101 with the protective film is mounted on the substrate. To do. At that time, the cover tape 103 is peeled off, and the semiconductor chip 101 with the protective film is taken out from the pocket 102a of the embossed carrier tape 102.
  • the semiconductor chip 101 with the protective film adheres to the cover tape 103 by the protective film, and the protective film In some cases, the process of mounting the attached semiconductor chip 101 on the substrate may be an obstacle.
  • the present invention can form a protective film on the back surface of the semiconductor wafer or the semiconductor chip, and when the semiconductor chip with the protective film picked up by dicing is stored in the pocket of the embossed carrier tape, the protective film is attached to the cover tape. It aims at providing the composite film for protective film formation provided with the film for energy film curable protective film formation which has the characteristic which can suppress that a semiconductor chip adheres, and the said film for protective film formation.
  • the present invention provides an energy ray-curable protective film-forming film, wherein when the protective film-forming film is irradiated with energy rays to form a protective film, the protective film has a JIS Provided is a protective film-forming film having a ball tack value of 2 or less measured at an inclination angle of 30 ° according to Z0237: 2010.
  • the protective film-forming film preferably contains an energy ray-curable component (a).
  • the protective film-forming film further contains a photopolymerization initiator (c).
  • the content of the photopolymerization initiator (c) is 2.0 to 12.0 parts by mass with respect to 100 parts by mass of the energy ray-curable component (a).
  • this invention provides the composite sheet for protective film formation provided with the film for protective film formation in any one on a support sheet.
  • the present invention includes the following aspects.
  • An energy ray-curable protective film-forming film When the protective film-forming film is irradiated with energy rays to form a protective film, the protective film has a characteristic that the ball tack value measured at an inclination angle of 30 ° according to JIS Z0237: 2010 is 2 or less.
  • a film for forming a protective film [2] The protective film-forming film according to [1], wherein the protective film-forming film contains an energy ray-curable component (a). [3] The film for forming a protective film according to [2], wherein the film for forming a protective film further contains a photopolymerization initiator (c).
  • the content of the photopolymerization initiator (c) is 2.0 to 12.0 parts by mass with respect to 100 parts by mass of the energy ray curable component (a).
  • Film for forming a protective film [5] A protective film-forming composite sheet comprising the protective film-forming film according to any one of [1] to [4] on a support sheet.
  • the semiconductor chip with a protective film when the semiconductor chip with a protective film is accommodated in the pocket of an embossed carrier tape, it has the characteristic which can suppress that the semiconductor chip with a protective film adheres to a cover tape, and forms an energy-beam curable protective film And a protective film-forming composite sheet comprising the protective film-forming film.
  • the protective film-forming film of the present invention is an energy ray-curable protective film-forming film, and when the protective film-forming film is irradiated with energy rays to form a protective film,
  • the protective film has a characteristic that the ball tack value measured at an inclination angle of 30 ° according to JIS Z0237: 2010 is 2 or less.
  • the protective film-forming film of the present invention may have a first release film on at least one surface, and may further have a second release film on the other surface.
  • the film for forming a protective film of the present invention can be provided as a long film wound in a roll shape.
  • FIG. 1 is a cross-sectional view schematically showing one embodiment of a protective film-forming film of the present invention.
  • a first release film 15 ′, a protective film forming film 13 and a second release film 15 ′′ are laminated in this order.
  • the surface to be attached to the back surface of the semiconductor wafer that is, the surface opposite to the circuit surface
  • front surface ( ⁇ ) the surface to be attached to the back surface of the semiconductor wafer
  • surface ( ⁇ ) the surface opposite to the surface
  • the protective film-forming film of the present invention When the protective film-forming film of the present invention is irradiated with energy rays to form a protective film, the protective film is measured at an inclination angle of 30 ° according to JIS Z0237: 2010 on at least one surface ( ⁇ ) of the protective film.
  • the ball tack value is 2 or less. That is, as one aspect, the protective film-forming film of the present invention has energy ray curability and is a protective film-forming film for forming a protective film on the back surface of a semiconductor wafer or a semiconductor chip.
  • the surface of the protective film on the side ( ⁇ ) opposite to the surface ( ⁇ ) attached to the semiconductor wafer or semiconductor chip is JIS.
  • the ball tack value measured at an inclination angle of 30 ° according to Z0237: 2010 preferably has a property of 0 or more and 2 or less, and more preferably has a property of 0 or more and less than 2.
  • the composition of the protective film-forming film will be described later.
  • the protective film-forming film of the present invention can be used as a protective film-forming film constituting a protective film-forming composite sheet described later.
  • a protective film-forming film can be attached to the back surface of the semiconductor wafer, and then a support sheet can be attached to the protective film-forming film.
  • the protective film-forming film and the base material sheet the protective film-forming film and the base material sheet described in the description of the protective film-forming composite sheet described later can be used as appropriate.
  • the protective film-forming film is used as a protective film-forming composite sheet, which will be described later, or as a protective film-forming sheet in which a protective film-forming film is provided on a release film, which is applied to the back surface of the semiconductor wafer.
  • a support sheet can be attached and used.
  • FIG. 1 is a cross-sectional view schematically showing an embodiment of a protective film-forming sheet 2F using the protective film-forming film of the present invention.
  • the protective film forming sheet 2 ⁇ / b> F shown here includes a protective film forming film 13 on the first release film 15 ′ and a second release film 15 ′′ on the protective film forming film 13. is there.
  • the protective film forming film 13 has the surface 13a of the protective film forming film 13 (that is, the first film in the protective film forming film 13 in a state where the second release film 15 ′′ on the light release side is removed). 2) the rear surface of the semiconductor wafer (not shown) is affixed to a partial region on the center side, and the first release film 15 ′ on the heavy release side is removed. In this state, a base sheet is pasted on the other surface 13b of the protective film forming film 13 opposite to the surface 13a, and the region in the vicinity of the peripheral edge of the protective film forming film 13 is a ring frame.
  • the release film having the smaller release force is referred to as a light release side release film
  • the release film having the higher release force is referred to as a heavy release side release film.
  • the protective film formation film may float from the release film on the heavy release side, or a protective film is formed to follow both release films. The film can be prevented from being stretched and deformed.
  • the protective film-forming composite sheet of the present invention comprises an energy ray-curable protective film-forming film on a support sheet.
  • the “protective film-forming film” means a film before curing
  • the “protective film” means a film obtained by curing the protective film-forming film.
  • energy beam means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
  • Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp or the like as an ultraviolet ray source.
  • the electron beam can be emitted by an electron beam accelerator or the like.
  • energy ray curable means a property that cures when irradiated with energy rays
  • non-energy ray curable means a property that does not cure even when irradiated with energy rays. To do.
  • the adhesive force between the support sheet and the protective film-forming film of the laminate is not particularly limited, and may be, for example, 80 mN / 25 mm or more, or 100 mN / 25 mm or more, It may be 150 mN / 25 mm or more, may be 200 mN / 25 mm or more, and the upper limit is not particularly limited, but may be 10,000 mN / 25 mm or less, or 8000 mN / 25 mm or less, It may be 7000 mN / 25 mm or less.
  • the adhesive force between the support sheet and the protective film-forming film of the laminate may be 80 to 10,000 mN / 25 mm, 150 to 8000 mN / 25 mm, or 200 to 7000 mN / It may be 25 mm.
  • the adhesive force to be equal to or higher than the lower limit value scattering of the silicon chip is suppressed during dicing, and cutting water can be prevented from entering between the protective film-forming film and the support sheet.
  • the adhesive strength between the protective film and the support sheet is appropriately adjusted when the protective film is cured by irradiation with energy rays. Can be made easier.
  • the protective film-forming film is cured by irradiation with energy rays and becomes a protective film.
  • This protective film is for protecting the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer or semiconductor chip.
  • the protective film-forming film is soft and can be easily attached to an object to be attached.
  • the adhesive force between the protective film and the support sheet is preferably 50 to 1500 mN / 25 mm, and preferably 52 to 1450 mN. / 25 mm is more preferable, and 53 to 1430 mN / 25 mm is particularly preferable.
  • the adhesive force is equal to or higher than the lower limit value
  • pickup of a semiconductor chip with a protective film other than the target is suppressed during pickup of the semiconductor chip with a protective film, and the target semiconductor chip with a protective film is highly selectively picked up. it can.
  • the adhesive force is equal to or less than the upper limit value
  • cracking and chipping of the semiconductor chip are suppressed when the semiconductor chip with a protective film is picked up.
  • the composite sheet for forming a protective film has good pickup suitability.
  • the protective film-forming film is energy ray-curable, so that the conventional protective film provided with the thermosetting protective film-forming film is used.
  • the protective film can be formed by curing in a shorter time than in the case of the forming composite sheet.
  • the thickness of the semiconductor wafer or semiconductor chip that is the target of use of the composite sheet for forming a protective film of the present invention is not particularly limited, but is preferably 30 to 1000 ⁇ m because the effects of the present invention can be obtained more remarkably. 100 to 300 ⁇ m is more preferable.
  • the configuration of the present invention will be described in detail.
