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WO2017188202A1 - Film pour former un film de protection et feuille composite pour former un film de protection - Google Patents

Film pour former un film de protection et feuille composite pour former un film de protection Download PDF

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Publication number
WO2017188202A1
WO2017188202A1 PCT/JP2017/016260 JP2017016260W WO2017188202A1 WO 2017188202 A1 WO2017188202 A1 WO 2017188202A1 JP 2017016260 W JP2017016260 W JP 2017016260W WO 2017188202 A1 WO2017188202 A1 WO 2017188202A1
Authority
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/JP2017/016260
Other languages
English (en)
Japanese (ja)
Inventor
力也 小橋
洋一 稲男
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 JP2018514597A priority Critical patent/JP7285075B2/ja
Priority to CN201780019966.1A priority patent/CN108886023B/zh
Priority to KR1020187027332A priority patent/KR102445025B1/ko
Publication of WO2017188202A1 publication Critical patent/WO2017188202A1/fr
Anticipated expiration legal-status Critical
Priority to JP2022061944A priority patent/JP7290771B2/ja
Ceased legal-status Critical Current

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Classifications

    • H10W74/01—
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • H10P72/0442—
    • H10P72/7402—
    • H10W72/30—
    • H10W74/10—
    • H10W99/00—
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • H10P72/7422—

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.
  • Patent Document 1 an energy ray curable film-forming component containing a polymer component made of an acrylic copolymer, an energy ray curable component, a dye or pigment, an inorganic filler, and a photopolymerization initiator is peeled off.
  • a film for protecting a chip having a structure sandwiched between sheets is disclosed.
  • the film for chip protection can form a protective film with improved laser marking recognizability, hardness, and adhesion with a wafer by irradiation with energy rays. The process can be simplified as compared with conventional film for chip protection.
  • Patent Document 2 discloses a dicing tape integrated type having a dicing tape having a base material and an adhesive, and a wafer back surface protective film that is colored and has a predetermined elastic modulus on the adhesive layer of the dicing tape.
  • a wafer back surface protective film is disclosed. According to the description in Patent Document 2, the wafer back surface protective film can exhibit excellent holding force with the semiconductor wafer in the dicing process of the semiconductor wafer.
  • the protective film disclosed in Patent Documents 1 and 2 is attached so that the position of the protective film is shifted or the foreign substance is included without being aware of the foreign substance on the wafer. In such a case, it is difficult to rework the wafer by peeling off the protective film. Since the protective films disclosed in Patent Documents 1 and 2 are intended to improve adhesion to the wafer at the time of sticking and holding power with the wafer after sticking, once attached to the wafer, Since the adhesion to the wafer is high, there is a problem in reworkability.
  • Patent Documents 1 and 2 Although the protective film described has been studied from the viewpoint of adhesion to the wafer at the time of sticking and holding power to the wafer at the time of sticking, the reworkability of the protective film No consideration has been given to.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a protective film-forming film and a protective film-forming composite sheet that are excellent in reworkability.
  • the present invention is an energy ray-curable protective film-forming film, wherein the surface roughness (Ra) of at least one surface ( ⁇ ) is 0.
  • a protective film-forming film having a thickness of 038 ⁇ m or more is provided.
  • the surface ( ⁇ ) preferably has a surface roughness (Ra) of 2.0 ⁇ m or less.
  • this invention comprises the said film for protective film formation on a support sheet, and the surface ((beta)) on the opposite side to the said surface ((alpha)) of the said film for protective film formation faces the said support sheet.
  • a composite sheet for forming a protective film is provided.
  • a protective film can be formed on the back surface of a semiconductor wafer or a semiconductor chip, and has a good rework property, and includes an energy ray curable protective film forming film and such a protective film forming film.
  • a protective sheet-forming composite sheet is provided.
  • “reworkability” refers to a property that allows the semiconductor wafer to be peeled without being damaged when it is peeled again after being attached to the semiconductor wafer.
  • the protective film-forming film of the present invention is an energy ray-curable protective film-forming film, and in the protective film-forming film, the surface roughness of at least one surface ( ⁇ ) ( Ra) is 0.038 ⁇ m or more.
  • the protective film-forming film of the present invention may have a first release film on at least one surface, and may further have a second release film on the other surface.
  • the film for forming a protective film of the present invention can be provided as a long film wound in a roll shape.
  • FIG. 6 is a cross-sectional view schematically showing one embodiment of the protective film-forming film of the present invention. In FIG.
  • the 1st peeling film 15b, the protective film formation film 13 (23), and the 2nd peeling film 15a are laminated
  • the surface to be attached to the back surface of the semiconductor wafer that is, the surface opposite to the circuit surface
  • front surface ( ⁇ ) is referred to as “front surface ( ⁇ )” and is attached to the back surface of the semiconductor wafer.
  • the surface opposite to the surface may be referred to as “surface ( ⁇ )”.
  • the surface roughness (Ra) of at least one surface ( ⁇ ) is preferably 0.038 ⁇ m or more, and preferably 2.0 ⁇ m or less.
  • surface roughness (Ra) means a so-called arithmetic average roughness obtained in accordance with JIS B0601: 2001 unless otherwise specified.
  • One aspect of the present invention is a protective film-forming film having energy ray curability and for forming a protective film on the back surface of a semiconductor wafer or semiconductor chip, wherein the semiconductor
  • the present invention relates to a protective film forming film in which the surface roughness (Ra) of the surface ( ⁇ ) attached to the wafer or semiconductor chip is 0.038 ⁇ m or more.
  • the surface roughness (Ra) of the surface ( ⁇ ) on the side attached to the semiconductor wafer or semiconductor chip is: It is preferable that it is 2.0 micrometers or less.
  • Another aspect of the present invention is a protective film-forming sheet comprising a first release film and a protective film-forming film that directly contacts the first release film and has energy ray curability
  • the present invention relates to a protective film forming sheet in which the surface roughness (Ra) of the surface ( ⁇ ) on the side in direct contact with the first release film is 0.038 ⁇ m or more.
  • the surface roughness (Ra) of the surface ( ⁇ ) on the side attached to the first release film is preferably 2.0 ⁇ m or less.
  • the surface roughness (Ra) of the surface ( ⁇ ) of the protective film-forming film can be measured by the measurement method described in the examples.
  • the composite sheet for forming a protective film of the present invention comprises an energy ray-curable protective film-forming film on a support sheet, and the surface ( ⁇ ) of the protective film-forming film.
  • 2 is a composite sheet for forming a protective film having a surface ( ⁇ ) opposite to that facing the support sheet.
  • the surface roughness (Ra) of the surface ( ⁇ ) of the protective film-forming film in the protective film-forming composite sheet of the present invention is preferably 0.038 ⁇ m or more, and more preferably 2.0 ⁇ m or less.
  • 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 surface roughness (Ra) of the surface ( ⁇ ) of the protective film-forming film in the protective film-forming composite sheet can be measured by the measuring method described in the examples.
  • 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 surface roughness (Ra) of at least one surface ((alpha)) of the said film for protective film formation is 0.038 micrometer or more
  • the composite sheet for protective film formation of this invention has favorable rework property. Have. For example, even when the protective film forming composite sheet is attached to a position shifted from the target position on the back surface of the semiconductor wafer, the semiconductor wafer is damaged by peeling the protective film forming composite sheet from the semiconductor wafer.
