WO2015030031A1 - Laminate and application therefor - Google Patents

Laminate and application therefor Download PDF

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Publication number
WO2015030031A1
WO2015030031A1 PCT/JP2014/072369 JP2014072369W WO2015030031A1 WO 2015030031 A1 WO2015030031 A1 WO 2015030031A1 JP 2014072369 W JP2014072369 W JP 2014072369W WO 2015030031 A1 WO2015030031 A1 WO 2015030031A1
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Prior art keywords
group
adhesive layer
polymerizable monomer
polymerizable
resin
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PCT/JP2014/072369
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French (fr)
Japanese (ja)
Inventor
悠 岩井
一郎 小山
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富士フイルム株式会社
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Publication of WO2015030031A1 publication Critical patent/WO2015030031A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
    • H01L2221/68386—Separation by peeling

Definitions

  • the present invention relates to a laminate, a protective layer forming composition, an adhesive layer precursor or an adhesive layer forming composition, and a kit thereof. More specifically, a laminate temporarily bonded to an adhesive support using a temporary adhesive for manufacturing a semiconductor device, a protective layer forming composition used therefor, an adhesive layer precursor or an adhesive layer forming composition, and The present invention relates to a kit comprising the protective layer forming composition and an adhesive layer precursor or an adhesive layer forming composition.
  • a wire bonding method As an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known.
  • a silicon substrate is used.
  • a method is known in which a through-hole is provided in the semiconductor device and a metal plug as an external terminal is connected to an integrated circuit so as to pass through the through-hole (so-called silicon through electrode (TSV) forming method).
  • TSV silicon through electrode
  • a technique for improving the degree of integration per unit area of a silicon substrate by multilayering integrated circuits in an IC chip is known.
  • the multilayered integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the members constituting the IC chip.
  • the thinning of the silicon substrate is being considered as the thinning of such a member, which not only leads to the miniaturization of the IC chip, but also saves labor in the through hole manufacturing process of the silicon substrate in the manufacture of the silicon through electrode. Because it is possible, it is considered promising.
  • a semiconductor silicon wafer having a thickness of about 700 to 900 ⁇ m is widely known as a semiconductor silicon wafer used in a semiconductor device manufacturing process.
  • the thickness of a semiconductor silicon wafer has been reduced for the purpose of miniaturizing an IC chip. Attempts have been made to reduce the thickness to 200 ⁇ m or less.
  • the semiconductor silicon wafer having a thickness of 200 ⁇ m or less is very thin, and the semiconductor device manufacturing member based on this is also very thin, such a member can be further processed, or When such a member is simply moved, it is difficult to support the member stably and without causing damage.
  • the wafer is supported by a support layer system, and a plasma polymer layer obtained by a plasma deposition method is interposed as a separation layer between the wafer and the support layer system.
  • the adhesive bond between the support layer system and the separation layer is made larger than the bond bond between the wafer and the separation layer, so that when the wafer is detached from the support layer system, the wafer is easily detached from the separation layer.
  • a technique configured to be separated is also known (see Patent Document 2).
  • a pressure-sensitive adhesive film made of syndiotactic 1,2-polybutadiene and a photopolymerization initiator and having an adhesive force that changes by irradiation with radiation is known (see Patent Document 6). Further, the support substrate and the semiconductor wafer are temporarily bonded with an adhesive made of polycarbonate, the semiconductor wafer is processed, irradiated with irradiation radiation, and then heated, thereby processing the processed semiconductor wafer. A technique for detaching the substrate from the support substrate is known (see Patent Document 7).
  • the support substrate and the semiconductor wafer are temporarily bonded with two layers having different softening points, and after processing the semiconductor wafer, the support substrate and the semiconductor wafer are detached by heating and sliding laterally.
  • the technology to do is known. (See Patent Document 8).
  • the surface of the semiconductor wafer on which the device is provided (that is, the device surface of the device wafer) and the support substrate (carrier substrate) are temporarily bonded via a layer made of an adhesive known in Patent Document 1 or the like.