  • the support sheet may be composed of one layer (single layer) or may be composed of two or more layers.
  • the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
  • the plurality of layers may be the same or different from each other” means “all the layers may be the same or all the layers are different. Means that only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and thickness of each layer is different from each other ”. Means.
  • Preferred support sheets include, for example, those in which the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate, those in which the pressure-sensitive adhesive layer is laminated on the substrate via an intermediate layer, and only the substrate. And the like.
  • FIG. 2 is a cross-sectional view schematically showing one embodiment of the composite sheet for forming a protective film of the present invention.
  • the protective film-forming composite sheet 1 ⁇ / b> A shown here is provided with a pressure-sensitive adhesive layer 12 on a substrate 11 and a protective film-forming film 13 on the pressure-sensitive adhesive layer 12.
  • the support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and in other words, the protective film-forming composite sheet 1 ⁇ / b> A is one surface 10 a of the support sheet 10 (for example, the pressure-sensitive adhesive layer 12 in the support sheet 10).
  • the protective film-forming film 13 is laminated on the side surface.
  • the protective film-forming composite sheet 1 ⁇ / b> A further includes a release film 15 on the protective film-forming film 13.
  • the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and is in contact with the surface 12a of the pressure-sensitive adhesive layer 12 (that is, the base material 11 in the pressure-sensitive adhesive layer 12).
  • the protective film forming film 13 is laminated on the entire surface of the protective film forming film 13 (that is, the side in contact with the pressure-sensitive adhesive layer 12 in the protective film forming film 13).
  • the jig adhesive layer 16 is laminated on a part of the surface 13a, that is, in the vicinity of the peripheral edge of the surface 13a, and the jig adhesive on the surface 13a of the protective film forming film 13 is laminated.
  • the adhesive force between the cured protective film-forming film 13 (that is, the protective film) and the support sheet 10 is 50 to 1500 mN / 25 mm is preferable.
  • the adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both surfaces of a core sheet. It may be of a structure.
  • the composite sheet 1A for forming a protective film shown in FIG. 2 has a back surface of a semiconductor wafer (not shown) attached to the front surface 13a of the protective film forming film 13 with the release film 15 removed.
  • the upper surface of the surface 16a of the adhesive layer 16 is used by being attached to a jig such as a ring frame.
  • FIG. 3 is a sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
  • the same components as those shown in the already explained figures are given the same reference numerals as those in the already explained figures, and their detailed explanations are omitted.
  • the protective film-forming composite sheet 1B shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 2 except that the jig adhesive layer 16 is not provided. That is, in the protective film-forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the surface 12a of the pressure-sensitive adhesive layer 12 (ie, the base material 11 in the pressure-sensitive adhesive layer 12 is in contact).
  • the protective film-forming film 13 is laminated on the entire surface opposite to the side on which the protective film is formed, and is in contact with the surface 13a of the protective film-forming film 13 (that is, in contact with the adhesive layer 12 in the protective film-forming film 13).
  • a release film 15 is laminated on the entire surface of the surface opposite to the side on which it is present.
  • the protective sheet-forming composite sheet 1B shown in FIG. 3 has a semiconductor wafer (not shown) in a partial region on the center side of the surface 13a of the protective film-forming film 13 with the release film 15 removed.
  • the back surface is affixed, and the region near the periphery of the protective film-forming film 13 is affixed to a jig such as a ring frame and used.
  • FIG. 4 is a sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
  • the protective sheet-forming composite sheet 1 ⁇ / b> C shown here is the same as the protective film-forming composite sheet 1 ⁇ / b> A shown in FIG. 2, except that the adhesive layer 12 is not provided. That is, in the protective film-forming composite sheet 1 ⁇ / b> C, the support sheet 10 is made of only the base material 11. Then, the protective film forming film 13 is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), and the surface 13a of the protective film forming film 13 (that is, in the protective film forming film 13).
  • the surface of the protective film-forming film 13 is formed by laminating a jig adhesive layer 16 on a part of the surface on the side opposite to the side in contact with the substrate 11, that is, in the vicinity of the peripheral edge of the surface 13a. 13a, the surface on which the jig adhesive layer 16 is not laminated, and the surface 16a of the jig adhesive layer 16 (the upper surface, that is, the contact with the protective film forming film 13 on the jig adhesive layer 16).
  • a release film 15 is laminated on the surface opposite to the side and the side surface of the jig adhesive layer 16.
  • the adhesive force between the protective film-forming film 13 after curing (ie, the protective film) and the support sheet 10 is: It is preferably 50 to 1500 mN / 25 mm.
  • the protective film forming composite sheet 1C is formed on the surface 13a of the protective film forming film 13 with the release film 15 removed.
  • the back surface of (not shown) is attached, and the upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.
  • FIG. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
  • the protective sheet-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1C shown in FIG. 4 except that it does not include the jig adhesive layer 16. That is, in the protective film-forming composite sheet 1D, the protective film-forming film 13 is laminated on one surface 11a of the substrate 11, and the surface 13a of the protective film-forming film 13 (that is, in the protective film-forming film 13).
  • a release film 15 is laminated on the entire surface of the surface opposite to the side in contact with the substrate 11.
  • the protective film-forming composite sheet 1D shown in FIG. 5 is the same as the protective film-forming composite sheet 1B shown in FIG. 3, with the release film 15 being removed, of the surface 13a of the protective film-forming film 13,
  • the back surface of a semiconductor wafer (not shown) is affixed to a partial area on the center side, and the area near the periphery of the protective film forming film 13 is affixed to a jig such as a ring frame. .
  • FIG. 6 is a cross-sectional view schematically showing still another embodiment of the protective sheet-forming composite sheet of the present invention.
  • the protective film-forming composite sheet 1E shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 2 except that the shape of the protective film-forming film is different. That is, the protective film-forming composite sheet 1 ⁇ / b> E includes the pressure-sensitive adhesive layer 12 on the base material 11 and the protective film-forming film 23 on the pressure-sensitive adhesive layer 12.
  • the support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and in other words, the protective film-forming composite sheet 1 ⁇ / b> E is one surface 10 a of the support sheet 10 (for example, the pressure-sensitive adhesive layer 12 in the support sheet 10).
  • a protective film-forming film 23 is laminated on the side surface.
  • the protective film-forming composite sheet 1 ⁇ / b> E further includes a release film 15 on the protective film-forming film 23.
  • the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the surface 12a of the pressure-sensitive adhesive layer 12 (that is, the side in contact with the base material 11 in the pressure-sensitive adhesive layer 12) Is a part of the opposite surface), that is, a protective film-forming film 23 is laminated on a central region of the surface 12a.
  • a protective film-forming film 23 is laminated on a central region of the surface 12a.
  • the surface 12 a of the pressure-sensitive adhesive layer 12 the surface on which the protective film-forming film 23 is not laminated and the surface 23 a of the protective film-forming film 23 (upper surface, ie, the pressure-sensitive adhesive layer 12 in the protective film-forming film 23.
  • the release film 15 is laminated on the surface opposite to the side in contact with the surface and the side surface of the protective film-forming film 23).
  • the protective film-forming film 23 When the protective film-forming composite sheet 1E is viewed from above and viewed in plan, the protective film-forming film 23 has a smaller surface area than the pressure-sensitive adhesive layer 12, and has a circular shape or the like, for example.
  • the adhesive force between the cured protective film-forming film 23 (that is, the protective film) and the support sheet 10 is 50 to 1500 mN / 25 mm is preferable.
  • the back surface of the semiconductor wafer (not shown) is pasted on the front surface 23a of the protective film-forming film 23 with the release film 15 removed.
  • the surface on which the protective film forming film 23 is not laminated is attached to a jig such as a ring frame and used.
  • the surface 12a of the pressure-sensitive adhesive layer 12 is the same as that shown in FIGS. 2 and 4 on the surface on which the protective film-forming film 13 is not laminated.
  • An adhesive layer for jigs may be laminated (not shown).
  • the protective film-forming composite sheet 1E provided with such a jig adhesive layer has a jig frame whose surface has a ring frame or the like, similar to the protective film-forming composite sheet shown in FIGS. Affixed to the jig and used.
  • the protective sheet-forming composite sheet of the present invention may have any form of the support sheet and the protective film-forming film, or may be provided with an adhesive layer for jigs. However, usually, as shown in FIGS. 2 and 4, the protective film-forming composite sheet of the present invention having a jig adhesive layer is provided with a jig adhesive layer on the protective film-forming film. Are preferred.
  • the composite sheet for forming a protective film of the present invention is not limited to the one shown in FIGS. 2 to 6, and a part of the structure shown in FIGS. 2 to 6 is changed or deleted within a range not impairing the effect of the present invention.
  • another configuration may be added to what has been described so far.
  • an intermediate layer may be provided between the base material 11 and the protective film-forming film 13. Any intermediate layer can be selected according to the purpose.
  • an intermediate layer may be provided between the base material 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by laminating a base material, an intermediate layer, and an adhesive layer in this order.