  • the product can be manufactured using the semiconductor wafer by re-applying (reworking) a new protective film-forming composite sheet without re-working.
  • the protective film-forming composite sheet of the present invention the protective film-forming composite sheet of the conventional protective film-forming composite sheet provided with the thermosetting protective film-forming film is formed by the energy film-curable film.
  • the protective film can be formed by curing in a shorter time than the case.
  • “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays and electron beams.
  • Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp or the like as an ultraviolet ray source.
  • the electron beam can be emitted by an electron beam accelerator or the like.
  • “energy ray curable” means the property of being cured by irradiation with energy rays
  • “non-energy ray curable” means the property of not being cured even when irradiated with energy rays. .
  • the thickness of the semiconductor wafer or semiconductor chip that is the target of use of the composite sheet for forming a protective film of the present invention is not particularly limited, but is preferably 30 to 1000 ⁇ m because the effects of the present invention can be obtained more remarkably. 100 to 300 ⁇ m is more preferable.
  • the configuration of the present invention will be described in detail.
  • the support sheet may be composed of one layer (single layer) or may be composed of two or more layers.
  • the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
  • the plurality of layers may be the same or different from each other” means “all the layers may be the same or all the layers are different. Means that only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and thickness of each layer is different from each other ”. Means.
  • Preferred support sheets include, for example, those in which the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate, those in which the pressure-sensitive adhesive layer is laminated on the substrate via an intermediate layer, and only the substrate. And the like.
  • FIG. 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 11a of the substrate 11, and the protective film-forming film 13 is laminated on the entire surface 12a of the pressure-sensitive adhesive layer 12, thereby forming the protective film.
  • the jig adhesive layer 16 is laminated on a part of the surface 13 a of the film 13, that is, in the vicinity of the peripheral edge, and the jig adhesive layer 16 is laminated on the surface 13 a of the protective film forming film 13.
  • a release film 15 is laminated on the surface that is not formed and the surface 16 a (upper surface and side surface) of the adhesive layer 16 for jigs.
  • the adhesive force between the cured protective film-forming film 13 (that is, the protective film) and the support sheet 10 is 50 to 1500 mN / 25 mm is preferable.
  • the adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both surfaces of a core sheet. It may be of a structure.
  • the back surface of the semiconductor wafer (not shown) is pasted on the front surface 13a of the protective film forming film 13 with the release film 15 removed.
  • the upper surface of the surface 16a of the adhesive layer 16 is used by being attached to a jig such as a ring frame.
  • FIG. 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 sheet-forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the protective film-forming film 13 is laminated on the entire surface 12a of the pressure-sensitive adhesive layer 12. A release film 15 is laminated on the entire surface 13 a of the 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 surface is affixed, and the region near the periphery of the protective film-forming film 13 is affixed to a jig such as a ring frame and used.
  • FIG. 3 is a cross-sectional view schematically showing still another embodiment of the protective film-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), and a part of the surface 13a of the protective film forming film 13, that is, in the vicinity of the peripheral portion.
  • the jig adhesive layer 16 is laminated in the region, and the surface 13 a of the protective film forming film 13 on which the jig adhesive layer 16 is not laminated and the surface 16 a of the jig adhesive layer 16.
  • a release film 15 is laminated on the upper surface and the side surface.
  • the adhesive force between the protective film-forming film 13 after curing (ie, the protective film) and the support sheet 10 is: It is preferably 50 to 1500 mN / 25 mm.
  • the protective film forming composite sheet 1C is formed on the surface 13a of the protective film forming film 13 with the release film 15 removed.
  • the back surface of (not shown) is attached, and the upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.
  • FIG. 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 sheet-forming composite sheet 1D, the protective film-forming film 13 is laminated on one surface 11a of the substrate 11, and the release film 15 is laminated on the entire surface 13a of the protective film-forming film 13. Yes.
  • 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 affixed to a partial area on the center side, and the area near the periphery of the protective film forming film 13 is affixed to a jig such as a ring frame. .
  • FIG. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
  • the protective sheet-forming composite sheet 1E shown here is the same as the protective film-forming composite sheet 1B shown in FIG. 2 except that the shape of the protective film-forming film is different. That is, the protective film-forming composite sheet 1 ⁇ / b> E includes the pressure-sensitive adhesive layer 12 on the base material 11 and the protective film-forming film 23 on the pressure-sensitive adhesive layer 12.
  • the support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and in other words, the protective film-forming composite sheet 1E is formed by laminating the protective film-forming film 23 on one surface 10a of the support sheet 10. Have a configuration.
  • 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 adhesive force between the cured protective film-forming film 23 (that is, the protective film) and the support sheet 10 is 50 to 1500 mN / 25 mm is preferable.
  • the back surface of the semiconductor wafer (not shown) is pasted on the front surface 23a of the protective film-forming film 23 with the release film 15 removed.
  • the surface on which the protective film forming film 23 is not laminated is attached to a jig such as a ring frame and used.
  • the surface 12a of the pressure-sensitive adhesive layer 12 is the same as that shown in FIGS. 1 and 3 on the surface on which the protective film-forming film 23 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. 1 to 5, and a part of the structure shown in FIGS. 1 to 5 is changed or deleted within a range not impairing the effect of the present invention.
  • another configuration may be added to what has been described so far.
  • an intermediate layer may be provided between the base material 11 and the protective film-forming film 13. Any intermediate layer can be selected according to the purpose.
  • an intermediate layer may be provided between the base material 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by laminating a base material, an intermediate layer, and an adhesive layer in this order.
  • the intermediate layer is the same as the intermediate layer that may be provided in the protective film-forming composite sheet shown in FIGS. 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 polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin.
  • Polyolefins such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as a monomer)
  • a copolymer obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Naphtha Polyesters such as polyesters, polybutylene terephthalates, polyethylene isophthalates, polyethylene-2,6-naphthalene dicarboxylates, wholly aromatic polyesters in which all the structural units have an aromatic cyclic group; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin
  • 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 such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Is mentioned.
  • the base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin. May be.
  • the substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.
  • the film for protective film formation has energy-beam sclerosis
  • the substrate is subjected to a roughening treatment such as sandblast treatment, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment.
  • the surface may be subjected to oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
  • the base material may have a surface subjected to primer treatment.
  • the base material prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the antistatic coating layer and the protective film-forming composite sheet are stored in an overlapping manner. It may have a layer or the like.
  • the substrate preferably has a surface subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the substrate due to blade friction during dicing is suppressed.
  • the base material can be manufactured by a known method.
  • a base material containing a resin can be produced by molding a resin composition containing the resin.
  • the said adhesive layer is a sheet form or a film form, and contains an adhesive.
  • the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, and acrylic resins are preferable. .
  • the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin.
  • the resin itself has an adhesive property
  • resins that exhibit tackiness when used in combination with other components such as additives, and resins that exhibit 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), may be composed of two or more layers, and when composed of a plurality of layers, these layers may be the same or different from each other.
