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WO2017188199A1 - 保護膜形成用フィルムおよび保護膜形成用複合シート - Google Patents

保護膜形成用フィルムおよび保護膜形成用複合シート Download PDF

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Publication number
WO2017188199A1
WO2017188199A1 PCT/JP2017/016257 JP2017016257W WO2017188199A1 WO 2017188199 A1 WO2017188199 A1 WO 2017188199A1 JP 2017016257 W JP2017016257 W JP 2017016257W WO 2017188199 A1 WO2017188199 A1 WO 2017188199A1
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WO
WIPO (PCT)
Prior art keywords
protective film
forming
film
meth
sensitive adhesive
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2017/016257
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English (en)
French (fr)
Japanese (ja)
Inventor
裕之 米山
洋一 稲男
力也 小橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
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 Lintec Corp filed Critical Lintec Corp
Priority to CN202411359173.2A priority Critical patent/CN119141993A/zh
Priority to KR1020187028258A priority patent/KR102399678B1/ko
Priority to CN201780023956.5A priority patent/CN109072009A/zh
Priority to JP2018514594A priority patent/JP7170534B2/ja
Publication of WO2017188199A1 publication Critical patent/WO2017188199A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H10P95/00—
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

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.
  • the support sheet can be used as a dicing sheet, and the protective film-forming film and the dicing sheet can be integrated.
  • a composite sheet for forming a protective film 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.
  • the protective film-forming composite sheet is attached to the back surface (the surface opposite to the electrode-forming surface) of the semiconductor wafer with a thermosetting protective film-forming film.
  • the protective film-forming film is cured by heating to form a protective film, and the semiconductor wafer is divided together with the protective film by dicing to form semiconductor chips. Curing and dicing of the protective film-forming film 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 beam curable protective film (see Patent Document 1) formed on a release film, or an energy beam curable chip protective film that can form a protective film having high hardness and excellent adhesion to a semiconductor chip. Reference 2) is disclosed.
  • FIG. 7A to 7C are schematic cross-sectional views schematically showing a conventional process from dicing a semiconductor wafer to curing and picking up.
  • the semiconductor wafer 18 has a protective film forming composite sheet 10 affixed to the back surface thereof, and then there are two types: a type in which the protective film forming film 13 'is cured after a dicing step and a type in which dicing is performed after curing. is there.
  • the semiconductor wafer 18 is cut into a plurality of semiconductor chips 181, 181,... By the dicing blade 20 by dicing (FIG. 17A). At this time, the side surface of the cut semiconductor chip 181 is exposed, and the protective film forming film 13 attached to the back surface of the semiconductor chip 181 is also cut to expose the cross section.
  • an object of the present invention is to provide an energy ray-curable protective film-forming film and a protective film-forming composite sheet that does not cause poor curing even when cured in the presence of oxygen and does not cause pickup failure. .
  • the inventors of the present invention have made extensive studies to solve the above problems.
  • the above-mentioned problem can be obtained by blending a protective film-forming film or a protective-film-forming composite sheet with a photoradical initiator having an absorption coefficient of 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more at a wavelength of 365 nm.
  • the present invention has been completed.
  • the present invention is an energy ray-curable film for forming a protective film, and in the protective film-forming film, light having an extinction coefficient at a wavelength of 365 nm of 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more. It is a film for protective film formation containing a radical initiator.
  • the photo radical initiator is preferably a hydrogen abstraction type photo radical initiator having three or more aromatic rings in one molecule.
  • the photoradical initiator is preferably a photoradical initiator having two or more photodegradable groups in one molecule.
  • the present invention may also be a protective film-forming composite sheet comprising the protective film-forming film described above on a support sheet.
  • an energy ray-curable protective film-forming film and a protective film-forming composite sheet that do not cause curing failure even when cured in the presence of oxygen and do not cause pickup failure.
  • ⁇ protective film forming film for the protective film forming film present invention relates to a protective film formation film of an energy ray-curable, in the protective film forming film, the absorption coefficient of the wavelength 365nm is 4.0 ⁇ 10 1 It contains a photoradical initiator of ml / (g ⁇ cm) or more.
  • the photo radical initiator according to the present invention may be a hydrogen abstraction type photo radical initiator having three or more aromatic rings in one molecule.
  • the photoradical initiator according to the present invention may be a photoradical initiator having two or more photodegradable groups in one molecule.
  • the photoradical initiator according to the present invention preferably has an extinction coefficient at a wavelength of 365 nm of 1.0 ⁇ 10 4 ml / (g ⁇ cm) or less.
  • the extinction coefficient at a wavelength of 365 nm of the photoradical initiator is not more than the above value, it is possible to suppress unintentional reaction when used under a fluorescent lamp or natural light, and the composite sheet can be used stably.