  • the adhesive layer is required to have a certain degree of adhesion to stably support the semiconductor wafer. Therefore, in the case of temporarily bonding the entire device surface of the semiconductor wafer and the support through the adhesive layer, the temporary bonding between the semiconductor wafer and the support is sufficient, and the semiconductor wafer is stably and However, the temporary adhesion between the semiconductor wafer and the support is too strong, so that the device may be damaged or detached from the semiconductor wafer. There is a tendency for the device to be detached.
  • a plasma polymer layer as a separation layer is formed between the wafer and the support layer system by a plasma deposition method.
  • the forming method is (1) the equipment cost for carrying out the plasma deposition method is usually high; (2) the layer formation by the plasma deposition method requires time for vacuuming and monomer deposition in the plasma apparatus; and (3) Even when a separation layer composed of a plasma polymer layer is provided, when supporting a wafer to be processed, the wafer is released from support while the adhesive bond between the wafer and the separation layer is sufficient. In such a case, it is not easy to control the adhesive bond so that the wafer is easily detached from the separation layer;
  • Patent Documents 3, 4, 5, and 8 the method of releasing temporary adhesion by heating tends to cause a problem that the device is damaged when the semiconductor wafer is detached.
  • the present invention has been made in view of the above background, and its purpose is to temporarily support a processing member with a high adhesive force when mechanically or chemically processing the processing member (such as a semiconductor wafer).
  • the object is to provide a protective layer forming composition, an adhesive layer precursor or an adhesive layer forming composition, and a kit thereof.
  • the present inventors have (B) an adhesive layer precursor, (C) a protective layer, and (D) a device wafer in this order on a support.
  • the laminate (B) (b-1) containing a polymerizable monomer and / or polymerizable oligomer and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70% is used, The present inventors have found that the device wafer and the support can be temporarily supported by a high adhesive force, and the temporary support of the device wafer can be easily released, and the present invention has been completed.
  • a protective layer and an adhesive precursor are formed by a polymer of polymerizable monomer and / or polymerizable oligomer.
  • a mixture of a polymer and a polymerizable monomer and / or a polymerizable oligomer Since an appropriate anchoring effect works at the interface and further the polymerization proceeds after bonding, the elastic modulus of the adhesive layer can be set high, so that the wafer thickness Both the adhesiveness at the time of forming and the peelability after thinning can be achieved. Based on the above view, the present inventors have found that an adhesive layer having high adhesiveness and can be easily peeled can be formed, and the present invention has been completed.
  • Adhesive layer precursor (B) Adhesive layer precursor, (C) Protective layer, (D) Device wafer in this order on (A) support, (B) Adhesive layer precursor is (b- 1) A laminate comprising a polymerizable monomer and / or polymerizable oligomer, and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70%.
  • ⁇ 2> (b-1) The laminate according to ⁇ 1>, wherein the polymerizable monomer and / or polymerizable oligomer includes at least one radically polymerizable monomer having three or more functions.
  • ⁇ 3> (b-1) The laminate according to ⁇ 1> or ⁇ 2>, wherein the polymerizable monomer and / or polymerizable oligomer includes at least one radical polymerizable compound having a fluorine atom and / or a silicon atom. .
  • the polymerizable monomer and / or the polymerizable oligomer includes any one of ⁇ 1> to ⁇ 3>, including a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer.
  • ⁇ 6> The laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the adhesive layer precursor further contains (b-3) a thermal radical initiator.
  • ⁇ 7> The laminate according to any one of ⁇ 1> to ⁇ 6>, wherein the adhesive layer precursor further contains (b-4) a polymer compound.
  • the adhesive layer precursor further contains (b-4) a polymer compound.
  • ⁇ 10> (C) The laminate according to any one of ⁇ 1> to ⁇ 9>, wherein the protective layer is a thermoplastic resin.