  • the intermediate layer is the same as the intermediate layer that may be provided in the protective film-forming composite sheet shown in FIGS. In the composite sheet for forming a protective film shown in FIGS.
  • a layer other than the intermediate layer may be provided at an arbitrary position.
  • a gap may be partially formed between the release film and the layer that is in direct contact with the release film.
  • the size and shape of each layer can be arbitrarily adjusted according to the purpose.
  • a layer such as an adhesive layer that is in direct contact with the protective film-forming film in the support sheet is preferably non-energy ray curable.
  • Such a composite sheet for forming a protective film can more easily pick up a semiconductor chip having a protective film on the back surface.
  • the support sheet may be transparent, opaque, or colored depending on the purpose. Among them, in the present invention in which the protective film-forming film has energy ray curability, the support sheet is preferably capable of transmitting energy rays.
  • the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
  • the upper limit value of the transmittance of light having a wavelength of 375 nm is not particularly limited, but may be 95%, for example. That is, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30 to 95%, more preferably 50 to 95%, and particularly preferably 70 to 95%.
  • the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
  • the upper limit value of the transmittance of light having a wavelength of 532 nm is not particularly limited, but can be, for example, 95%. That is, the transmittance of light having a wavelength of 532 nm in the support sheet is preferably 30 to 95%, more preferably 50 to 95%, and particularly preferably 70 to 95%.
  • the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
  • the upper limit value of the transmittance of light having a wavelength of 1064 nm is not particularly limited, but can be, for example, 95%. That is, in the support sheet, the light transmittance at a wavelength of 1064 nm is preferably 30 to 95%, more preferably 50 to 95%, and particularly preferably 70 to 95%.
  • the base material is in the form of a sheet or film, and examples of the constituent material include various resins.
  • the resin include polyethylene such as low density polyethylene (may be abbreviated as LDPE), linear low density polyethylene (may be abbreviated as LLDPE), and high density polyethylene (sometimes abbreviated as HDPE); polypropylene, Polyolefins other than polyethylene such as polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- Ethylene copolymer such as norbornene copolymer (copolymer obtained using ethylene as monomer); Vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (obtained using vinyl chloride as monomer) Resin); polystyrene; polycycloolefin Polyester
  • the polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
  • the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.
  • (meth) acrylic acid is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid.
  • the resin constituting the substrate may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.
  • the substrate may be composed of one layer (single layer) or may be composed of two or more layers. When the substrate is composed of a plurality of layers, these layers may be the same or different from each other.
  • the combination of layers is not particularly limited.
  • the thickness of the substrate is preferably 50 to 300 ⁇ m, more preferably 60 to 100 ⁇ m.
  • the thickness of the substrate means the thickness of the entire substrate.
  • the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. means.
  • thickness means a value represented by an average of thicknesses measured with a contact-type thickness meter at any five locations.
  • the base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part.
  • materials that can be used to construct such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Is mentioned.
  • the base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin. May be.
  • the substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.
  • the film for protective film formation has energy-beam sclerosis
  • the substrate is subjected to a roughening treatment such as sandblast treatment, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment.
  • the surface may be subjected to oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
  • the base material may have a surface subjected to primer treatment.
  • the base material prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the antistatic coating layer and the protective film-forming composite sheet are stored in an overlapping manner. It may have a layer or the like.
  • the substrate preferably has a surface subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the substrate due to blade friction during dicing is suppressed.
  • the base material can be manufactured by a known method.
  • a base material containing a resin can be produced by molding a resin composition containing the resin.
  • the said adhesive layer is a sheet form or a film form, and contains an adhesive.
  • the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, and acrylic resins are preferable. .
  • the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin.
  • the resin itself is not only adhesive.
  • a resin exhibiting tackiness by using in combination with other components such as additives, a resin exhibiting adhesiveness due to the presence of a trigger such as heat or water, and the like are also included.
  • the pressure-sensitive adhesive layer may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, these layers may be the same or different from each other.
  • the combination of the multiple layers is not particularly limited.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and particularly preferably 1 to 30 ⁇ m.
  • the “thickness of the pressure-sensitive adhesive layer” means the thickness of the whole pressure-sensitive adhesive layer.
  • the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness.
  • the optical properties of the pressure-sensitive adhesive layer only need to satisfy the optical properties of the support sheet described above. That is, the pressure-sensitive adhesive layer may be transparent, opaque, or colored depending on the purpose. In the present invention in which the protective film-forming film has energy ray curability, the pressure-sensitive adhesive layer is preferably capable of transmitting energy rays.
  • the pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
  • the pressure-sensitive adhesive layer can be formed from a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive.
  • an adhesive layer can be formed in the target site
  • a more specific method for forming the pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers.
  • the ratio of the content of components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the content of the components of the pressure-sensitive adhesive layer.
  • “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.
  • the adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. And a method using various coaters such as a Meyer bar coater and a kiss coater.
  • the drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferably heated and dried. In this case, for example, at 70 to 130 ° C. for 10 seconds to It is preferable to dry under conditions of 5 minutes.
  • the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive that is, the energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray-curable pressure-sensitive adhesive
  • Energy-ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the linear-curable adhesive resin (I-1a) hereinafter referred to as “adhesive resin (I-2a)”
  • the pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound.
  • the adhesive resin (I-1a) is preferably an acrylic resin.
  • the acrylic resin the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
  • the acrylic resin may have only one type of structural unit, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • “derived” means that the chemical structure is changed due to polymerization.
  • Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred. More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-
  • the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms.
  • the alkyl group preferably has 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms.
  • the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.
  • the acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
  • the functional group-containing monomer for example, the functional group reacts with a cross-linking agent described later to become a starting point of cross-linking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound described later. And those that allow introduction of an unsaturated group into the side chain of the acrylic polymer.
  • Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group. That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc .; Examples thereof include saturated alcohols (that is, unsaturated alcohols that do not have a (meth) acryloyl skeleton).
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (that is, monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, itaconic acid, maleic acid Ethylenically unsaturated dicarboxylic acids such as citraconic acid (ie, dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate Examples include esters.
  • monocarboxylic acids such as (meth) acrylic acid and crotonic acid
  • fumaric acid, itaconic acid maleic acid
  • Ethylenically unsaturated dicarboxylic acids such as citraconic acid (ie, dicarboxylic acids having an ethylenically
  • the functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
  • the functional group-containing monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass with respect to the total mass of the structural units constituting the acrylic polymer. More preferably, it is more preferably 3 to 30% by mass.
  • the acrylic polymer may further have a structural unit derived from another monomer.
  • the other monomer is not particularly limited as long as it is a monomer copolymerizable with (meth) acrylic acid alkyl ester or the like.
  • the other monomer include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.
  • the other monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
  • the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (also referred to as energy ray polymerizable group). It can be used as an adhesive resin (I-2a).
  • energy beam polymerizability means a property of polymerizing by irradiation with energy rays.
  • the pressure-sensitive adhesive composition (I-1) contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the pressure-sensitive adhesive resin (I-1a) is preferably 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-1). It is more preferably 10 to 95% by mass, particularly preferably 15 to 90% by mass.
  • Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
  • examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4.
  • Polybutyl (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
  • examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
  • the energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer from the viewpoint that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly lowered.
  • the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the energy ray-curable compound is preferably 1 to 95% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-1). It is more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.
  • a pressure-sensitive adhesive composition ( I-1) preferably further contains a crosslinking agent.
  • the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a).
  • crosslinking agents include tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based crosslinking agents such as adducts of these diisocyanates (that is, crosslinking agents having an isocyanate group), and epoxy-based crosslinking such as ethylene glycol glycidyl ether.
  • crosslinking agent ie, crosslinker having glycidyl group
  • Aziridine type crosslinker such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (ie, crosslinker having aziridinyl group)
  • Metal such as aluminum chelate
  • examples thereof include chelate-based crosslinking agents (that is, crosslinking agents having a metal chelate structure); isocyanurate-based crosslinking agents (that is, crosslinking agents having an isocyanuric acid skeleton) and the like.
  • the crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoints of improving the cohesive strength of the pressure-sensitive adhesive and improving the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer, and being easily available.
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a).
  • the amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
  • the pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently proceeds with a curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
  • photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy Acetophenone compounds such as -2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethy
  • ⁇ -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
  • a quinone compound such as 1-chloroanthraquinone
  • a photosensitizer such as amine
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable compound.
  • the amount is more preferably 0.03 to 10 parts by weight, and particularly preferably 0.05 to 5 parts by weight.
  • the pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers.
  • known additives such as reaction retarders and crosslinking accelerators (catalysts).
  • the reaction retarding agent means, for example, an undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage by the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). It suppresses progress.
  • the reaction retarder include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C ( ⁇ O) —) in one molecule. Can be mentioned.
  • the other additive contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
  • the solvent is preferably an organic solvent.
  • the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (for example, carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane, n- Examples thereof include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.
  • the solvent used in the production of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a).
  • the same or different type of solvent used in the production of the adhesive resin (I-1a) may be added separately during the production of the adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be adjusted as appropriate.