  • the combination of the multiple layers is not particularly limited.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and particularly preferably 1 to 30 ⁇ m.
  • the “thickness of the pressure-sensitive adhesive layer” means the thickness of the whole pressure-sensitive adhesive layer.
  • the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness.
  • the optical properties of the pressure-sensitive adhesive layer only need to satisfy the optical properties of the support sheet described above. That is, the pressure-sensitive adhesive layer may be transparent, opaque, or colored depending on the purpose. In the present invention in which the protective film-forming film has energy ray curability, the pressure-sensitive adhesive layer is preferably capable of transmitting energy rays.
  • the pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
  • the pressure-sensitive adhesive layer can be formed 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 that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.
  • the adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. And a method using various coaters such as a Meyer bar coater and a kiss coater.
  • the drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferably heat-dried. In this case, for example, at 70 to 130 ° C. for 10 seconds to It is preferable to dry under conditions of 5 minutes.
  • the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive that is, the energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray-curable pressure-sensitive adhesive
  • Energy-ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the linear-curable adhesive resin (I-1a) hereinafter referred to as “adhesive resin (I-2a)”
  • the pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound.
  • the adhesive resin (I-1a) is preferably an acrylic resin.
  • the acrylic resin the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
  • the acrylic resin may have only one type of structural unit, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred. More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-
  • the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms.
  • the alkyl group preferably has 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms.
  • the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.
  • the acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
  • the functional group-containing monomer for example, the functional group reacts with a cross-linking agent described later to become a starting point of cross-linking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound described later. And those that allow introduction of an unsaturated group into the side chain of the acrylic polymer.
  • Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group. That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-methacrylates such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.
  • Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl esters of (meth) acrylic acid such as 2-carboxyethyl methacrylate, etc. It is done.
  • monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
  • fumaric acid, itaconic acid maleic acid, citracone
  • Ethylenically unsaturated dicarboxylic acids such as acids (dica
  • the functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
  • the functional group-containing monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, 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 only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
  • the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (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 only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the pressure-sensitive 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 monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4.
  • Polybutyl (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
  • examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
  • the energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer from the viewpoint that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly lowered.
  • the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the energy ray-curable compound is preferably 1 to 95% by mass, 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).
  • a crosslinking agent for example, 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 agent having a glycidyl group); Aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; Metal chelate-based cross-linking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent (
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a).
  • the amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
  • the pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently proceeds with a curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
  • photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy Acetophenone compounds such as -2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethy
  • ⁇ -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
  • a quinone compound such as 1-chloroanthraquinone
  • a photosensitizer such as amine
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable compound.
  • the amount is more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers.
  • known additives such as reaction retarders and crosslinking accelerators (catalysts).
  • the reaction retarding agent means, for example, an undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage by the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). It suppresses progress.
  • the reaction retarder include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C ( ⁇ O) —) in one molecule. Can be mentioned.
  • the other additive contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
  • the solvent is preferably an organic solvent.
  • 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; cyclohexane and n-hexane and the like.
  • ketones such as methyl ethyl ketone and
  • the solvent used in the production of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a).
  • the same or different type of solvent used in the production of the adhesive resin (I-1a) may be added separately during the production of the adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be adjusted as appropriate.
  • the pressure-sensitive adhesive composition (I-2) is an energy-ray-curable pressure-sensitive adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a). (I-2a) is contained.
  • the adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
  • the unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.
  • 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 only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the pressure-sensitive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass. It is particularly preferable that the content is% by mass.
  • an adhesive composition ( I-2) may further contain a crosslinking agent.
  • Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include the same crosslinking agents as in the pressure-sensitive adhesive composition (I-1).
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a).
  • the amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
  • the pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-2) containing the photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
  • Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (I-1).
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a). 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.
  • the pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • Examples of the other additive in the pressure-sensitive adhesive composition (I-2) include the same additives as those in the pressure-sensitive adhesive composition (I-1).
  • the other additive contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
  • Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be adjusted as appropriate.
  • the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.
  • the content of the pressure-sensitive resin (I-2a) 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-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. Examples thereof include the same energy ray curable compounds contained in the product (I-1).
  • the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). It is preferably 0.03 to 200 parts by mass, more preferably 0.05 to 100 parts by mass.
  • the pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
  • Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (I-1).
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is 0.01 to about 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray curable compound.
  • the amount is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
  • the other additive contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
  • Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be adjusted as appropriate.
  • Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy ray-curable pressure-sensitive adhesive composition.
  • Non-energy ray curable pressure-sensitive adhesive compositions include, for example, acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc.
  • An adhesive composition (I-4) containing an adhesive resin (I-1a) is preferable, and an adhesive composition containing an acrylic resin is preferred.
  • the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contains one or more kinds of crosslinking agents, and the content thereof is the above-mentioned pressure-sensitive adhesive composition. It can be the same as in the case of (I-1).
  • Adhesive resin (I-1a) 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 only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the pressure-sensitive 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.
  • a pressure-sensitive adhesive composition ( I-4) preferably further contains a crosslinking agent.
  • Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) include the same crosslinking agents as those in the pressure-sensitive adhesive composition (I-1).
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a).
  • the amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
  • the pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
  • Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
  • the other additive contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
  • Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited and may be appropriately adjusted.
  • the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because when the pressure-sensitive adhesive layer is energy ray curable, it is sometimes impossible to suppress the pressure-sensitive adhesive layer from being simultaneously cured when the protective film-forming film is cured by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, the cured protective film-forming film and the pressure-sensitive adhesive layer may stick to the interface so as not to be peeled off.
  • a cured protective film-forming film that is, a semiconductor chip provided with a protective film on the back surface (in this specification, sometimes referred to as “semiconductor chip with protective film”) is cured adhesive layer. It becomes difficult to peel off from the support sheet provided with, and the semiconductor chip with a protective film cannot be picked up normally.
  • the pressure-sensitive adhesive layer non-energy ray curable with the support sheet in the present invention, such a problem can be reliably avoided and a semiconductor chip with a protective film can be picked up more easily.
  • the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive composition (I-4) It is obtained by blending each component for constituting the pressure-sensitive adhesive composition, 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 it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance.
  • the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
  • the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
  • ⁇ ⁇
  • Ra surface roughness
  • the protective film forming film when at least one surface ( ⁇ ) has a surface roughness (Ra) of 0.038 ⁇ m or more, appropriate reworkability is imparted. That is, when a protective film forming film is attached to a position shifted from a predetermined position with respect to the semiconductor wafer, the protective film forming film can be smoothly peeled off from the semiconductor wafer, and the protective film forming film is peeled off. By attaching another new protective film-forming film to the correct position on the semiconductor wafer, the semiconductor wafer can be used for manufacturing without wasting the semiconductor wafer.
  • the adhesive strength between the protective film obtained by curing the protective film-forming film and the support sheet is preferably 50 to 1500 mN / 25 mm, and preferably 52 to 1450 mN / 25 mm. More preferably, it is 53 to 1430 mN / 25 mm.
  • the adhesive force is equal to or higher than the lower limit value, pickup of a semiconductor chip with a protective film other than the target is suppressed during pickup of the semiconductor chip with a protective film, and the target semiconductor chip with a protective film is highly selectively picked up. it can.