  • the protective layer is at least one thermoplastic selected from polyethersulfone resin, polyimide resin, polyester resin, polybenzimidazole resin, polyamideimide resin, polycarbonate resin, polystyrene resin and polyetheretherketone resin.
  • ⁇ 12> (D) The laminate according to any one of ⁇ 1> to ⁇ 11>, wherein the device wafer has a structure having a height of 1 ⁇ m to 150 ⁇ m on the surface.
  • a composition comprising a solvent and (b-1) a polymerizable monomer and / or a polymerizable oligomer.
  • the polymerizable monomer and / or the polymerizable oligomer includes any one of ⁇ 15> to ⁇ 17>, including a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer.
  • the composition as described. ⁇ 19> The composition according to any one of ⁇ 15> to ⁇ 18>, further comprising (b-2) a photoradical initiator.
  • ⁇ 20> The composition according to any one of ⁇ 15> to ⁇ 18>, further comprising (b-2) a thermal radical initiator.
  • ⁇ 21> The composition according to any one of ⁇ 15> to ⁇ 20>, further comprising (b-4) a polymer compound.
  • kits comprising a protective layer forming composition containing a resin and a solvent, and an adhesive layer precursor or an adhesive layer forming composition containing a solvent and a polymerizable monomer and / or a polymerizable oligomer.
  • kit comprising a protective layer forming composition containing a resin and a solvent, and an adhesive layer precursor or an adhesive layer forming composition containing a solvent and a polymerizable monomer and / or a polymerizable oligomer.
  • the member to be treated when performing mechanical or chemical treatment on a member to be treated, the member to be treated can be temporarily supported by a high adhesive force, and the treated member can be temporarily treated without damaging the treated member. It has become possible to provide a laminate, a protective layer forming composition, an adhesive layer precursor or an adhesive layer forming composition, and a kit thereof that can be easily released from support.
  • FIG. 1A, 1B, 1C, 1D, 1E, and 1F are schematic cross-sectional views illustrating temporary bonding between a support and a device wafer, a state in which a device wafer temporarily bonded to the support is thinned, and support, respectively. It is a schematic sectional drawing which shows the state after peeling the body and the device wafer, and the state after washing
  • FIG. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the adhesive support and the device wafer.
  • substitution and non-substitution includes those having no substituent and those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like. In the present invention, “light” means actinic rays or radiation.
  • the term “exposure” in the present specification is not limited to exposure by far-ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc. It also means drawing with particle beams.
  • “(meth) acrylate” represents acrylate and methacrylate
  • “(meth) acryl” represents acryl and methacryl
  • “(meth) acryloyl” represents acryloyl and methacryloyl.
  • “monomer” and “monomer” are synonymous.
  • the monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a mass average molecular weight of 2,000 or less.
  • the laminate of the present invention has (B) an adhesive layer precursor, (B) an adhesive layer precursor, (C) a protective layer, and (D) a device wafer in this order.
  • (B-1) includes a polymerizable monomer and / or polymerizable oligomer, and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70%.
  • the laminate of the present invention also relates to a laminate obtained by further curing the laminate. That is, (B) adhesive layer, (C) protective layer, and (D) device wafer are provided in this order on (A) support, and (B2) adhesive layer is (B) adhesive layer precursor. It is a cured product.
  • the laminate of the present invention is highly valuable in that it can be used in an environment of 250 ° C. or higher. According to the laminate of the present invention, when performing mechanical or chemical treatment on the treatment member, the treatment member can be temporarily supported by a high adhesive force, and the treated member is treated without damage. Temporary support for the member can be released.
  • the laminate of the present invention is preferably used for forming a silicon through electrode. The formation of the through silicon via will be described in detail later.
  • the laminate of the present invention has (B) an adhesive layer precursor, and the adhesive layer precursor includes (b-1) a polymerizable monomer and / or a polymerizable oligomer, and the polymerizable monomer and / or Alternatively, the polymerization rate of the polymerizable oligomer is 10 to 70%.