  • the pressure-sensitive adhesive composition (I-2) is an energy-ray-curable pressure-sensitive adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a). (I-2a) is contained.
  • the adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
  • the unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.
  • the energy beam polymerizable unsaturated group include (meth) acryloyl group, vinyl group (also referred to as ethenyl group), allyl group (also referred to as 2-propenyl group), and (meth) acryloyl group is preferable. .
  • Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. Etc.
  • Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate, and the like.
  • the pressure-sensitive adhesive composition (I-2) contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the pressure-sensitive adhesive resin (I-2a) is preferably 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-2).
  • the content is more preferably 10 to 95% by mass, and particularly preferably 10 to 90% by mass.
  • an adhesive composition ( I-2) may further contain a crosslinking agent.
  • Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include the same crosslinking agents as in the pressure-sensitive adhesive composition (I-1).
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a).
  • the amount is more preferably 0.1 to 20 parts by weight, and particularly preferably 0.3 to 15 parts by weight.
  • the pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-2) containing the photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
  • Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (I-1).
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a). 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.
  • the pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • Examples of the other additive in the pressure-sensitive adhesive composition (I-2) include the same additives as those in the pressure-sensitive adhesive composition (I-1).
  • the other additive contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
  • Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be adjusted as appropriate.
  • the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.
  • the content of the pressure-sensitive adhesive resin (I-2a) is preferably 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-3). It is more preferably 10 to 95% by mass, particularly preferably 15 to 90% by mass.
  • Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. Examples thereof include the same energy ray curable compounds contained in the product (I-1).
  • the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). It is preferably 0.03 to 200 parts by mass, more preferably 0.05 to 100 parts by mass.
  • the pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
  • Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (I-1).
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is 0.01 to about 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray curable compound.
  • the amount is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
  • the other additive contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
  • Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be adjusted as appropriate.
  • Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy ray-curable pressure-sensitive adhesive composition.
  • Non-energy ray curable pressure-sensitive adhesive compositions include, for example, acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc.
  • An adhesive composition (I-4) containing an adhesive resin (I-1a) is preferable, and an adhesive composition containing an acrylic resin is preferred.
  • the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contains one or more kinds of crosslinking agents, and the content thereof is the above-mentioned pressure-sensitive adhesive composition. It can be the same as in the case of (I-1).
  • Adhesive Resin (I-1a) in Adhesive Composition (I-4) examples include the same as the pressure-sensitive adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-1).
  • the adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the pressure-sensitive adhesive resin (I-1a) is preferably 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-4). It is more preferably 10 to 95% by mass, particularly preferably 15 to 90% by mass.
  • a pressure-sensitive adhesive composition (I-4) preferably further contains a crosslinking agent.
  • Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) include the same crosslinking agents as those in the pressure-sensitive adhesive composition (I-1).
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a).
  • the amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
  • the pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
  • the other additive contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
  • Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited and may be appropriately adjusted.
  • the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because when the pressure-sensitive adhesive layer is energy ray curable, it is sometimes impossible to suppress the pressure-sensitive adhesive layer from being simultaneously cured when the protective film-forming film is cured by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, the cured protective film-forming film and the pressure-sensitive adhesive layer may stick to the interface so as not to be peeled off.
  • a cured protective film-forming film that is, a semiconductor chip provided with a protective film on the back surface (in this specification, sometimes referred to as “semiconductor chip with protective film”) is cured adhesive layer. It becomes difficult to peel off from the support sheet provided with, and the semiconductor chip with a protective film cannot be picked up normally.
  • the pressure-sensitive adhesive layer non-energy ray curable with the support sheet in the present invention, such a problem can be reliably avoided and a semiconductor chip with a protective film can be picked up more easily.
  • the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive composition (I-4) It is obtained by blending each component for constituting the pressure-sensitive adhesive composition, that is, the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive as necessary.
  • the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
  • a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance.
  • the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
  • the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
  • the adhesive force between the protective film obtained by curing the protective film-forming film and the support sheet is 50 to 1500 mN / 25 mm. It is preferably 52 to 1450 mN / 25 mm, particularly preferably 53 to 1430 mN / 25 mm.
  • the adhesive force is equal to or higher than the lower limit value, pickup of a semiconductor chip with a protective film other than the target is suppressed during pickup of the semiconductor chip with a protective film, and the target semiconductor chip with a protective film is highly selectively picked up. it can.
  • the adhesive force is equal to or less than the upper limit value, cracking and chipping of the semiconductor chip are suppressed when the semiconductor chip with a protective film is picked up.
  • the adhesive force is within a specific range, the composite sheet for forming a protective film has good pickup suitability.
  • the laminated structure of the cured product of the support sheet and the protective film-forming film (in other words, the support sheet and the protective film) is maintained.
  • this laminated structure is referred to as a “composite sheet for forming a protective film”.
  • the adhesive force between the protective film and the support sheet can be measured by the following method. That is, a protective film-forming composite sheet having a width of 25 mm and an arbitrary length is attached to an adherend by the protective film-forming film. Next, after irradiating energy rays to cure the protective film-forming film to form a protective film, the support sheet is peeled off at a peeling speed of 300 mm / min from this protective film applied to the adherend. At this time, the support sheet is peeled in the length direction (the length direction of the composite sheet for forming the protective film) so that the surfaces of the protective film and the support sheet that are in contact with each other form an angle of 180 °. The so-called 180 ° peeling is performed. And the load (peeling force) at the time of this 180 degree
  • the length of the composite sheet for forming a protective film used for the measurement is not particularly limited as long as the adhesive force can be stably detected, but is preferably 100 to 300 mm. In the measurement, it is preferable that the protective sheet-forming composite sheet is stuck on the adherend and the sticking state of the protective film-forming composite sheet is stabilized.
  • the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and may be, for example, 80 mN / 25 mm or more, preferably 100 mN / 25 mm or more, It is more preferably 150 mN / 25 mm or more, and particularly preferably 200 mN / 25 mm or more.
  • peeling between the protective film-forming film and the support sheet is suppressed during dicing. For example, from a support sheet for a semiconductor chip having a protective film-forming film on the back surface Is prevented from scattering.
  • the upper limit value of the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and can be any of, for example, 4000 mN / 25 mm, 3500 mN / 25 mm, 3000 mN / 25 mm, and the like. However, these are examples. That is, the adhesive force between the protective film-forming film and the support sheet may be 80 to 4000 mN / 25 mm as one side surface, preferably 100 to 3500 mN / 25 mm, and preferably 150 to 3500 mN / More preferably, it is 25 mm, particularly preferably 200 to 3000 mN / 25 mm.
  • the adhesive force between the protective film-forming film and the support sheet is between the protective film and the support sheet, except that the protective film-forming film used for measurement is not cured by irradiation with energy rays. It can be measured by the same method as adhesive strength.
  • the above-mentioned adhesive force between the protective film and the support sheet and the adhesive force between the protective film-forming film and the support sheet are, for example, the types and amounts of the components contained in the protective film-forming film, It can adjust suitably by adjusting the constituent material of the layer which provides the film for protective film formation, the surface state of this layer, etc.
  • the type and amount of the component contained in the protective film-forming film can be adjusted by the type and amount of the component contained in the protective film-forming composition described below. And among the components of the composition for forming a protective film, for example, the type and content of the polymer (b) having no energy ray curable group, the content of the filler (d), or the crosslinking agent (f) By adjusting the content of, the adhesive force between the protective film or the protective film-forming film and the support sheet can be adjusted more easily.
  • the constituent material can be adjusted as appropriate by adjusting the type and amount of components contained in the adhesive layer. .
  • the kind and quantity of the component of an adhesive layer can be adjusted with the kind and quantity of the component of an above-mentioned adhesive composition.
  • the adhesive force between the protective film or the protective film-forming film and the support sheet is not limited to the constituent material of the base material. The surface condition of the substrate can also be adjusted.
  • the surface state of the base material is, for example, the surface treatment mentioned above as improving the adhesion with the other layers of the base material, that is, the concavo-convex treatment by sandblasting, solvent treatment, etc .; corona discharge treatment, It can be adjusted by performing any one of an electron beam irradiation treatment, a plasma treatment, an ozone / ultraviolet ray irradiation treatment, a flame treatment, a chromic acid treatment, a hot air treatment and the like; and a primer treatment.
  • the protective film-forming film has energy beam curability, and examples thereof include those containing an energy beam curative component (a).
  • the energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky.
  • the protective film-forming film may be only one layer (single layer), or may be two or more layers. In the case of a plurality of layers, these layers may be the same or different from each other. The combination is not particularly limited.
  • the thickness of the protective film-forming film is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
  • the thickness of the protective film-forming film is equal to or more than the lower limit value, a protective film having higher protective ability can be formed.
  • the thickness of the protective film-forming film is equal to or less than the upper limit, an excessive thickness is suppressed.
  • the “thickness of the protective film-forming film” means the thickness of the entire protective film-forming film.
  • the thickness of the protective film-forming film composed of a plurality of layers means the protective film-forming film. Means the total thickness of all the layers that make up.