  • the adhesive force is equal to or less than the upper limit value, cracking and chipping of the semiconductor chip are suppressed when the semiconductor chip with a protective film is picked up.
  • the composite sheet for forming a protective film has better 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, after irradiating energy rays to cure the protective film-forming film to form a protective film, the support sheet is peeled off at a peeling speed of 300 mm / min from this protective film applied to the adherend. At this time, the support sheet is peeled in the length direction (the length direction of the composite sheet for forming the protective film) so that the surfaces of the protective film and the support sheet that are in contact with each other form an angle of 180 °. The so-called 180 ° peeling is performed. And the load (peeling force) at the time of this 180 degree
  • the length of the composite sheet for forming a protective film used for the measurement is not particularly limited as long as the adhesive force can be stably detected, but is preferably 100 to 300 mm. In the measurement, it is preferable that the protective sheet-forming composite sheet is stuck on the adherend and the sticking state of the protective film-forming composite sheet is stabilized.
  • the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and may be, for example, 80 mN / 25 mm or more, preferably 100 mN / 25 mm or more, It is more preferably 150 mN / 25 mm or more, and particularly preferably 200 mN / 25 mm or more.
  • peeling between the protective film-forming film and the support sheet is suppressed during dicing. For example, from a support sheet for a semiconductor chip having a protective film-forming film on the back surface Is prevented from scattering.
  • the upper limit value of the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and can be any of, for example, 4000 mN / 25 mm, 3500 mN / 25 mm, 3000 mN / 25 mm, and the like. However, these are examples.
  • the adhesive force between the protective film-forming film and the support sheet is between the protective film and the support sheet, except that the protective film-forming film used for measurement is not cured by irradiation with energy rays. It can be measured by the same method as adhesive strength.
  • the above-mentioned adhesive force between the protective film and the support sheet and the adhesive force between the protective film-forming film and the support sheet are, for example, the types and amounts of the components contained in the protective film-forming film, It can adjust suitably by adjusting the constituent material of the layer which provides the film for protective film formation, the surface state of this layer, etc.
  • the type and amount of the component contained in the protective film-forming film can be adjusted by the type and amount of the component contained in the protective film-forming composition described below. And among the components of the composition for forming a protective film, for example, the type and content of the polymer (b) having no energy ray curable group, the content of the filler (d), or the crosslinking agent (f) By adjusting the content of, the adhesive force between the protective film or the protective film-forming film and the support sheet can be adjusted more easily.
  • the constituent material can be adjusted as appropriate by adjusting the type and amount of components contained in the adhesive layer. .
  • the kind and quantity of the component of an adhesive layer can be adjusted with the kind and quantity of the component of an above-mentioned adhesive composition.
  • the adhesive force between the protective film or the protective film-forming film and the support sheet is not limited to the constituent material of the base material. The surface condition of the substrate can also be adjusted.
  • the surface state of the base material is, for example, the surface treatment mentioned above as improving the adhesion with the other layers of the base material, that is, the concavo-convex treatment by sandblasting, solvent treatment, etc .; corona discharge treatment, It can be adjusted by performing any one of an electron beam irradiation treatment, a plasma treatment, an ozone / ultraviolet ray irradiation treatment, a flame treatment, a chromic acid treatment, a hot air treatment and the like; and a primer treatment.
  • the protective film-forming film has energy beam curability, and examples thereof include those containing an energy beam curative component (a).
  • the energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky.
  • the protective film-forming film may be only one layer (single layer), or may be two or more layers. In the case of a plurality of layers, these layers may be the same or different from each other. The combination is not particularly limited.
  • the thickness of the protective film-forming film is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
  • the thickness of the protective film-forming film is equal to or more than the lower limit value, a protective film having higher protective ability can be formed.
  • the thickness of the protective film-forming film is equal to or less than the upper limit, an excessive thickness is suppressed.
  • the “thickness of the protective film-forming film” means the thickness of the entire protective film-forming film.
  • the thickness of the protective film-forming film composed of a plurality of layers means the protective film-forming film. Means the total thickness of all the layers that make up.
  • the curing conditions for forming the protective film by curing the protective film-forming film are not particularly limited as long as the protective film has a degree of curing that sufficiently exhibits its function, and the type of the protective film-forming film is not limited. Accordingly, it may be appropriately selected.
  • the illuminance of the energy rays when the protective film-forming film is cured is preferably 4 to 280 mW / cm 2 .
  • the amount of energy rays during the curing is preferably 3 to 1000 mJ / cm 2 .
  • the protective film-forming film can be formed using a protective film-forming composition containing the constituent materials.
  • the protective film-forming film can be formed at the target site by applying the protective film-forming composition to the surface on which the protective film-forming film is to be formed and drying it as necessary.
  • the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the film for forming a protective film.
  • “normal temperature” is as described above.
  • Coating of the composition for forming a protective film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
  • the drying conditions of the protective film-forming composition are not particularly limited, but the protective film-forming composition is preferably heat-dried when it contains a solvent described later. In this case, for example, 70 to 130 ° C. It is preferable to dry under conditions of 10 seconds to 5 minutes.
  • composition for forming protective film (IV-1) examples include a protective film forming composition (IV-1) containing the energy ray curable component (a).
  • the energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming property, flexibility, and the like to the protective film-forming film.
  • Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and an energy ray-curable group and a molecular weight of 100 to 80000.
  • a compound (a2) is mentioned.
  • the polymer (a1) may be at least partially crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
  • 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 an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, An acrylic resin (a1-1) obtained by polymerizing a group that reacts with a functional group and an energy ray curable compound (a12) having an energy ray curable group such as an energy ray curable double bond. .
  • Examples of the functional group capable of reacting with a group possessed by another compound 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 hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-methacrylates such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.
  • Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl esters of (meth) acrylic acid such as 2-carboxyethyl methacrylate, etc. It is done.
  • monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
  • fumaric acid, itaconic acid maleic acid, citracone
  • Ethylenically unsaturated dicarboxylic acids such as acids (dica
  • the acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
  • the acrylic monomer having the functional group that constitutes the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • acrylic monomer having no functional group examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n.
  • acrylic monomer having no functional group examples include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
  • the acrylic monomer which does not have the functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • non-acrylic monomer examples include olefins such as ethylene and norbornene; vinyl acetate; styrene.
  • the said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
  • the 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. %, 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, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • the content of the acrylic resin (a1-1) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass. A content of ⁇ 20% by weight is particularly preferred.
  • the energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferred, and those having an isocyanate group as the group are more preferred. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
  • the energy ray curable compound (a12) preferably has 1 to 5 energy ray curable groups in one molecule, and more preferably 1 to 3 energy ray curable groups.
  • Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl).
  • Ethyl isocyanate An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; Examples thereof include an acryloyl monoisocyanate compound obtained by a reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
  • the energy beam curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
  • the energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the content of the energy beam curable group derived from the energy beam curable compound (a12) with respect to the content of the functional group derived from the acrylic polymer (a11). is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is within such a range, the adhesive force of the protective film formed by curing is further increased.