  • the protective film-forming film of the 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.
  • FIG. 6 is a cross-sectional view schematically showing one embodiment of the protective film-forming film of the present invention.
  • the 1st peeling film 15b, the protective film formation film 13 (23), and the 2nd peeling film 15a are laminated
  • the composite sheet for protective film formation of the present invention is provided with an energy ray-curable protective film-forming film on a support sheet, and in the protective film-forming film, the absorption wavelength is 365 nm.
  • a photo radical initiator having a coefficient of 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more is blended.
  • the “protective film-forming film” means a film before curing
  • the “protective film” means a film obtained by curing the protective film-forming film.
  • 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 composite sheet for protective film formation of this invention has antistatic property by making the surface resistance value rate of the film for protective film formation into 10 ⁇ 12 > ohm * cm or less.
  • the semiconductor chip can be prevented from being charged even after the dicing process. As a result, the semiconductor chips are prevented from adhering to the cover tape when shipped in reels and peeled off in the next step. Further, since the semiconductor chip itself is prevented from being charged, it is possible to prevent dust or dirt from adhering to the semiconductor chip due to static electricity.
  • “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 beam curability” means a property of being cured by irradiation with energy rays.
  • “Non-energy radiation curable” means a property that does not cure even when irradiated with energy rays.
  • the thickness of the semiconductor wafer or the 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. In order to obtain the effects of the present invention more remarkably, the thickness is preferably 30 to 1000 ⁇ m, more preferably 100 to 300 ⁇ m.
  • 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. It means that only some of the layers may be the same.
  • “a plurality of layers are different from each other” means “at least one of the constituent material and thickness of each layer is different from each other”.
  • 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. 1 is a cross-sectional view schematically showing one embodiment of a composite sheet for forming a protective film of the present invention.
  • the protective film-forming composite sheet 1 ⁇ / b> A shown here comprises a pressure-sensitive adhesive layer 12 on a base material 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.
  • the protective film-forming composite sheet 1 ⁇ / b> A has a protective film-forming film 13 laminated on one surface 10 a of the support sheet 10. Have a configuration.
  • 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 11 a of the substrate 11.
  • a protective film forming film 13 is laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12.
  • a jig adhesive layer 16 is laminated on a part of the surface 13a of the protective film-forming film 13, that is, in the vicinity of the peripheral edge.
  • the release film 15 is laminated on the surface on which the jig adhesive layer 16 is not laminated and on the surface 16a (upper surface and side face) of the jig adhesive layer 16. ing.
  • the protective film-forming film 13 contains a photoradical initiator having an absorption coefficient of 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more at a wavelength of 365 nm. Further, the adhesive force between the cured protective film-forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is 50 to 1500 mN / 25 mm. Preferably there is.
  • 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 back surface of a semiconductor wafer (not shown) is attached to the front surface 13a of the film 13 for forming a protective film with the release film 15 removed.
  • the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.
  • FIG. 2 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. 1 except that it does not include the jig adhesive layer 16. That is, in the protective film-forming composite sheet 1 ⁇ / b> B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11. A protective film-forming film 13 is laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12, and a release film 15 is laminated on the entire surface 13 a of the protective film-forming film 13.
  • the composite sheet 1B for forming a protective film shown in FIG. 2 has a semiconductor wafer (not shown) formed 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 side is affixed.
  • region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.
  • FIG. 3 is a cross-sectional view schematically showing still another embodiment of the protective sheet-forming composite sheet 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. 1, 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). Next, the jig adhesive layer 16 is laminated on a part of the surface 13 a of the protective film forming film 13, that is, in the vicinity of the peripheral edge. Of the surface 13a of the protective film forming film 13, the release film 15 is laminated on the surface on which the jig adhesive layer 16 is not laminated and on the surface 16a (upper surface and side face) of the jig adhesive layer 16. ing.
  • the protective film-forming film 13 includes a photoradical initiator having an absorption coefficient of wavelength of 365 nm of 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more. Further, the adhesive force between the cured protective film-forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the substrate 11 is 50 to 1500 mN / 25 mm. It is preferable.
  • 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 side of (not shown) is attached.
  • the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.
  • 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 1D shown here is the same as the protective film-forming composite sheet 1C shown in FIG. 3 except that it does not include the jig adhesive layer 16. That is, in the protective film forming composite sheet 1 ⁇ / b> D, the protective film forming film 13 is laminated on one surface 11 a of the substrate 11. And the peeling film 15 is laminated
  • the protective film-forming composite sheet 1D shown in FIG. 4 is the same as the protective film-forming composite sheet 1B shown in FIG. 2, with the release film 15 removed, of the surface 13a of the protective film-forming film 13,
  • the back surface of a semiconductor wafer (not shown) is attached to a partial area on the center side. Furthermore, the area
  • 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 film-forming composite sheet 1E shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 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.