  • the curing conditions for forming the protective film by curing the protective film-forming film are not particularly limited as long as the protective film has a degree of curing that sufficiently exhibits its function, and the type of the protective film-forming film is not limited. Accordingly, it may be appropriately selected.
  • the illuminance of the energy rays when the protective film-forming film is cured is preferably 4 to 280 mW / cm 2 .
  • the amount of energy rays during the curing is preferably 3 to 1000 mJ / cm 2 .
  • the protective film-forming film can be formed using a protective film-forming composition containing the constituent materials.
  • the protective film-forming film can be formed at the target site by applying the protective film-forming composition to the surface on which the protective film-forming film is to be formed and drying it as necessary.
  • the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the film for forming a protective film.
  • “normal temperature” is as described above.
  • Coating of the composition for forming a protective film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
  • the drying conditions of the protective film-forming composition are not particularly limited, but the protective film-forming composition is preferably heat-dried when it contains a solvent described later. In this case, for example, 70 to 130 ° C. It is preferable to dry under conditions of 10 seconds to 5 minutes.
  • composition for forming protective film (IV-1) examples include a protective film forming composition (IV-1) containing the energy ray curable component (a).
  • the energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming property, flexibility, and the like to the protective film-forming film.
  • Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and an energy ray-curable group and a molecular weight of 100 to 80000.
  • a compound (a2) is mentioned.
  • the polymer (a1) may be at least partially crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
  • “weight average molecular weight” means a polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
  • Polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 examples include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, An acrylic resin (a1-1) obtained by polymerizing a group that reacts with a functional group and an energy ray curable compound (a12) having an energy ray curable group such as an energy ray curable double bond. .
  • Examples of the functional group capable of reacting with a group possessed by another compound in the acrylic polymer (a11) include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are A group substituted with a group other than a hydrogen atom), an epoxy group, and the like.
  • the functional group is preferably a group other than a carboxy group from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor chip.
  • the functional group is preferably a hydroxyl group.
  • the acrylic polymer (a11) having the functional group examples include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to monomers, monomers other than acrylic monomers (non-acrylic monomers) may be copolymerized.
  • the acrylic polymer (a11) may be a random copolymer or a block copolymer.
  • acrylic monomer having a functional group examples include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc .; Examples thereof include saturated alcohols (that is, unsaturated alcohols that do not have a (meth) acryloyl skeleton).
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (that is, monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, itaconic acid, maleic acid Ethylenically unsaturated dicarboxylic acids such as citraconic acid (ie, dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate Examples include esters.
  • monocarboxylic acids such as (meth) acrylic acid and crotonic acid
  • fumaric acid, itaconic acid maleic acid
  • Ethylenically unsaturated dicarboxylic acids such as citraconic acid (ie, dicarboxylic acids having an ethylenically
  • the acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
  • the acrylic monomer having the functional group that constitutes the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • an alkyl group constituting the alkyl ester is preferably a (meth) acrylic acid alkyl ester having a chain structure having 1 to 18 carbon atoms, such as (meth) acrylic.
  • acrylic monomer having no functional group examples include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
  • the acrylic monomer which does not have the functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • non-acrylic monomer examples include olefins such as ethylene and norbornene; vinyl acetate; styrene.
  • the said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
  • the proportion (content) of the structural unit derived from the acrylic monomer having the functional group is based on the total mass of the structural units constituting the acrylic polymer (a11).
  • the content is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass.
  • the degree of curing of the first protective film can be easily adjusted to a preferred range.
  • the acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferred, and those having an isocyanate group as the group are more preferred. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
  • the energy ray curable compound (a12) preferably has 1 to 5 energy ray curable groups in one molecule, and more preferably 1 to 3 energy ray curable groups.
  • Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl).
  • Ethyl isocyanate An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; Examples thereof include an acryloyl monoisocyanate compound obtained by a reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
  • the energy beam curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
  • the energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the content of the acrylic resin (a1-1) is preferably 1 to 40% by mass relative to the total mass of the protective film-forming composition (IV-1) other than the solvent, and 2 to 30% by mass. More preferably, the content is 3 to 20% by mass.
  • the content of the energy beam curable group derived from the energy beam curable compound (a12) with respect to the content of the functional group derived from the acrylic polymer (a11). is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is within such a range, the adhesive force of the protective film formed by curing is further increased.
  • the upper limit of the content ratio is 100 mol%
  • the energy ray curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule)
  • the upper limit of the content ratio may exceed 100 mol%.
  • the weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1500,000.
  • the polymer (a1) is at least partly crosslinked by the crosslinking agent (f)
  • the polymer (a1) is described as constituting the acrylic polymer (a11).
  • a monomer that does not correspond to any of the above-described monomers and has a group that reacts with the crosslinking agent (f) is polymerized to be crosslinked at the group that reacts with the crosslinking agent (f).
  • the group which reacts with the said functional group derived from the said energy-beam curable compound (a12) what was bridge
  • the polymer (a1) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000 examples include a group containing an energy ray curable double bond. Preferred examples include (meth) An acryloyl group, a vinyl group, etc. are mentioned.
  • the compound (a2) is not particularly limited as long as it satisfies the above-mentioned conditions.
  • the compound (a2) is a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, an energy ray curable group. Examples thereof include phenol resins.
  • examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
  • examples of the acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4 -((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane,
  • the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group are described in, for example, paragraph 0043 of “JP 2013-194102 A”. Things can be used.
  • Such a resin corresponds to a resin constituting the thermosetting component (h) described later, but is treated as the compound (a2) in the present invention.
  • the compound (a2) preferably has a weight average molecular weight of 100 to 30,000, more preferably 300 to 10,000.
  • the protective film-forming composition (IV-1) and the compound (a2) contained in the protective film-forming film may be only one kind, two kinds or more, and combinations of two or more kinds.
  • the ratio can be arbitrarily selected.
  • Polymer (b) having no energy ray curable group When the protective film forming composition (IV-1) and the protective film forming film contain the compound (a2) as the energy ray curable component (a), the polymer further does not have an energy ray curable group. It is also preferable to contain (b).
  • the polymer (b) may be at least partially crosslinked by the crosslinking agent (f) or may not be crosslinked.
  • polymer (b) having no energy ray curable group examples include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethanes. Examples thereof include resins.
  • the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as “acrylic polymer (b-1)”).
  • the acrylic polymer (b-1) may be a known one, for example, a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or two or more acrylic monomers and a monomer (non-acrylic monomer) other than one or two or more acrylic monomers.
  • acrylic monomer constituting the acrylic polymer (b-1) examples include (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth) acrylic acid ester, Examples include hydroxyl group-containing (meth) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters.
  • substituted amino group is as described above.
  • the (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms, such as (meth) acrylic acid.
  • Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl esters such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; (Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl; (Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester; Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester.
  • Examples of the glycidyl group-containing (meth) acrylic ester include glycidyl (meth) acrylate.
  • Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. Examples include propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
  • Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylate.
  • non-acrylic monomer constituting the acrylic polymer (b-1) examples include olefins such as ethylene and norbornene; vinyl acetate; styrene.
  • the reactive functional group in the polymer (b) is a crosslinking agent (f ).
  • the reactive functional group may be appropriately selected according to the type of the crosslinking agent (f) and the like, and is not particularly limited.
  • the crosslinking agent (f) is a polyisocyanate compound
  • examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. Among these, a hydroxyl group having high reactivity with an isocyanate group. Is preferred.
  • the crosslinking agent (f) is an epoxy compound
  • examples of the reactive functional group include a carboxy group, an amino group, an amide group, etc. Among them, a carboxy group having high reactivity with an epoxy group. Groups are preferred.
  • the reactive functional group is preferably a group other than a carboxy group in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip.
  • Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group.
  • examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester.
  • Examples of the acrylic monomer or non-acrylic monomer include those obtained by polymerizing a monomer in which one or two or more hydrogen atoms are substituted with the reactive functional group.
  • the proportion (content) of the structural units derived from the monomer having a reactive functional group is the total mass of the structural units constituting the polymer (b).
  • the content is preferably 1 to 25% by mass, more preferably 2 to 20% by mass.
  • the weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is 10,000 to 2,000,000 from the viewpoint that the film-forming property of the protective film-forming composition (IV-1) becomes better. It is preferably 100000 to 1500,000.
  • the polymer (b) having no energy ray-curable group contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind or two or more kinds. In the case of more than species, their combination and ratio can be arbitrarily selected.
  • Examples of the protective film-forming composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2).
  • the protective film-forming composition (IV-1) contains the compound (a2), it preferably contains a polymer (b) that does not have an energy ray-curable group. It is also preferable to contain (a1). Further, the protective film-forming composition (IV-1) does not contain the compound (a2) and contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. It may be.
  • the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group
  • the protective film-forming composition The content of the compound (a2) in (IV-1) is 10 to 10 when the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group is 100 parts by mass.
  • the amount is preferably 400 parts by mass, and more preferably 30 to 350 parts by mass.