  • the upper limit of the content ratio is 100 mol%
  • the energy ray curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule)
  • the upper limit of the content ratio may exceed 100 mol%.
  • the weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1500,000.
  • the polymer (a1) is at least partly crosslinked by the crosslinking agent (f)
  • the polymer (a1) is described as constituting the acrylic polymer (a11).
  • a monomer that does not correspond to any of the above-described monomers and has a group that reacts with the crosslinking agent (f) is polymerized to be crosslinked at the group that reacts with the crosslinking agent (f).
  • the group which reacts with the said functional group derived from the said energy-beam curable compound (a12) what was bridge
  • the polymer (a1) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000 examples include a group containing an energy ray curable double bond. Preferred examples include (meth) An acryloyl group, a vinyl group, etc. are mentioned.
  • the compound (a2) is not particularly limited as long as it satisfies the above conditions, but has a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and an energy ray curable group.
  • a phenol resin etc. are mentioned.
  • examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
  • examples of the acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4 -((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane,
  • the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group are described in, for example, paragraph 0043 of “JP 2013-194102 A”. Things can be used.
  • Such a resin corresponds to a resin constituting the thermosetting component (h) described later, but is treated as the compound (a2) in the present invention.
  • the compound (a2) preferably has a weight average molecular weight of 100 to 30,000, more preferably 300 to 10,000.
  • the protective film-forming composition (IV-1) and the compound (a2) contained in the protective film-forming film may be only one kind, two kinds or more, and combinations of two or more kinds.
  • the ratio can be arbitrarily selected.
  • Polymer (b) having no energy ray curable group When the protective film forming composition (IV-1) and the protective film forming film contain the compound (a2) as the energy ray curable component (a), the polymer further does not have an energy ray curable group. It is also preferable to contain (b).
  • the polymer (b) may be at least partially crosslinked by the crosslinking agent (f) or may not be crosslinked.
  • polymer (b) having no energy ray curable group examples include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethanes. Examples thereof include resins.
  • the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as “acrylic polymer (b-1)”).
  • the acrylic polymer (b-1) may be a known one, for example, a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or two or more acrylic monomers and a monomer (non-acrylic monomer) other than one or two or more acrylic monomers.
  • acrylic monomer constituting the acrylic polymer (b-1) examples include (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth) acrylic acid ester, Examples include hydroxyl group-containing (meth) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters.
  • substituted amino group is as described above.
  • Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
  • Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl esters such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; (Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl; (Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester; Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester.
  • Examples of the glycidyl group-containing (meth) acrylic ester include glycidyl (meth) acrylate.
  • Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. Examples include propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
  • Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylate.
  • non-acrylic monomer constituting the acrylic polymer (b-1) examples include olefins such as ethylene and norbornene; vinyl acetate; styrene.
  • the reactive functional group in the polymer (b) is a crosslinking agent (f ).
  • the reactive functional group may be appropriately selected according to the type of the crosslinking agent (f) and the like, and is not particularly limited.
  • the crosslinking agent (f) is a polyisocyanate compound
  • examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. Among these, a hydroxyl group having high reactivity with an isocyanate group. Is preferred.
  • the crosslinking agent (f) is an epoxy compound
  • examples of the reactive functional group include a carboxy group, an amino group, an amide group, etc. Among them, a carboxy group having high reactivity with an epoxy group. Groups are preferred.
  • the reactive functional group is preferably a group other than a carboxy group in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip.
  • Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group.
  • examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester.
  • Examples of the acrylic monomer or non-acrylic monomer include those obtained by polymerizing a monomer in which one or two or more hydrogen atoms are substituted with the reactive functional group.
  • the 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.
  • the mass is preferably 2, and more preferably 2 to 20 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 preferably 100000 to 1500,000.
  • the polymer (b) having no energy ray-curable group contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind or two or more kinds. In the case of more than species, their combination and ratio can be arbitrarily selected.
  • Examples of the protective film-forming composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2).
  • the protective film-forming composition (IV-1) contains the compound (a2), it preferably contains a polymer (b) that does not have an energy ray-curable group. It is also preferable to contain (a1). Further, the protective film-forming composition (IV-1) does not contain the compound (a2) and contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. It may be.
  • the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group
  • the protective film-forming composition 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 95% by mass. It is preferably 10 to 93% by mass, more preferably 15 to 91% by mass. When the ratio of the total content is within such a range, the energy ray curability of the protective film-forming film becomes better.
  • the protective film forming composition (IV-1) contains the energy beam curable component (a) and the polymer (b) having no energy beam curable group
  • the protective film forming composition (IV-1) ) And the protective film-forming film the content of the polymer (b) is preferably 3 to 160 parts by mass with respect to 100 parts by mass of the energy ray-curable component (a). More preferably, it is ⁇ 130 parts by mass.
  • the content of the polymer (b) is in such a range, the energy ray curability of the protective film-forming film becomes better.
  • the protective film-forming composition (IV-1) comprises a photopolymerization initiator (c) depending on the purpose.
  • the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h) the protective film-forming film formed is heated. Adhesive strength to the adherend is improved, and the strength of the protective film formed from this protective film-forming film is also improved.
  • Photopolymerization initiator (c) examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone, 2 Acetophenone compounds such as -hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide Compound; ⁇ -ketol compound such as 1-hydroxy
  • the photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the content of the photopolymerization initiator (c) is 100 parts by mass of the energy ray-curable compound (a).
  • the amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the protective film-forming film contains the filler (d)
  • the protective film obtained by curing the protective film-forming film can easily adjust the thermal expansion coefficient.
  • the reliability of the package obtained using the composite sheet for forming a protective film is further improved.
  • the moisture absorption rate of a protective film can be reduced or heat dissipation can be improved because the film for protective film formation contains a filler (d).
  • the surface roughness (Ra) of the surface ( ⁇ ) can be easily adjusted in the protective film-forming film. is there.
  • the filler (d) include those made of a heat conductive material.
  • the filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
  • Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
  • the inorganic filler is preferably silica or alumina, and more preferably epoxy-modified silica.
  • the average particle size of the filler (d) is not particularly limited, but is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 15 ⁇ m, and particularly preferably 0.3 to 10 ⁇ m. .
  • the filler (d) has an average particle size of 0.05 to 0.1 ⁇ m.
  • “average particle size” means the value of the particle size (D 50 ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. .
  • the protective film-forming composition (IV-1) and the filler (d) contained in the protective film-forming film may be only one type, two or more types, and combinations of two or more types.
  • the ratio can be arbitrarily selected.
  • the 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 2 to 83% by mass, more preferably 3 to 68% by mass, and further preferably 4 to 30% by mass.
  • 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.
  • silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropi Examples include trimethoxysilane, 3-
  • the protective film-forming composition (IV-1) and the coupling agent (e) contained in the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • the content of the coupling agent (e) in the composition for forming a protective film (IV-1) and the film for forming a protective film includes the energy ray curable component (a) and the energy. It is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 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 particularly preferably 0.1 to 5 parts by mass.