  • the protective film-forming composite sheet 1 ⁇ / b> E has a configuration in which the protective film-forming film 23 is laminated on one surface 10 a of the support sheet 10.
  • 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 substrate 11, and a part of the surface 12a of the pressure-sensitive adhesive layer 12, that is, a protective film-forming film is formed in the central region. 23 are stacked. And the peeling film 15 is laminated
  • 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 protective film-forming film 23 includes a photoradical initiator having an absorption coefficient of wavelength of 365 nm of 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more.
  • the adhesive force between the protective film-forming film 23 after curing (ie, the protective film) and the support sheet 10 is 50 to 1500 mN / 25 mm. Preferably there is.
  • the back surface of the semiconductor wafer (not shown) is attached to the front surface 23a of the protective film-forming film 23 with the release film 15 removed. Further, the surface of the pressure-sensitive adhesive layer 12 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. 1 and 3 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 having 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.
  • the protective film-forming composite sheet of the present invention having a jig adhesive layer has 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.
  • a part of the structure shown in FIGS. 1 to 5 is changed or deleted, or another structure is added to what has been described so far. Also good.
  • 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. Further, in the composite sheet for forming a protective film shown in FIGS.
  • layers other than the intermediate layer may be provided at an arbitrary location.
  • 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 of 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 degree of curing of the protective film-forming film is further improved.
  • 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.
  • 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%.
  • 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%.
  • the base material is in the form of a sheet or film, and examples of the constituent material include various resins.
  • the resin include the following. Polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), etc .; polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate Polymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-based copolymers such as ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer) Polymer); vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene terephthalate
  • polymer alloys such as a mixture of the said polyester and other resin
  • 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.
  • 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 a base material having such a high thickness accuracy include the following.
  • 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 pressure-sensitive adhesive include the following. Examples thereof include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, and acrylic resins are preferred.
  • the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin.
  • the resin itself has adhesiveness, but also includes a resin that exhibits adhesiveness in combination with other components such as additives, and a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water.
  • the pressure-sensitive adhesive layer may be composed of one layer (single layer) or may be composed of two or more layers. In the case of a plurality of layers, these layers may be the same as or different from each other, and the combination of these 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 entire pressure-sensitive adhesive layer.
  • the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the pressure-sensitive adhesive layer.
  • 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 using 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 at which cooling or heating is not performed, that is, a normal temperature. For example, a temperature of 15 to 25 ° C. can be mentioned.
  • Application of the pressure-sensitive adhesive composition may be performed by a known method.
  • Examples thereof include methods using various coaters such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, and kiss coater.
  • the drying conditions for the pressure-sensitive adhesive composition are not particularly limited.
  • the pressure-sensitive adhesive composition is preferably heat-dried when it contains a solvent described later. In this case, for example, drying is preferably performed at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • examples of the pressure sensitive adhesive composition containing the energy ray curable pressure sensitive adhesive include the following.
  • a pressure-sensitive adhesive containing a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter sometimes abbreviated as “pressure-sensitive resin (I-1a)”) and an energy beam-curable compound Composition (I-1); energy ray curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of non-energy ray curable adhesive resin (I-1a) (hereinafter referred to as “ A pressure-sensitive adhesive composition (I-2) containing a pressure-sensitive adhesive resin (I-2a); and the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.
  • Examples thereof include a pressure-sensitive adhesive composition (I-3).
  • 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.
  • 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.
  • the alkyl group is preferably linear or branched. 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-o
  • 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 the following. For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol ((meth) acryloyl) And unsaturated alcohol having no skeleton).
  • carboxy group-containing monomer examples include the following.
  • ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (monocarboxylic acids having an ethylenically unsaturated bond); ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid
  • acids dicarboxylic acids having an ethylenically unsaturated bond
  • anhydrides of the ethylenically unsaturated dicarboxylic acids (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like.
  • 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. 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, and more preferably 2 to 32% by mass with respect to the total amount of the structural unit. It is particularly 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 copolymerizable with (meth) acrylic acid alkyl ester or the like.
  • Examples of 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 one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof 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 (energy ray-polymerizable group). It can be used as the resin (I-2a).
  • the pressure-sensitive adhesive composition (I-1) contained in the pressure-sensitive adhesive composition (I-1) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the pressure-sensitive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and 15 to 90%. It is particularly preferable that the content is% 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 energy ray curable compounds include the following.
  • trimethylolpropane tri (meth) acrylate pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6 -Polyvalent (meth) acrylates such as hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy (meth) acrylate and the like.