  • the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group (with respect to the total mass of components other than the solvent) ( That is, the total content (mass) of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group is 5 to 90 mass% with respect to the total mass of the protective film-forming film. Preferably, it is 10 to 80% by mass, more preferably 15 to 70% by mass. When the ratio of the total content is within such a range, the energy ray curability of the protective film-forming film becomes better.
  • the content of the energy ray-curable component (a) with respect to the total content (total mass) of components other than the solvent is (that is, the total amount of the protective film-forming film).
  • the content of the energy ray-curable component (a) with respect to the mass) is preferably 6 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 30% by mass. Even more preferred is 19.5 to 27% by weight.
  • the protective film forming composition (IV-1) contains the energy beam curable component (a) and the polymer (b) having no energy beam curable group
  • the protective film forming composition (IV-1) ) And the protective film-forming film the content of the polymer (b) is preferably 3 to 160 parts by mass with respect to 100 parts by mass of the energy ray-curable component (a). More preferably, it is ⁇ 130 parts by mass.
  • the content of the polymer (b) is in such a range, the energy ray curability of the protective film-forming film becomes better.
  • the protective film-forming composition (IV-1) comprises a photopolymerization initiator (c) depending on the purpose.
  • the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h) the protective film-forming film formed is heated. Adhesive strength to the adherend is improved, and the strength of the protective film formed from this protective film-forming film is also improved.
  • Photopolymerization initiator (c) examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone, 2 Acetophenone compounds such as -hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide Compound; ⁇ -ketol compound such as 1-hydroxy
  • the photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the content of the photopolymerization initiator (c) is 100 parts by mass of the energy ray-curable compound (a). Is preferably 0.01 to 20 parts by mass, more preferably 2.0 to 12.0 parts by mass, and particularly preferably 2 to 10 parts by mass.
  • the protective film-forming film contains the filler (d)
  • the protective film obtained by curing the protective film-forming film can easily adjust the thermal expansion coefficient.
  • the reliability of the package obtained using the composite sheet for forming a protective film is further improved.
  • the moisture absorption rate of a protective film can be reduced or heat dissipation can be improved because the film for protective film formation contains a filler (d).
  • the filler (d) include those made of a heat conductive material.
  • the filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
  • Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
  • the inorganic filler is preferably silica or alumina, and more preferably epoxy-modified silica.
  • the average particle diameter of the filler (d) is not particularly limited, but is preferably 0.01 to 20 ⁇ m, more preferably 0.08 to 15 ⁇ m, and more preferably 0.1 to 15 ⁇ m. 0.1 to 10 ⁇ m is more preferable, 0.3 to 10 ⁇ m is more preferable, and 0.5 to 8 ⁇ m is particularly preferable.
  • average particle size means the value of the particle size (D 50 ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. .
  • the protective film-forming composition (IV-1) and the filler (d) contained in the protective film-forming film may be only one type, two or more types, and combinations of two or more types.
  • the ratio can be arbitrarily selected.
  • the content of the filler (d) relative to the total content (total mass) of all components other than the solvent in the protective film-forming composition (IV-1) (that is, the protective film)
  • the content of the filler (d) relative to the total mass of the forming film) is preferably 5 to 83% by mass, and more preferably 7 to 78% by mass.
  • the content of the filler (d) is preferably 5 to 83% by mass, and preferably 5 to 70% by mass with respect to the total mass of the protective film-forming film. More preferred.
  • the content of the filler (d) is based on the total mass of the protective film-forming film.
  • the content is preferably 5 to 83% by mass, more preferably 5 to 70% by mass.
  • the average particle diameter of the filler (d) is 0.5 to 8 ⁇ m
  • the content of the filler (d) is based on the total mass of the protective film-forming film.
  • the content is preferably 5 to 8% by mass.
  • the surface roughness (Ra) of at least one surface ( ⁇ ) in the protective film-forming film is 0.04 ⁇ m or more, more preferably 0.8. It becomes easier to adjust to 049 ⁇ m or more, and it becomes easier to adjust the surface roughness (Ra) of the surface ( ⁇ ) to 0.15 ⁇ m or less, more preferably 0.129 ⁇ m or less. That is, when the content of the filler (d) is in the above range, the surface roughness (Ra) of at least one surface ( ⁇ ) in the protective film-forming film is preferably 0.04 to 0.15 ⁇ m, More preferably, it becomes easy to adjust to 0.049 to 0.129 ⁇ m.
  • Coupleling agent (e) By using a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesion of the protective film-forming film to the adherend can be improved. Further, by using the coupling agent (e), the protective film obtained by curing the protective film-forming film has improved water resistance without impairing the heat resistance.
  • the coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the energy beam curable component (a), the polymer (b) having no energy beam curable group, and the like. More preferably, it is a silane coupling agent.
  • silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropi Examples include trimethoxysilane, 3-
  • the protective film-forming composition (IV-1) and the coupling agent (e) contained in the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • the content of the coupling agent (e) in the composition for forming a protective film (IV-1) and the film for forming a protective film includes the energy ray curable component (a) and the energy.
  • the total content of the polymer (b) having no linear curable group is 100 parts by mass, it is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass. 0.1 to 5 parts by mass is particularly preferable.
  • the content of the coupling agent (e) is equal to or higher than the lower limit, the dispersibility of the filler (d) in the resin is improved and the adhesion of the protective film-forming film to the adherend is improved.
  • the effect by using a coupling agent (e) etc. is acquired more notably.
  • production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.
  • Crosslinking agent (f) By using the crosslinking agent (F) and crosslinking the polymer (b) having no energy beam curable component (a) or energy beam curable group, the initial adhesive force and cohesive force of the protective film-forming film. Can be adjusted.
  • crosslinking agent (f) examples include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.
  • organic polyvalent isocyanate compound examples include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”).
  • a trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc.
  • the “adduct body” includes the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound, or the alicyclic polyvalent isocyanate compound, and a low amount of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, or the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include an xylylene diisocyanate adduct of trimethylolpropane as described later.
  • the “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.
  • organic polyvalent isocyanate compound for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.
  • a polyol such as propane.
  • organic polyvalent imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, and tetramethylolmethane.
  • -Tri- ⁇ -aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.
  • the crosslinking agent (f) When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray curable component (a) or the polymer (b) having no energy ray curable group.
  • the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray-curable property.
  • a cross-linked structure can be easily introduced into the protective film-forming film by reaction with the component (a) or the polymer (b) having no energy ray-curable group.
  • the crosslinking agent (f) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, or a combination of two or more types.
  • the ratio can be arbitrarily selected.
  • the content of the crosslinking agent (f) in the protective film-forming composition (IV-1) is such that the energy ray-curable component (a) and the energy ray-curable group having no energy ray-curable group are contained.
  • the total content of the combined (b) is 100 parts by mass, it is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass. It is particularly preferred that When the content of the cross-linking agent (f) is equal to or higher than the lower limit value, the effect of using the cross-linking agent (f) is more remarkably obtained. Moreover, the excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.
  • Colorant (g) examples include known pigments such as inorganic pigments, organic pigments, and organic dyes.
  • organic pigments and organic dyes examples include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanines.
  • the inorganic pigment examples include carbon black, cobalt dye, iron dye, chromium dye, titanium dye, vanadium dye, zirconium dye, molybdenum dye, ruthenium dye, platinum dye, ITO (That is, indium tin oxide) dyes, ATO (that is, antimony tin oxide) dyes, and the like can be given.
  • the protective film-forming composition (IV-1) and the colorant (g) contained in the protective film-forming film may be only one kind, two kinds or more, and combinations of two or more kinds.
  • the ratio can be arbitrarily selected.
  • the content of the colorant (g) in the protective film-forming film may be appropriately adjusted according to the purpose.
  • the protective film may be printed by laser irradiation, and by adjusting the content of the colorant (g) in the protective film-forming film and adjusting the light transmittance of the protective film, the print visibility is improved. Can be adjusted.
  • the content of the colorant (g) relative to the total content of all components other than the solvent that is, the colorant relative to the total mass of the protective film-forming film (
  • the content of g) is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass. .
  • the effect by using a colorant (g) is acquired more notably because the content of the colorant (g) is not less than the lower limit. Moreover, the excessive use of a coloring agent (g) is suppressed because the said content of a coloring agent (g) is below the said upper limit.
  • thermosetting component (h) The thermosetting component (h) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind, two kinds or more, and if two or more kinds, These combinations and ratios can be arbitrarily selected.
  • thermosetting component (h) examples include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy thermosetting resins are preferable.
  • the epoxy thermosetting resin includes an epoxy resin (h1) and a thermosetting agent (h2).
  • the epoxy thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • Epoxy resin (h1) examples include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.
  • an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (h1).
  • An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the composite sheet for forming a protective film is improved by using an epoxy resin having an unsaturated hydrocarbon group.
  • Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group. Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple
  • the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and a (meth) acryloyl group. , (Meth) acrylamide groups and the like, and an acryloyl group is preferred.