  • the adhesive layer precursor includes (b-1) a polymerizable monomer and / or a polymerizable oligomer, and the polymerizable monomer and / or Alternatively, the polymerization rate of the polymerizable oligomer is 10 to 70%.
  • Adhesive layer precursor >> ((B-1) polymerizable monomer and / or polymerizable oligomer)
  • the adhesive layer precursor has (b-1) a polymerizable monomer and / or a polymerizable oligomer.
  • Arbitrary things can be used as a polymerizable monomer and it can select arbitrarily from the radically polymerizable monomer and / or polymerizable oligomer which are demonstrated below. From the viewpoint of adhesiveness and peelability, it is preferable to include at least one bifunctional or higher polymerizable monomer, and more preferable to include at least one trifunctional or higher polymerizable monomer.
  • the polymerizable monomer and / or polymerizable oligomer preferably contains a fluorine atom and / or a silicon atom, and more preferably contains at least a fluorine atom.
  • the polymerizable monomer and / or polymerizable oligomer is preferably a polymerizable compound in which 5% by mass or more contains a fluorine atom, and 10% by mass or more is a polymerizable compound containing a fluorine atom. It is preferably a compound, and more preferably 20% by mass or more is a polymerizable compound containing a fluorine atom.
  • the polymerization rate of the polymerizable monomer and / or polymerizable oligomer in the adhesive layer precursor is 10 to 70%, preferably 20 to 60%, more preferably 25 to 50%.
  • a composition containing the polymerizable monomer and / or polymerizable oligomer is 50.
  • examples thereof include a method of heating at ⁇ 300 ° C., a method of irradiating actinic rays or radiation, and selection of a polymerization initiator.
  • the heating temperature in the method of heating the adhesive layer precursor forming composition at 50 to 300 ° C. is preferably 50 to 300 ° C., more preferably 100 to 200 ° C., and further preferably 140 to 170 ° C.
  • the heating time is preferably 30 seconds to 10 minutes, more preferably 1 to 7 minutes, and further preferably 2 to 5 minutes.
  • the polymerizable monomer and / or polymerizable oligomer is polymerized by exposing the composition for forming an adhesive layer precursor using a UV exposure apparatus. Exposure is preferably 100 ⁇ 5000mJ / cm 2, more preferably 300 ⁇ 3000mJ / cm 2, more preferably 400 ⁇ 1500mJ / cm 2.
  • the polymerization rate of the polymerizable monomer and / or polymerizable oligomer should be measured, for example, by performing IR measurement before and after polymerization of the polymerizable monomer and / or polymerizable oligomer, and from the reduction rate of the peak area in the vicinity of 800 to 820 cm ⁇ 1. Can do.
  • a polymerizable monomer and / or a polymerizable oligomer means a compound having a polymerizable group, and a radical polymerizable group is preferable as the polymerizable group. That is, the polymerizable monomer and / or polymerizable oligomer is preferably a radical polymerizable monomer and / or polymerizable oligomer.
  • the number of functional groups of the radical polymerizable monomer and / or polymerizable oligomer in the present invention means the number of radical polymerizable groups in one molecule.
  • the radical polymerizable group is typically a group that can be polymerized by irradiation with actinic rays or radiation, or by the action of radicals.
  • the polymerizable monomer is a compound different from the polymer compound.
  • the polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably it is.
  • the molecular weight is usually 100 or more.
  • the polymerizable oligomer is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 monomers are bonded.
  • the polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) method is preferably 2000 to 20000, more preferably 2000 to 15000, and most preferably 2000 to 10,000.
  • the polymerizable group is preferably, for example, a functional group that can undergo an addition polymerization reaction, and examples of the functional group that can undergo an addition polymerization reaction include an ethylenically unsaturated bond group.
  • the ethylenically unsaturated bond group a styryl group, a (meth) acryloyl group and an allyl group are preferable, and a (meth) acryloyl group is more preferable.