  • 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. 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, more preferably 5 to 90% by mass, and 10 to 85% by mass. % Is particularly preferred.
  • 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).
  • the following are mentioned as a crosslinking agent.
  • tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking having a glycidyl group) Agent); aziridine-based crosslinking agent (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; metal chelate-based crosslinking agent such as aluminum chelate (cross-linking having a metal chelate structure) Agent); isocyanurate-based crosslinking agent (crosslinking agent
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one kind or two or more kinds. 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 mass with respect to 100 parts by mass 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 the following.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl Acetophenone compounds such as propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6- Acylphosphine oxide compounds such as trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; 1-hydroxycyclo ⁇ -ketol compounds such as xylphenyl ketone;
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be one kind or two or more kinds. 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. More specifically, one 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 one type or two or more types. 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-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.
  • organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; toluene and xylene. Aromatic hydrocarbons; 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 one kind or two or more kinds. 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.
  • a compound having a group examples include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, 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 one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the pressure-sensitive resin (I-2a) is preferably 5 to 99% by mass.
  • 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 kind or two or more kinds. 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 mass with respect to 100 parts by mass 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). .
  • the amount is 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-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 one kind or two or more kinds. 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 kind or two or more kinds. 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 resin (I-2a) is preferably 5 to 99% by mass. It is more preferably 10 to 95% by mass, and 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. Furthermore, the same thing as the energy-beam curable compound which adhesive composition (I-1) contains is mentioned.
  • the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. 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 preferable.
  • the amount is more preferably 0.03 to 200 parts by mass, and particularly 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 kind or two or more kinds. 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. It is preferably 20 parts by mass. The amount is 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 one kind or two or more kinds. 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. 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.
  • Examples of the non-energy ray curable pressure-sensitive adhesive composition include the following. For example, it contains non-energy ray-curable adhesive resin (I-1a) such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc.
  • An adhesive composition (I-4) can be mentioned. Among these, those containing an acrylic resin are preferable.
  • the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contain one or more kinds of crosslinking agents.
  • the content can be the same as in the case of the above-mentioned pressure-sensitive adhesive composition (I-1) and the like.
  • Adhesive resin (I-1a) examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) 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 one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the pressure-sensitive resin (I-1a) is preferably 5 to 99% by mass. It is more preferably 10 to 95% by mass, and 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 kind or two or more kinds. 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 one type or two or more types. 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 make it peel from the support sheet provided with. As a result, the semiconductor chip with a protective film cannot be picked up normally.
  • the effect when the pressure-sensitive adhesive layer is non-energy ray curable has been described.
  • the layer in direct contact with the protective film-forming film of the support sheet is a layer other than the pressure-sensitive adhesive layer, the same effect can be obtained as long as this layer is non-energy ray curable.
  • 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, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive, if 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 When using 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. Moreover, you may use by mixing a solvent with these compounding components, without diluting any compounding components other than a solvent previously.
  • the method of mixing each component at the time of mixing is not particularly limited.
  • the method may be appropriately selected from known methods 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.
  • 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 preferably 50 to 1500 mN / 25 mm. More preferably, it is 52 to 1450 mN / 25 mm, and further preferably 53 to 1430 mN / 25 mm.
  • the adhesive force is greater than or equal to the lower limit, pickup of a semiconductor chip with a protective film that is not the purpose is suppressed during pickup of the semiconductor chip with a protective film. As a result, the target semiconductor chip with a protective film can be picked up with high selectivity.
  • 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 laminate 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, the protective film-forming film is cured by irradiating energy rays to form a protective film. Thereafter, the support sheet is peeled off at a peeling speed of 300 mm / min from this protective film adhered 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 protective film-forming composite sheet used for measurement is not particularly limited as long as the adhesive force can be stably detected. It 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.
  • it may be 80 mN / 25 mm or more, but is 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. As a result, for example, scattering from the support sheet of the semiconductor chip provided with the protective film forming film on the back surface is suppressed.
  • the upper limit of the adhesive force between the protective film-forming film and the support sheet is not particularly limited.
  • it can be any of 4000 mN / 25 mm, 3500 mN / 25 mm, 3000 mN / 25 mm, and the like. However, these are examples.
  • 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 can be appropriately adjusted.
  • it can be adjusted by adjusting the type and amount of the components contained in the protective film-forming film, the constituent material of the layer on the support sheet where the protective film-forming film is provided, the surface state of this layer, and the like.
  • 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 a base material can be adjusted by performing the following processes.
  • the surface treatment mentioned above for improving the adhesion to other layers of the substrate that is, roughening treatment by sandblast treatment, solvent treatment, etc .; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone -Oxidation treatment such as ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc .;
  • the protective film-forming film has energy ray curability.