  • the number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30000 from the viewpoint of curability of the protective film-forming film and strength and heat resistance of the protective film, and is preferably 400 to 10,000. More preferably, it is more preferably 500 to 3000.
  • the “number average molecular weight” means a number average molecular weight represented by a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
  • the epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.
  • the “epoxy equivalent” means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.
  • epoxy resin (h1) one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.
  • thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
  • a thermosetting agent (h2) the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example.
  • the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
  • thermosetting agents (h2) examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
  • examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
  • the thermosetting agent (h2) may have an unsaturated hydrocarbon group.
  • the thermosetting agent (h2) having an unsaturated hydrocarbon group for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
  • the unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
  • thermosetting agent (h2) In the case where a phenolic curing agent is used as the thermosetting agent (h2), it is preferable that the thermosetting agent (h2) has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. .
  • thermosetting agent (h2) for example, the number average molecular weight of the resin component such as polyfunctional phenolic resin, novolac-type phenolic resin, dicyclopentadiene-based phenolic resin, aralkylphenolic resin, etc. is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
  • the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
  • thermosetting agent (h2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
  • the content of the thermosetting agent (h2) is 100% of the epoxy resin (h1).
  • the amount is preferably 0.01 to 20 parts by mass with respect to parts by mass.
  • thermosetting component (h) when used, the content of the thermosetting component (h) (for example, the epoxy resin (h1) and the heat in the protective film-forming composition (IV-1) and the protective film-forming film)
  • the total content of the curing agent (h2) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b) having no energy ray curable group.
  • the general-purpose additive (z) may be a known one, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. Is mentioned.
  • the general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind, two or more kinds, and when there are two or more kinds, Combinations and ratios can be arbitrarily selected.
  • the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited and is appropriately selected according to the purpose. do it.
  • the protective film-forming composition (IV-1) preferably further contains a solvent.
  • the protective film-forming composition (IV-1) containing a solvent has good handleability.
  • the solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. Esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
  • the solvent contained in the protective film-forming composition (IV-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the solvent contained in the protective film-forming composition (IV-1) is methyl ethyl ketone, toluene, ethyl acetate, or the like from the viewpoint that the components contained in the protective film-forming composition (IV-1) can be mixed more uniformly. It is preferable.
  • the composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending each component for constituting the composition.
  • the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
  • a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
  • the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
  • the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
  • the protective film-forming composite sheet of the present invention is affixed to the back surface opposite to the circuit surface of the semiconductor wafer or semiconductor chip, and as a composite sheet provided with a layer showing adhesion on the support sheet.
  • a dicing die bonding sheet There is a dicing die bonding sheet.
  • the adhesive layer provided in the dicing die bonding sheet functions as an adhesive when the semiconductor chip is picked up from the support sheet together with the semiconductor chip and then attached to the substrate, the lead frame, or another semiconductor chip.
  • the protective film-forming film in the protective film-forming composite sheet of the present invention is the same as the adhesive layer in that it is picked up from the support sheet together with the semiconductor chip, but eventually becomes a protective film by curing, It has a function of protecting the back surface of the semiconductor chip that is affixed.
  • the protective film-forming film in the present invention has a different use from the adhesive layer in the dicing die bonding sheet, and naturally the required performance is also different. Reflecting this difference in use, the protective film-forming film is usually harder and more difficult to pick up than the adhesive layer in the dicing die bonding sheet.
  • the composite sheet for forming a protective film according to the present invention is extremely excellent as compared with the conventional one with regard to the suitability for picking up a semiconductor chip with a protective film, provided with an energy ray curable protective film-forming film.
  • the protective film-forming composite sheet of the present invention can be produced by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship.
  • the method for forming each layer is as described above.
  • the above-described pressure-sensitive adhesive composition may be applied on the substrate and dried as necessary.
  • the protective film-forming composition is applied on the adhesive layer, It is possible to form the forming film directly.
  • Layers other than the protective film-forming film can also be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming this layer.
  • the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed.
  • the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers already formed.
  • the composition is preferably applied to the release-treated surface of the release film.
  • the release film may be removed as necessary after forming the laminated structure.
  • a protective film-forming composite sheet in which a pressure-sensitive adhesive layer is laminated on a base material and a protective film-forming film is laminated on the pressure-sensitive adhesive layer (the support sheet is a laminate of the base material and the pressure-sensitive adhesive layer)
  • a pressure-sensitive adhesive composition is coated on a base material and dried as necessary, whereby a pressure-sensitive adhesive layer is laminated on the base material
  • the protective film-forming composition is coated on the release film, and dried as necessary to form the protective film-forming film on the release film.
  • the exposed surface of the protective film-forming film is bonded to the exposed surface of the adhesive layer laminated on the substrate, and the protective film-forming film is laminated on the adhesive layer, thereby forming a protective film.
  • a composite sheet is obtained.
  • the pressure-sensitive adhesive composition is applied on the release film.
  • the pressure-sensitive adhesive layer is formed on the release film by drying as necessary, and the exposed surface of this layer is bonded to one surface of the base material so that the pressure-sensitive adhesive layer is placed on the base material. You may laminate. In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.
  • a layer that employs such a process may be appropriately selected to produce a protective sheet-forming composite sheet.
  • the composite sheet for forming a protective film is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) opposite to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a protective film-forming composition, is applied on this release film (preferably its release-treated surface) and dried as necessary. Then, a layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the release film by any of the methods described above. And the composite sheet for protective film formation is obtained also by leaving it in the state bonded together, without removing a peeling film.
  • a composition for forming a layer constituting the outermost layer such as a protective film-forming composition
  • the protective film-forming composite sheet of the present invention can be used, for example, by the method described below. That is, the protective film-forming composite sheet is attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer with the protective film-forming film. Next, the protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to form a protective film. Next, the semiconductor wafer is divided together with the protective film by dicing to form semiconductor chips. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is attached (that is, as a semiconductor chip with a protective film). Thereafter, the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then the semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.
  • the order of performing these steps is as follows: The reverse may be possible. That is, after a protective film-forming composite sheet is attached to the back surface of the semiconductor wafer, the semiconductor wafer is divided together with the protective film-forming film by dicing to form semiconductor chips. Next, the divided protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to form a protective film. Thereafter, in the same manner as described above, the semiconductor chip with the protective film may be pulled away from the support sheet and picked up to produce the target semiconductor device.
  • Energy ray curable component (a2) -1 Tricyclodecane dimethylol diacrylate (“KAYARAD R-684”, bifunctional ultraviolet curable compound, molecular weight 304, manufactured by Nippon Kayaku Co., Ltd.)
  • Acrylic resin weight average molecular weight 300000, glass transition temperature ⁇ 1 ° C.
  • Photopolymerization initiator (c) -1 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (“Irgacure (registered trademark) 369” manufactured by BASF)
  • C) -2 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Irgacure (registered by BASF)) Trademark) OXE02 ")
  • (Production of pressure-sensitive adhesive composition (I-4)) Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and further as a solvent
  • a non-energy ray-curable pressure-sensitive adhesive composition (I-4) containing methyl ethyl ketone and having a solid content concentration of 30% by mass was prepared.
  • the acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass).
  • the weight average molecular weight is 600,000.
  • the pressure-sensitive adhesive composition (I-4) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. ) And heated and dried at 120 ° C. for 2 minutes to form a non-energy ray curable pressure-sensitive adhesive layer having a thickness of 10 ⁇ m.
  • a support sheet provided with the pressure-sensitive adhesive layer on one surface of the base material by bonding a polypropylene film (Young's modulus 400 MPa, thickness 80 ⁇ m) as a base material to the exposed surface of the pressure-sensitive adhesive layer. (10) -1 was obtained.
  • the protective film-forming composition (IV) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) from which one side of a polyethylene terephthalate film was released by silicone treatment. -1) was coated with a knife coater and dried at 100 ° C. for 2 minutes to prepare an energy ray-curable protective film-forming film (13) -1 having a thickness of 25 ⁇ m.
  • SP-PET 381031 manufactured by Lintec Co., Ltd., thickness 38 ⁇ m
  • the release film is removed from the pressure-sensitive adhesive layer of the support sheet (10) -1 obtained above, and the protective film-forming film (13) -1 obtained above is exposed on the exposed surface of the pressure-sensitive adhesive layer.
  • the surfaces were bonded together to prepare a composite sheet for forming a protective film, in which a base material, an adhesive layer, a protective film-forming film (13) -1 and a release film were laminated in this order in the thickness direction.
  • Table 2 shows the structure of the obtained protective sheet-forming composite sheet.
  • the protective film-forming composite sheet obtained above is attached to the # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 ⁇ m) with the protective film-forming film (13) -1 and this sheet is further attached to the ring frame. Fixed and allowed to stand for 30 minutes.
  • the protective sheet-forming composite sheet is formed from the support sheet (10) -1 side under the conditions of an illuminance of 195 mW / cm 2 and a light amount of 170 mJ / cm 2.
  • the protective film-forming film (13) -1 was cured to form a protective film.