  • the content of the coupling agent (e) is equal to or higher than the lower limit, the dispersibility of the filler (d) in the resin is improved and the adhesion of the protective film-forming film to the adherend is improved. The effect by using a coupling agent (e) etc. is acquired more notably. Moreover, generation
  • Crosslinking agent (f) By using the crosslinking agent (F) and crosslinking the polymer (b) having no energy beam curable component (a) or energy beam curable group, the initial adhesive force and cohesive force of the protective film-forming film. Can be adjusted.
  • crosslinking agent (f) examples include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.
  • organic polyvalent isocyanate compound examples include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”).
  • a trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc.
  • the “adduct body” includes the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound, or the alicyclic polyvalent isocyanate compound, and a low amount of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, or the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include an xylylene diisocyanate adduct of trimethylolpropane as described later.
  • the “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.
  • organic polyvalent isocyanate compound for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.
  • a polyol such as propane.
  • organic polyvalent imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, and tetramethylolmethane.
  • -Tri- ⁇ -aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.
  • the crosslinking agent (f) When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray curable component (a) or the polymer (b) having no energy ray curable group.
  • the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray-curable property.
  • a cross-linked structure can be easily introduced into the protective film-forming film by reaction with the component (a) or the polymer (b) having no energy ray-curable group.
  • the crosslinking agent (f) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, or a combination of two or more types.
  • the ratio can be arbitrarily selected.
  • the content of the crosslinking agent (f) in the protective film-forming composition (IV-1) is such that the energy ray-curable component (a) and the energy ray-curable group having no energy ray-curable group are contained.
  • the total content of the combined (b) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight. It is particularly preferred.
  • the content of the cross-linking agent (f) is equal to or higher than the lower limit value, the effect of using the cross-linking agent (f) is more remarkably obtained.
  • the excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.
  • Colorant (g) examples include known pigments such as inorganic pigments, organic pigments, and organic dyes.
  • organic pigments and organic dyes examples include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanines.
  • the inorganic pigment examples include carbon black, cobalt dye, iron dye, chromium dye, titanium dye, vanadium dye, zirconium dye, molybdenum dye, ruthenium dye, platinum dye, ITO ( Indium tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.
  • the protective film-forming composition (IV-1) and the colorant (g) contained in the protective film-forming film may be only one kind, two kinds or more, and combinations of two or more kinds.
  • the ratio can be arbitrarily selected.
  • the content of the colorant (g) in the protective film-forming film may be appropriately adjusted according to the purpose.
  • the protective film may be printed by laser irradiation, and by adjusting the content of the colorant (g) in the protective film-forming film and adjusting the light transmittance of the protective film, the print visibility is improved. Can be adjusted.
  • the 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, more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass.
  • the effect by using a colorant (g) is acquired more notably because the content of the colorant (g) is not less than the lower limit. Moreover, the excessive use of a coloring agent (g) is suppressed because the said content of a coloring agent (g) is below the said upper limit.
  • thermosetting component (h) The thermosetting component (h) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind, two kinds or more, and if two or more kinds, These combinations and ratios can be arbitrarily selected.
  • thermosetting component (h) examples include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy thermosetting resins are preferable.
  • the epoxy thermosetting resin includes an epoxy resin (h1) and a thermosetting agent (h2).
  • the epoxy thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
  • Epoxy resin (h1) examples include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.
  • an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (h1).
  • An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the composite sheet for forming a protective film is improved by using an epoxy resin having an unsaturated hydrocarbon group.
  • Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group. Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple
  • the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned, An acryloyl group is preferable.
  • the number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30000 from the viewpoint of curability of the protective film-forming film and strength and heat resistance of the protective film, and is preferably 400 to 10,000. More preferably, it is more preferably 500 to 3000.
  • the 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 a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
  • thermosetting agents (h2) examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
  • examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
  • the thermosetting agent (h2) may have an unsaturated hydrocarbon group.
  • the thermosetting agent (h2) having an unsaturated hydrocarbon group for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
  • the unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
  • thermosetting agent (h2) In the case where a phenolic curing agent is used as the thermosetting agent (h2), it is preferable that the thermosetting agent (h2) has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. .
  • thermosetting agent (h2) for example, the number average molecular weight of the resin component such as polyfunctional phenolic resin, novolac-type phenolic resin, dicyclopentadiene-based phenolic resin, aralkylphenolic resin, etc. is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
  • the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
  • thermosetting agent (h2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
  • the content of the thermosetting agent (h2) is 100% of the epoxy resin (h1).
  • the amount is preferably 0.01 to 20 parts by mass with respect to parts by mass.
  • thermosetting component (h) when used, the content of the thermosetting component (h) (for example, the epoxy resin (h1) and the heat in the protective film-forming composition (IV-1) and the protective film-forming film)
  • the total content of the curing agent (h2) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b) having no energy ray curable group.
  • the general-purpose additive (z) may be a known one, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. Is mentioned.
  • the general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind, two or more kinds, and when there are two or more kinds, Combinations and ratios can be arbitrarily selected.
  • the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited and is appropriately selected according to the purpose. do it.
  • the protective film-forming composition (IV-1) preferably further contains a solvent.
  • the protective film-forming composition (IV-1) containing a solvent has good handleability.
  • the solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. Esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
  • the solvent contained in the protective film-forming composition (IV-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the solvent contained in the protective film-forming composition (IV-1) is methyl ethyl ketone, toluene, ethyl acetate, or the like from the viewpoint that the components contained in the protective film-forming composition (IV-1) can be mixed more uniformly. It is preferable.
  • the composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending each component for constituting the composition.
  • the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
  • a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
  • the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
  • the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
  • a release film having a surface roughness (Ra) of at least one surface of 0.03 to 2.0 ⁇ m referred to as a first release film
  • the composition for forming a protective film can be coated on the surface having the surface roughness, and dried as necessary.
  • the surface roughness (Ra) of the surface of the first release film is preferably 0.03 to 1.8 ⁇ m.
  • the protective film-forming film of the present invention is a protective film-forming film produced as described above, on the surface opposite to the surface on which the first release film is pasted (that is, the surface ( ⁇ )).
  • Another release film (sometimes referred to as a second release film) may be attached.
  • a protective film-forming film provided with a release film may be referred to as a “protective film-forming sheet”.
  • the exposed surface (surface ⁇ ) of the protective film-forming film is blended with a filler having a predetermined average particle diameter in the protective film-forming composition.
  • a surface having a predetermined surface roughness (Ra) is formed.
  • a surface having a surface roughness (Ra) of 0.03 to 2.0 ⁇ m can be formed by blending a filler having an average particle size of 0.01 to 20 ⁇ m.
  • composition for forming a protective film on a surface having a surface roughness of a release film (sometimes referred to as a first release film) having a surface roughness (Ra) of at least one surface of 0.03 to 2.0 ⁇ m
  • a release film sometimes referred to as a first release film
  • Ra surface roughness
  • An object is applied and dried as necessary to form a protective film-forming film, and a second release film is bonded to the exposed surface of the protective film-forming film.
  • Producing the protective film-forming composite sheet of the present invention by bonding the exposed surface of the protective film-forming film from which the second release film has been peeled (that is, the surface ( ⁇ )) to the surface of the support sheet. Can do.