  • energy ray curability For example, what contains an energy-beam curable component (a) and a photoradical initiator (c ') is mentioned.
  • the energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky.
  • the protective film-forming film may be a single layer (single layer) or a plurality of layers of two or more layers. In the case of a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
  • the thickness of the protective film-forming film is preferably 1 to 100 ⁇ m. It is more preferably 5 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m. When 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. Moreover, when 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 total thickness of all layers constituting the protective film-forming film.
  • the curing conditions for forming the protective film by curing the protective film-forming film are not particularly limited as long as the degree of curing is such that the protective film sufficiently exhibits its function. What is necessary is just to select suitably according to the kind of film for protective film formation.
  • 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 protective film forming composition may be performed by a known method.
  • examples thereof include methods using various coaters such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, and kiss coater.
  • the drying conditions of the protective film forming composition are not particularly limited.
  • the composition for forming a protective film contains a solvent described later, it is preferably dried by heating. In this case, for example, it is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • composition for forming protective film (IV-1) examples include the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the photo radical initiator (c ′).
  • 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.
  • the 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 the following.
  • an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, a group that reacts with the functional group, and an energy ray curable group such as an energy ray curable double bond An acrylic resin (a1-1) obtained by polymerizing the energy beam curable compound (a12).
  • Examples of the functional group capable of reacting with a group possessed by another compound 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 substituted with a group other than a hydrogen atom). Group), 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 the following. For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol ((meth) acryloyl) And unsaturated alcohol having no skeleton).
  • carboxy group-containing monomer examples include the following.
  • ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (monocarboxylic acids having an ethylenically unsaturated bond); ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid
  • acids dicarboxylic acids having an ethylenically unsaturated bond
  • anhydrides of the ethylenically unsaturated dicarboxylic acids (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like.
  • 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 constituting the acrylic polymer (a11) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • acrylic monomer having no functional group examples include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Sec-butyl acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Isooctyl acid, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth
  • (meth) acrylic acid ester containing alkoxyalkyl groups such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate;
  • (meth) acrylic acid N, N-dimethylamino Examples also include (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as ethyl and N, N-dimethylaminopropyl (meth) acrylate.
  • the acrylic monomer which does not have the functional group constituting the acrylic polymer (a11) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily 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, and 2 or more types may be sufficient as it. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural unit constituting the polymer is 0.1 to 50 mass. % Is preferred.
  • the content is more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass.
  • the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) The content of the linear curable group can easily adjust the degree of curing of the first protective film within a preferable range.
  • the acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the acrylic resin (a1-1) is preferably 1 to 40% by mass.
  • the content is more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.
  • 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 the following.
  • 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. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the ratio is preferably 20 to 120 mol%. More preferably, it is 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 said energy-beam curable compound (a12) is a monofunctional (it has 1 said group in 1 molecule) compound, the upper limit of the ratio of the said content will be 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%. is there.
  • 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). .
  • crosslinked in the group which reacts with the said functional group derived from the said energy-beam curable compound (a12) may be used.
  • the polymer (a1) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000 examples include groups containing an energy beam curable double bond. Preferable examples include (meth) acryloyl group, vinyl group and the like.
  • the compound (a2) is not particularly limited as long as it satisfies the above conditions.
  • Examples thereof include a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and a phenol resin having an energy ray curable group.
  • 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 the following.
  • 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 compound (a2) 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 two or more types, the combination and ratio thereof 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 the following. Examples include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethane resins. Among these, 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 and includes the following.
  • a homopolymer of one kind of acrylic monomer may be used, a copolymer of two or more kinds of acrylic monomers may be used, one kind or two or more kinds of acrylic monomers, and 1 It may be a copolymer with a monomer (non-acrylic monomer) other than seeds or two or more acrylic monomers.
  • acrylic monomer constituting the acrylic polymer (b-1) examples include the following.
  • the “substituted amino group” is as described above.
  • Examples of the (meth) acrylic acid alkyl ester include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Sec-butyl acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Isooctyl acid, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, unde
  • Examples of the (meth) acrylic acid ester having a cyclic skeleton include the following.
  • (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 of the glycidyl group-containing (meth) acrylic ester include glycidyl (meth) acrylate.
  • Examples of the hydroxyl group-containing (meth) acrylic acid ester include the following. For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Examples include 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • 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.
  • the acrylic monomer or non-acrylic monomer mentioned above was obtained by polymerizing a monomer in which one or two or more hydrogen atoms were substituted with the reactive functional group. Things.
  • the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group to the total amount of the structural unit constituting the polymer (b) is 1 to 25. It is preferable that it is mass%. It is more preferably 2 to 20% by mass. When the ratio is within such a range, the degree of cross-linking becomes a more preferable range in the polymer (b).