  • the silicon wafer was diced together with the protective film using a dicing blade, and a silicon chip having a length of 3 mm ⁇ width of 3 mm, a protective layer thickness of 25 ⁇ m, and a Si layer thickness of 350 ⁇ m was obtained.
  • 20 silicon chips with a protective film were picked up using a die bonder (“BESTEM-D02” manufactured by Canon Machinery Co., Ltd.). Square grid-like positions of 4 x 4 x silicon chips with a protective film obtained on a 12 cm long x 12 cm wide, 5 mm thick iron plate with the above-mentioned protective film being evenly spaced from each other.
  • a cover tape (CSL-Z7302 made by Sumitomo Bakelite Co., Ltd., 12 cm long and 3.8 cm wide) is placed on the plate, placed on a hot plate heated to 40 ° C., and a metal plate is placed thereon. It was set so that the pressure applied to the silicon chip with the protective film applied was 350 gf and heated for one minute. Thereafter, the metal plate was removed, the cover tape was peeled off, and it was tested whether or not the silicon chip with a protective film adhered to the cover tape. The results are shown in Table 2. As a determination method, if any one of the 16 silicon chips with a protective film adheres to the cover tape, the determination is “A”, and one of the 16 silicon chips with the protective film is also applied to the cover tape. When it did not adhere, it was determined to be “B”.
  • Example 2 ⁇ Manufacture and evaluation of composite sheet for protective film formation> As shown in Table 1, the protective film was formed in the same manner as in Example 1 except that 20 parts by mass of the content (blending amount) of the energy ray curable component (a2) -1 was replaced with 30 parts by mass. Composition (IV-1) was prepared. Except for the use of the protective film-forming composition (IV-1) obtained above, the energy ray-curable protective film-forming film (13) -25 having a thickness of 25 ⁇ m was prepared in the same manner as in Example 1. Was made. Then, a protective sheet-forming composite sheet was produced in the same manner as in Example 1 except that the protective film-forming film (13) -1 was replaced with the protective film-forming film (13) -25. Table 2 shows the structure of the obtained protective sheet-forming composite sheet. Using the protective film-forming composite sheet obtained above, the ball tack value was measured and the cover tape adhesion was evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Example 3 ⁇ Manufacture and evaluation of composite sheet for protective film formation> As shown in Table 1, 0.3 parts by mass of the content (blending amount) of photopolymerization initiator (c) -1 was replaced with 1.0 part by mass, and the content of photopolymerization initiator (c) -2 A protective film-forming composition (IV-1) was prepared in the same manner as in Example 1 except that 0.3 part by mass of (blending amount) was changed to 1.0 part by mass. Except for the use of the protective film-forming composition (IV-1) obtained above, the energy ray-curable protective film-forming film (13) -26 having a thickness of 25 ⁇ m was prepared in the same manner as in Example 1. Was made.
  • a protective film-forming composite sheet was produced in the same manner as in Example 1 except that the protective film-forming film (13) -1 was replaced with the protective film-forming film (13) -26.
  • Table 2 shows the structure of the obtained protective sheet-forming composite sheet. Using the protective film-forming composite sheet obtained above, the ball tack value was measured and the cover tape adhesion was evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Example 1 ⁇ Manufacture and evaluation of composite sheet for protective film formation>
  • the protective film was formed in the same manner as in Example 1 except that 20 parts by mass of the content (blending amount) of the energy beam curable component (a2) -1 was changed to 5 parts by mass.
  • Composition (IV-1) was prepared. Except for the use of the protective film-forming composition (IV-1) obtained above, the energy ray-curable protective film-forming film (13) -27 having a thickness of 25 ⁇ m was prepared in the same manner as in Example 1. Was made. Then, a protective film-forming composite sheet was produced in the same manner as in Example 1, except that the protective film-forming film (13) -1 was replaced with the protective film-forming film (13) -27.
  • Table 2 shows the structure of the obtained protective sheet-forming composite sheet. Using the protective film-forming composite sheet obtained above, the ball tack value was measured and the cover tape adhesion was evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • a protective film-forming composite sheet was produced in the same manner as in Example 1, except that the protective film-forming film (13) -1 was replaced with the protective film-forming film (13) -28.
  • Table 2 shows the structure of the obtained protective sheet-forming composite sheet. Using the protective film-forming composite sheet obtained above, the ball tack value was measured and the cover tape adhesion was evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • the ball tack value measured at an inclination angle of 30 ° according to JIS Z0237: 2010 of the protective film was 2 It was as follows and it was suppressed that the semiconductor chip with a protective film adhered to a cover tape.
  • the ball tack value measured at an inclination angle of 30 ° according to JIS Z0237: 2010 of the protective film was 3 to 4. If there is, it is assumed that it was easy to adhere to the cover tape.
  • the protective film-forming composite sheet of Comparative Example 1 the energy ray-curable component (a) in the protective film-forming composition (IV-1) with respect to the total content of components other than the solvent Since the proportion of the content was as low as 5.8% by mass, it is presumed that the energy ray curing was not sufficient and the ball tack value was increased.
  • the content of the photopolymerization initiator (c) in the protective film-forming film is 100 parts by mass of the energy ray-curable component (a). Since the amount was as small as 1 part by mass, it was estimated that the composite sheet for forming a protective film was not sufficiently cured and the ball tack value was increased.
  • the present invention is industrially useful because it can be used for manufacturing semiconductor devices.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un film durcissable par rayonnement d'énergie pour former un revêtement protecteur, ledit film étant destiné à former un revêtement protecteur ayant une caractéristique selon laquelle, lorsque ledit film destiné à former un revêtement protecteur a été exposé à un rayonnement d'énergie et transformé en un revêtement protecteur, l'indice de collage dudit revêtement protecteur est égal ou inférieur à 2, ledit indice de collage étant mesuré selon la norme JIS Z 0237 : 2010 selon un angle d'inclinaison de 30 °.
PCT/JP2017/016335 2016-04-28 2017-04-25 Film pour former un revêtement protecteur et feuille composite pour former un revêtement protecteur WO2017188231A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020187030754A KR102407322B1 (ko) 2016-04-28 2017-04-25 보호막 형성용 필름 및 보호막 형성용 복합 시트
CN201780025032.9A CN109071845A (zh) 2016-04-28 2017-04-25 保护膜形成用膜以及保护膜形成用复合片
JP2018514615A JP6971977B2 (ja) 2016-04-28 2017-04-25 保護膜形成用フィルム及び保護膜形成用複合シート、並びに、保護膜付き半導体チップの製造方法及び保護膜付き半導体チップの梱包方法

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JP2016-092013 2016-04-28
JP2016092013 2016-04-28

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KR (1) KR102407322B1 (fr)
CN (1) CN109071845A (fr)
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JP2022026312A (ja) * 2020-07-30 2022-02-10 日亜化学工業株式会社 発光装置およびその製造方法ならびに梱包体

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KR102519799B1 (ko) * 2018-03-30 2023-04-10 린텍 가부시키가이샤 지지 시트 및 보호막 형성용 복합 시트
KR20200133288A (ko) 2019-05-16 2020-11-27 삼성디스플레이 주식회사 고분자 수지, 이를 포함하는 윈도우 모듈, 및 이를 포함하는 표시 장치

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KR100815383B1 (ko) * 2006-12-28 2008-03-20 제일모직주식회사 점착필름 형성용 광경화성 조성물 및 이를 포함하는 다이싱다이본딩 필름
JP2010031183A (ja) 2008-07-30 2010-02-12 Furukawa Electric Co Ltd:The エネルギー線硬化型チップ保護用フィルム
JP5144433B2 (ja) * 2008-08-28 2013-02-13 古河電気工業株式会社 チップ保護用フィルム
WO2014092200A1 (fr) * 2012-12-14 2014-06-19 リンテック株式会社 Film constituant une membrane de retenue
CN104937712B (zh) * 2013-03-22 2018-03-27 琳得科株式会社 保护膜形成用膜及保护膜形成用复合片
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JP2010212474A (ja) * 2009-03-11 2010-09-24 Nitto Denko Corp 半導体ウエハ保護用基材レス粘着シート、その粘着シートを用いた半導体ウエハ裏面研削方法及びその粘着シートの製造方法
JP2012028404A (ja) * 2010-07-20 2012-02-09 Nitto Denko Corp フリップチップ型半導体裏面用フィルム、及び、ダイシングテープ一体型半導体裏面用フィルム
JP2013181109A (ja) * 2012-03-02 2013-09-12 Nitto Denko Corp 粘着シート

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Publication number Priority date Publication date Assignee Title
JP2022026312A (ja) * 2020-07-30 2022-02-10 日亜化学工業株式会社 発光装置およびその製造方法ならびに梱包体
JP7288200B2 (ja) 2020-07-30 2023-06-07 日亜化学工業株式会社 発光装置および梱包体

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KR20190002471A (ko) 2019-01-08
JPWO2017188231A1 (ja) 2019-03-07
TW201806767A (zh) 2018-03-01
CN109071845A (zh) 2018-12-21
TWI781099B (zh) 2022-10-21
JP6971977B2 (ja) 2021-11-24

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