  • the protective film forming film or protective film forming sheet of the present invention can be used, for example, by the following method. That is, the surface ( ⁇ ) on the side having the first release film of the protective film forming sheet is attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer with the protective film forming film. At this time, when the protective film-forming film is attached to the back surface of the semiconductor wafer at a position shifted from the position to be originally attached, the protective film-forming film attached to the back surface of the semiconductor wafer is peeled off.
  • a protective film forming film that has failed to be applied at an appropriate position is affixed to a surface opposite to the surface applied to the semiconductor wafer, that is, the surface ( ⁇ ). Then, the adhesive sheet for rework and the film for forming a protective film that has failed to be adhered are integrally peeled from the semiconductor wafer.
  • the pasted protective film-forming film is used as a rework pressure-sensitive adhesive sheet. And can be removed smoothly. That is, it is possible to remove the semiconductor wafer cleanly without damaging the semiconductor wafer due to the peeling force or leaving a part of the protective film forming film on the back surface of the semiconductor wafer. Therefore, after the back surface of the semiconductor wafer is cleaned as it is or as much as necessary, another new protective film forming sheet (protective film forming film) is prepared and the first peeling is performed. The film is peeled off and attached again at an appropriate position on the back surface of the semiconductor wafer.
  • Ra surface roughness
  • the protective film forming film is irradiated with energy rays, the protective film forming film is cured to form a protective film, the second release film is peeled off, and the protective film is exposed.
  • the surface (surface ( ⁇ )) is attached to the support sheet, and the semiconductor wafer is divided together with the protective film by dicing to form semiconductor chips.
  • the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then the semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.
  • the composite sheet for protective film formation of this invention can be used by the method shown below, for example. 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. At this time, when the protective film forming composite sheet is attached to the back surface of the semiconductor wafer at a position shifted from the position to be originally applied, the protective film forming composite sheet attached to the back surface of the semiconductor wafer is peeled off. . Specifically, the composite sheet for forming a protective film that has failed to stick to an appropriate position is peeled off from the semiconductor wafer.
  • the attached protective film-forming composite sheet can be smoothly smoothed. Can be peeled off. That is, it is possible to remove the semiconductor wafer cleanly without damaging the semiconductor wafer due to the peeling force or leaving a part of the composite sheet for forming the protective film on the back surface of the semiconductor wafer. Therefore, after the back surface of the semiconductor wafer is cleaned as it is or with the minimum necessary, a new composite sheet for forming a protective film is prepared, and the first release film is peeled off to remove the semiconductor. Affix again at the appropriate position on the back of the wafer.
  • the semiconductor wafer is divided together with the protective film into semiconductor chips by the same method as the conventional method, that is, by irradiating and curing energy rays and dicing. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is attached (that is, as a semiconductor chip with a protective film). Thereafter, the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then the semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.
  • the protective film-forming film or the protective film-forming composite sheet of the present invention when using the protective film-forming film or the protective film-forming composite sheet of the present invention, these The order in which the steps are performed may be reversed. That is, after a protective film-forming composite sheet is attached to the back surface of the semiconductor wafer, the semiconductor wafer is divided together with the protective film-forming film by dicing to form semiconductor chips. Next, the divided protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to form a protective film. Thereafter, in the same manner as described above, the semiconductor chip with the protective film may be pulled away from the support sheet and picked up to produce the target semiconductor device.
  • Step (1) The surface of the pressure-sensitive adhesive sheet for rework having a base material and a pressure-sensitive adhesive layer on the side opposite to the surface ( ⁇ ) attached to the silicon wafer of the protective film-forming film of the laminate.
  • Step (2) for attaching to ( ⁇ ) Step of peeling off the protective film-forming film attached to the silicon wafer by peeling off the rework adhesive sheet attached in Step (1).
  • the above silicon wafer recycling method has excellent reworkability so that the silicon wafer can be peeled without damaging and producing a residue when it is peeled off after being attached to the silicon wafer. It utilizes the properties of the protective film-forming film of the present invention. Note that this silicon wafer recycling method is not limited to a laminate immediately after the silicon wafer and the surface ( ⁇ ) of the protective film-forming film of the present invention are pasted, but after about 24 hours have passed since the pasting. The present invention can also be applied to a laminate in which the adhesion between the wafer and the protective film-forming film is improved.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet having a base material and a pressure-sensitive adhesive layer is a surface ( ⁇ ) opposite to the surface ( ⁇ ) affixed to the silicon wafer of the protective film-forming film of the laminate. ).
  • the rework pressure-sensitive adhesive sheet used in this step has a base material and a pressure-sensitive adhesive layer.
  • a support body which consists of an adhesive sheet
  • a resin film is preferable.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited as long as the pressure-sensitive adhesive has an adhesive force that can peel the protective film-forming sheet from the silicon wafer in the step (2).
  • Specific examples of the pressure sensitive adhesive include acrylic pressure sensitive adhesive, urethane pressure sensitive adhesive, and silicone pressure sensitive adhesive.
  • the shape of the pressure-sensitive adhesive sheet for rework is not particularly limited, but from the viewpoint of operability in the next step (2), the same shape as the protective film-forming sheet or the protective film-forming composite sheet, or protective film formation An adhesive sheet having a shape larger than that of the protective sheet or the protective film-forming composite sheet is preferred.
  • a support sheet in the composite sheet for forming a protective film of the present invention or a commercially available dicing sheet can be used.
  • the present step as a method for applying the surface ( ⁇ ) and the adhesive layer of the adhesive sheet, it may be applied using an apparatus or may be performed manually.
  • Step (2) is a step of peeling off the protective film-forming film attached to the silicon wafer by peeling off the rework adhesive sheet attached in step (1).
  • the surface roughness (Ra) of the surface ( ⁇ ) affixed to the silicon wafer of the protective film-forming film of the present invention is adjusted to the above range, the surface ( ⁇ ) in step (1) is adjusted.
  • the protective film-forming film is also peeled off together, and the protective film-forming film can be peeled off from the silicon wafer.
  • the adhesive tape may be peeled off using an apparatus, but from the viewpoint of operability, the adhesive sheet may be peeled off manually to peel the protective film-forming film from the silicon wafer. preferable.
  • the surface of the silicon wafer may be washed with an organic solvent such as ethanol as necessary.
  • an organic solvent such as ethanol
  • Energy ray curable component (a2) -1 Tricyclodecane dimethylol diacrylate (“KAYARAD R-684”, bifunctional ultraviolet curable compound, molecular weight 304, manufactured by Nippon Kayaku Co., Ltd.)
  • Acrylic resin weight average molecular weight 300000, glass transition temperature ⁇ 1 ° C.
  • Photopolymerization initiator (c) -1 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (“Irgacure (registered trademark) 369” manufactured by BASF)
  • D) -2 Silica filler (surface modifying group: epoxy group) average particle size 50 nm
  • 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).
  • a protective film-forming composition (IV-1) having a solid content concentration of 50% by mass was prepared.
  • the compounding quantity of each component shown here is all solid content.
  • the description of “-” in the column of the component in Table 1 means that the protective film-forming composition (IV-1) does not contain the component.