  • 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 preferable. More preferably, it is 100,000 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 two or more types, the combination and ratio thereof 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 further contains a polymer (b) having no energy ray-curable group. In this case, it is also preferable to further contain (a1).
  • 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 In (IV-1) the content of the compound (a2) is 10 to 10 parts per 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.
  • the amount is preferably 400 parts by mass, and more preferably 30 to 350 parts by mass.
  • the total content of the energy beam curable component (a) and the polymer (b) having no energy beam curable group with respect to the total content of components other than the solvent is 5 to 90% by mass.
  • the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the protective film-forming film is 5 to 90% by mass.
  • It is more preferably 10 to 80% by mass, and particularly preferably 15 to 70% by mass.
  • 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). It is more preferably 6 to 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. , A filler (d), a coupling agent (e), a crosslinking agent (f), a colorant (g), a thermosetting component (h), and a general-purpose additive (z). Or you may contain 2 or more types.
  • 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. Furthermore, the strength of the protective film formed from this protective film-forming film is also improved.
  • the photo radical initiator used in the composition for forming a protective film of the present invention has an extinction coefficient at a wavelength of 365 nm of 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more (in this specification, “photo radical initiation” Agent (c ′) ”).
  • the photo-radical initiator (c ′) is not particularly limited as long as it has an extinction coefficient of 365 nm and a wavelength of 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more. Examples of the photo radical initiator (c ′) include the following.
  • ⁇ -hydroxy ketone compounds for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.
  • phenyl ketone derivatives for example, acetophenone, propiophenone, benzophenone, 3-methyl
  • the photo radical initiator (c ′) is preferably one having two or more photodegradable groups in one molecule.
  • Examples of the photoradical initiator (c ′) having two or more photodegradable groups in one molecule include the following.
  • 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl-2-methyl-propan-1-one (trade name: 369IRGACURE127, manufactured by BASF Japan)
  • 1 -[4- (4-Benzoxylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one (trade name ESURE1001M), methylbenzoyl formate (trade name SPEDCURE MBF) LAMBSON), O-ethoxyimino-1-phenylpropan-1-one (trade name: SPEEDCURE PDO, manufactured by LAMBSON), oligo [2-hydroxy-2-methyl- [4- (1-
  • the photoradical initiator (c ′) is preferably a hydrogen abstraction type photoradical initiator having three or more aromatic rings in one molecule.
  • the hydrogen abstraction type radical initiator having three or more aromatic rings in one molecule include the following.
  • 1- [4- (phenylthio) -2- (O-benzoyloxime)] 1,2-octanedione (trade name IRGACURE OXE 01, manufactured by BASF Japan)
  • 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) ethanone (trade name IRGACURE OXE 02, manufactured by BASF Japan)
  • 4-benzoyl-4'methyldiphenyl sulfide 4-phenylbenzophenone, 4 , 4 ′, 4 ′′-(hexamethyltriamino) triphenylmethane and the like.
  • 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenylphosphine, which is characterized by improved deep curability
  • examples thereof include acyl phosphine oxide photo radical initiators such as oxide (trade name: IRGACURE 819, manufactured by BASF Japan) and bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
  • the photo radical initiator (c ′) is more preferably the following from the viewpoint of the balance between curability and storage stability of the protective film-forming composition (IV-1).
  • 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: IRGACURE184, manufactured by BASF Japan), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: DAROCUR1173, manufactured by BASF Japan), bis (4- Dimethylaminophenyl) ketone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade names IRGACURE127, BASF Made in Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name IRGACURE369, manufactured by BASF Japan), 2- (4-methylbenzyl) -2-dimethylamino- 1- (4-Morpholin-4-yl
  • the extinction coefficient of the photo radical initiator (c ′) at a wavelength of 365 nm is preferably 4.0 ⁇ 10 1 ml / (g ⁇ cm) or more. It is more preferably 1.0 ⁇ 10 2 ml / (g ⁇ cm) or more, and further preferably 1.0 ⁇ 10 3 ml / (g ⁇ cm) or more.
  • the upper limit value of the extinction coefficient of the photo radical initiator (c ′) at a wavelength of 365 nm is not particularly limited. For example, it can be 1.0 ⁇ 10 4 ml / (g ⁇ cm).
  • the photoradical initiator (c ′) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the photo radical initiator (c ′) may be used in combination with other compounds.
  • combinations with other compounds include the following. 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, diethanolmethylamine, dimethylethanolamine, triethanolamine, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethyl
  • an amine such as aminobenzoate
  • a combination with an iodonium salt such as diphenyliodonium chloride
  • a combination with a dye such as methylene blue and an amine, and the like.
  • the photo radical initiator (c ′) may be hydroquinone, hydroquinone monomethyl ether, benzoquinone, paratertiary butylcatechol, 2,2,6,6-tetramethylpiperidine-1-oxyl, N, N-diethylhydroxylamine, if necessary.
  • N, N-distearylhydroxylamine, N, N-dialkylhydroxylamine and the like may be used in combination with a photopolymerization initiator other than the photoradical initiator (c ′).
  • the photopolymerization initiator contained in the protective film-forming composition (IV-1) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photoradical initiator (c ′) is 0.01 to 20 masses with respect to 100 mass parts of the energy ray-curable compound (a). Part. The amount is more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.
  • the content of the photo radical initiator (c ′) is not more than the above upper limit value, it is possible to suppress unintentional reaction when used under a fluorescent lamp or natural light, and the composite sheet can be used stably. The effect that it can be obtained.
  • the content of the photo radical initiator (c ′) is equal to or more than the lower limit, an effect that the reaction shortage can be suppressed is obtained.
  • 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 the protective film is further improved by optimizing the thermal expansion coefficient for the object to be formed with the protective film.
  • 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.
  • the average particle size of the filler (d) is not particularly limited, but is preferably 0.01 to 20 ⁇ m.
  • the thickness is more preferably 0.1 to 15 ⁇ m, and particularly preferably 0.3 to 10 ⁇ m.
  • average particle size means the value of the particle size (D50) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified.
  • the filler (d) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, for forming the protective film) is preferably 5 to 83% by mass. It is more preferably 7 to 78% by mass. When the content of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient becomes easier.
  • 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. Preferred examples of the silane coupling agent include the following.
  • the coupling agent (e) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof 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 amount is preferably 0.03 to 20 parts by mass with respect to 100 parts by mass of the total content of the polymer (b) having no linear curable group.
  • the amount is more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass.
  • 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 the following.
  • aromatic polyvalent isocyanate compound examples include trimers such as aromatic polyisocyanate compounds, isocyanurates and adducts; and terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compounds and the like with polyol compounds.
  • 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 protective film forming composition (IV-1) and the protective film forming film may contain only one type of crosslinking agent (f), or two or more types. In the case of two or more types, the combination and ratio thereof 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 amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass as the total content of the combined (b).
  • the amount is more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.
  • Colorant (g) examples include known pigments such as inorganic pigments, organic pigments, and organic dyes.
  • organic pigment and organic dye examples include the following.
  • 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 ( Indium tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.
  • the colorant (g) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof 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 ratio of the content of the colorant (g) to the total content of all components other than the solvent (that is, the colorant (g )) Is preferably 0.1 to 10% by mass.
  • the content is 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 one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof 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) As an epoxy resin (h1), a well-known thing is mentioned. For example, polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy Bifunctional or higher functional epoxy compounds such as resins and phenylene skeleton type epoxy resins are exemplified.
  • 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.
  • an epoxy resin which has an unsaturated hydrocarbon group the compound etc. which the group which has an unsaturated hydrocarbon group directly couple
  • An unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) acrylamide group and the like, and acryloyl group is preferable.
  • the number average molecular weight of the epoxy resin (h1) is not particularly limited. However, from the viewpoint of the curability of the protective film-forming film and the strength and heat resistance of the protective film, it is preferably 300 to 30000. It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
  • the epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.
  • 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 phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxy groups, and groups in which acid groups have been anhydrideized.
  • a phenolic hydroxyl group, amino group, or acid group is preferably an anhydride group, and more preferably a phenolic hydroxyl group or 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 agents (h2) the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin is preferably 300 to 30,000, and more preferably 400 to 10,000. 500 to 3000 is particularly preferable.
  • 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, and may use 2 or more types together. When using 2 or more types together, those combinations and ratios can be arbitrarily selected.
  • 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, can be arbitrarily selected according to the purpose, and is not particularly limited. Preferable examples include plasticizers, antistatic agents, antioxidants, gettering agents and the like.
  • 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 or two or more kinds. In the case of two or more types, the combination and ratio thereof 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 said solvent is not specifically limited, The following are mentioned as a preferable thing.
  • 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 such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond), and the like.
  • the solvent contained in the protective film-forming composition (IV-1) may be only one kind or two or more kinds. 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.
  • the method of mixing each component at the time of mixing is not particularly limited.
  • the temperature and time during addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate.
  • the temperature 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.
  • any layer other than the base material constituting the composite sheet for forming a protective film can be laminated by a method in which the layer is formed in advance on the release film and bonded to the surface of the target layer. Therefore, a protective film-forming composite sheet may be produced by appropriately selecting a layer that employs such a process as necessary.