  • the release of the second release film (“SP-PET 382150” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m, hereinafter referred to as “P2”) in which one side of the polyethylene terephthalate film has been subjected to release treatment by silicone treatment.
  • the exposed surface of the protective film-forming film (13) -1 obtained above is bonded to the treated surface, so that the first release film, the protective film-forming film (13) -1 and the second release film are A protective film-forming sheet was produced that was laminated in this order in the thickness direction.
  • Example 2 As the first release film, the same as Example 1 except that instead of P3, a release film using polyethylene terephthalate with a surface roughness (Ra) of 0.040 ⁇ m (hereinafter sometimes referred to as “P4”) was used. Thus, a protective film-forming sheet was produced.
  • P4 polyethylene terephthalate with a surface roughness (Ra) of 0.040 ⁇ m
  • Example 3 As the second release film, a release film using polyethylene terephthalate having a surface roughness (Ra) of 0.040 ⁇ m (hereinafter sometimes referred to as “P4”) is used instead of P3, and a protective film-forming film (13 ) -1 was prepared in the same manner as in Example 1 except that the protective film-forming film (13) -2 was used.
  • the protective film-forming film (13) -2 is the protective film-forming film of Example 1 except that 5 parts by mass of filler (d) -2 was used instead of 2 parts by mass of filler (d) -1. It was produced in the same manner as film (13) -1.
  • Example 4 (Production of pressure-sensitive adhesive composition (I-4)) Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and further as a solvent A non-energy ray-curable pressure-sensitive adhesive composition (I-4) containing methyl ethyl ketone and having a solid content concentration of 30% by mass was prepared.
  • the acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass).
  • the weight average molecular weight is 600,000.
  • the pressure-sensitive adhesive composition (I-4) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. ) And dried by heating at 120 ° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 ⁇ m.
  • SP-PET 381031 manufactured by Lintec Co., Ltd., thickness 38 ⁇ m
  • 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 composite sheet for forming a protective film is produced by laminating the surfaces, a base material, an adhesive layer, a protective film forming film (13) -1 and a film (P3) laminated in this thickness direction in this order. did.
  • Table 2 shows the structure of the obtained protective sheet-forming composite sheet.
  • Example 1 The protective film was the same as in Example 1 except that a film using polyethylene terephthalate having a surface roughness (Ra) of 0.026 ⁇ m (hereinafter sometimes referred to as “P5”) was used as the first release film.
  • a forming sheet was prepared.
  • Comparative Example 2 A protective film as in Example 1 except that a film using polyethylene terephthalate having a surface roughness (Ra) of 0.020 ⁇ m (hereinafter sometimes referred to as “P6”) was used as the first release film. A forming sheet was prepared.
  • Example 3 As the first release film, a film (P6) using polyethylene terephthalate having a surface roughness (Ra) of 0.020 ⁇ m was used, and instead of the protective film-forming film (13) -1, a protective film-forming film (13 ) -2 was used, and a protective film-forming sheet was produced in the same manner as in Example 1.
  • the protective film-forming film (13) -2 is the protective film-forming film of Example 1 except that 5 parts by mass of filler (d) -2 was used instead of 2 parts by mass of filler (d) -1. It was produced in the same manner as film (13) -1.
  • Example 4 A protective film as in Example 4 except that a film (P5) using polyethylene terephthalate having a surface roughness (Ra) of 0.026 ⁇ m was used instead of the polyethylene terephthalate film (P3) as the release film. A forming sheet was prepared. The protective film-forming composition (IV-1) was applied to the surface of the film (P5) having the surface roughness (Ra).
  • the second release film is removed at room temperature (25 ° C.), and the surface of the exposed protective film-forming film is used as a rework pressure-sensitive adhesive sheet. Then, the pressure-sensitive adhesive layer surface of a commercially available general-purpose dicing tape (product name “Adwill D-510T” manufactured by Lintec Corporation) was attached.
  • a commercially available general-purpose dicing tape product name “Adwill D-510T” manufactured by Lintec Corporation
  • the reworkability of the protective film-forming sheet was evaluated according to the following criteria by observing whether or not the forming film could be peeled from the silicon wafer, and the presence or absence of residue on the surface of the peeled silicon wafer.
  • A The protective film-forming film was completely peeled from the silicon wafer. No residue of the protective film-forming film that can be visually confirmed was observed on the peeled silicon wafer. Or, the protective film-forming film could be peeled off from the silicon wafer, but some residual film of the protective film-forming film was seen on the peeled silicon wafer and could be completely removed by wiping with ethanol. Met.
  • X The silicon wafer was damaged during peeling.
  • the protective film-forming film could be peeled off without damaging the silicon wafer, but the remaining silicon film after the peeling was difficult to wipe off with ethanol. It was. Alternatively, it was judged as defective (x) when it was found that peeling was not possible even if the silicon wafer was not broken until it was damaged.
  • the surface roughness (Ra) of the surface ( ⁇ ) of the protective film-forming film Is less than 0.038 ⁇ m, the semiconductor wafer is damaged when the protective film forming film is peeled off from the back surface of the semiconductor wafer, or a part of the protective film forming film remains on the back surface of the semiconductor wafer. It happened and the reworkability was poor.
  • the present invention can be used for manufacturing semiconductor devices.
  • protective film forming composite sheet 1F protective film forming sheet 10 ... support sheet 10a ... support sheet surface 11 ... substrate 11a ... ⁇ Surface 12 of the substrate ⁇ Adhesive layer 12a ⁇ ⁇ ⁇ Surface 13 and 23 of the adhesive layer ⁇ ⁇ ⁇ Films 13a and 23a for protective film formation ⁇ ⁇ ⁇ 15 of the film for protective film formation ⁇ Peeling Film 16 ... Jig adhesive layer 16a ... Jig adhesive layer surface

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  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Dicing (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Physical Vapour Deposition (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

La présente invention concerne un film durcissable par rayonnement énergétique permettant de former un film protecteur. La rugosité de surface (Ra) d'au moins une surface (α) du film pour former le film protecteur vaut au moins 0,038 µm. La rugosité de surface (Ra) de ladite surface (α) est de préférence inférieure ou égale à 2,0 µm.
PCT/JP2017/016260 2016-04-28 2017-04-25 Film pour former un film de protection et feuille composite pour former un film de protection Ceased WO2017188202A1 (fr)

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JP2018514597A JP7285075B2 (ja) 2016-04-28 2017-04-25 保護膜形成用フィルム及び保護膜形成用複合シート
CN201780019966.1A CN108886023B (zh) 2016-04-28 2017-04-25 保护膜形成用膜及保护膜形成用复合片
KR1020187027332A KR102445025B1 (ko) 2016-04-28 2017-04-25 보호막 형성용 필름 및 보호막 형성용 복합 시트
JP2022061944A JP7290771B2 (ja) 2016-04-28 2022-04-01 保護膜形成用フィルム及び保護膜形成用複合シート

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JP7285075B2 (ja) 2023-06-01
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CN108886023A (zh) 2018-11-23
JP2022089876A (ja) 2022-06-16
TW201812879A (zh) 2018-04-01
KR102445025B1 (ko) 2022-09-20
TWI782911B (zh) 2022-11-11
KR20190004694A (ko) 2019-01-14

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