  • 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 semiconductor wafer is divided together with the protective film forming film by dicing to form a semiconductor chip with the protective film forming film. Next, the protective film forming film of the semiconductor chip with the protective film forming film is irradiated with energy rays to cure the protective film forming film to form a protective film. 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.
  • FIG. 6 is a cross-sectional view schematically showing a protective film forming film according to an embodiment of the protective film forming sheet of the present invention.
  • the protective film forming sheet 1 ⁇ / b> F according to the present embodiment is suitable for a “roll type”.
  • the protective film-forming sheet 1F is provided between the release film 15a (hereinafter sometimes referred to as “first release film”) and the release film 15b (hereinafter also referred to as “second release film”). It has a structure in which the protective film-forming composition is applied in layers so that the protective film-forming film 13 is disposed.
  • the protective film forming composition used for the protective film forming sheet 1F is in accordance with the above-described protective film forming composition.
  • the protective film forming sheet 1F is formed by, for example, coating the protective film forming composition on the release surface of the first release film 15a and drying to form the protective film forming film 13, and then It can form by sticking the peeling surface of the 2nd peeling film 15b to an exposed surface.
  • the method for applying the protective film forming composition is in accordance with the method for applying the protective film forming composition.
  • the protective film-forming film of the present invention can be used, for example, by the method described below. That is, a protective film-forming film is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface). Next, the semiconductor wafer is divided together with the protective film forming film by dicing to form a semiconductor chip with the protective film forming film. Next, the protective film forming film of the semiconductor chip with the protective film forming film is irradiated with energy rays to cure the protective film forming film to form a protective film. 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.
  • 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.
  • Photoradical initiator (c ′)-1 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (“Irgacure® 369” manufactured by BASF, wavelength 365 nm) Extinction coefficient of 7.9 ⁇ 10 3 )
  • C ′)-2 Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (“Irgacure ( (Registered trademark) OXE02 ", extinction coefficient of wavelength 365 nm: 7.7 ⁇ 10 3 )
  • C ′)-3 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] 1,2-octanedione) (“Irgacure® OXE01” manufactured by BASF, light absorption at 365 nm wavelength) Coefficient: 7.0 ⁇ 10 3 )
  • Colorant (g) -1 32 parts by mass of phthalocyanine blue pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow pigment (Pigment Yellow 139), and anthraquinone red pigment (Pigment Red 177)
  • a pigment obtained by mixing 50 parts by mass and pigmenting the mixture so that the total amount of the three kinds of dyes / the amount of styrene acrylic resin 1/3 (mass ratio).
  • (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.
  • a polypropylene film (Young's modulus: 400 MPa, thickness: 80 ⁇ m, hereinafter sometimes referred to as “S1”) is bonded to the exposed surface of the pressure-sensitive adhesive layer as a base material, thereby one surface of the base material.
  • a support sheet (10) -1 having the pressure-sensitive adhesive layer thereon was obtained.
  • a protective film-forming composition obtained as described above is formed on the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, thickness 38 ⁇ m, P1) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment.
  • (IV-1) was applied 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.
  • 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 350 ⁇ m) with the protective film-forming film (13) -1 and this sheet is further attached to the ring frame. Fixed. Next, using a dicing blade, the silicon wafer was diced together with the protective film-forming film (13) -1 and separated into individual pieces to obtain silicon chips of 5 mm ⁇ 5 mm.
  • a protective film-forming film (13) 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 using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation). ) -1 was irradiated with ultraviolet rays to cure the protective film-forming film (13) -1 to obtain a protective film.
  • RAD2000m / 8 manufactured by Lintec Corporation
  • Example 2 A protective film-forming film (13) -2 was produced in the same manner as in Example 1 except that (c ′)-1 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.
  • Example 3 A protective film-forming film (13) -3 was produced in the same manner as in Example 1 except that (c ′)-2 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.
  • Example 4 A protective film-forming film (13) -4 was produced in the same manner as in Example 1 except that (c ′)-3 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.
  • Example 5 A protective film-forming film (13) -5 was produced in the same manner as in Example 1 except that (c ′)-4 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.
  • Example 1 A protective film-forming film (13) -6 was produced in the same manner as in Example 1 except that (c) -1 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.
  • the present invention can be used for manufacturing semiconductor devices.

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CN111712764A (zh) * 2018-02-20 2020-09-25 汉高股份有限及两合公司 热固化和uv固化粘合剂组合物
JPWO2020116275A1 (ja) * 2018-12-05 2021-10-21 リンテック株式会社 保護膜形成用複合シート、及び半導体チップの製造方法

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JP7412915B2 (ja) * 2019-07-30 2024-01-15 東京応化工業株式会社 保護膜形成剤、及び半導体チップの製造方法

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