  • the radical polymerizable monomer used in the present invention is preferably a (meth) acrylate monomer, and more preferably an acrylate monomer.
  • the radical polymerizable monomer may be any of chemical forms such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, a mixture thereof, and a multimer thereof.
  • examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and polyhydric alcohol compounds amides of unsaturated carboxylic acids and polyhydric amine compounds, and multimers thereof.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate.
  • Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (me
  • Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
  • crotonic acid esters examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
  • isocrotonic acid esters examples include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
  • maleic acid esters examples include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
  • esters examples include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Those having an aromatic skeleton described in JP-A-59-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613 are also preferably used.
  • amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic.
  • examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
  • Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
  • urethane-based addition-polymerizable monomers produced using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Etc.
  • CH 2 C (R 4) COOCH 2 CH (R 5) OH (A) (However, R 4 and R 5 represent H or CH 3.
  • urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.
  • radical polymerizable monomer compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.
  • the radical polymerizable monomer is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure.
  • monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
  • a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group
  • preferable radical polymerizable monomers those having a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. It is also possible to use a compound having a functionality or higher, a cardo resin.
  • radical polymerizable monomer examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid-based compounds described in the Japanese Patent Publication. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.
  • Examples of the compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group include the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. Is preferred.
  • radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used.
  • T is an oxyalkylene group
  • the terminal on the carbon atom side is bonded to R.
  • n is an integer of 0 to 14, and m is an integer of 1 to 8.
  • a plurality of R and T present in one molecule may be the same or different.
  • at least one of the plurality of Rs is —OC ( ⁇ O) CH ⁇ CH 2 , or A group represented by —OC ( ⁇ O) C (CH 3 ) ⁇ CH 2 is represented.
  • Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.
  • compounds described in JP-A No. 10-62986 as general formulas (1) and (2) together with specific examples thereof are compounds obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol and then (meth) acrylated. Can be used as a radical polymerizable monomer.
  • dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (commercially available) KAYARAD D-310 (commercially available from Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues. These oligomer types can also be used.
  • the radical polymerizable monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is.
  • the acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride.
  • non-aromatic carboxylic acid anhydride examples include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.
  • the adhesive layer precursor in the present invention may have a monomer having an acid group.
  • the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • a preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be inferior.
  • the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.
  • the polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
  • the polyfunctional monomer which has a caprolactone structure represented with the following general formula (B) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group
  • “*” represents a bond.
  • Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd.
  • the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.
  • the polyfunctional monomer is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).
  • each E independently represents — ((CH 2 ) yCH 2 O) — or — ((CH 2 ) yCH (CH 3 ) O) —, y
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
  • the total number of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • any one of X is a carboxyl group.
  • the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • the compound represented by the general formula (i) or (ii) is a ring-opening skeleton obtained by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).
  • pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available radical polymerizable monomers represented by the general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • radical polymerizable monomer examples include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable monomers. Monomers can also be used.
  • urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha), Bremer PME400 (manufactured by NOF Corporation)) and the like.
  • the polymerizable monomer in the present invention may be used singly or in combination of two or more types for the bifunctional or lower radical polymerizable monomer and the trifunctional or higher radical polymerizable monomer. From the viewpoint of having an original cross-linked structure, it is preferable to include at least one trifunctional or higher functional radical polymerizable monomer and to be a mixture of a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer. .
  • the number of atoms between any two radically polymerizable groups in which at least one of a radically polymerizable monomer having a functionality of 2 or less and a radically polymerizable monomer having a functionality of 3 or more are contained in one molecule are both It is preferably 9 atoms or more from the viewpoints of adhesiveness and easy peelability. That is, when it has three or more polymerizable groups in one molecule, it means that the number of atoms between any two polymerizable groups is 9 atoms or more apart.
  • linking group consisting of 9 or more atoms linking any two radically polymerizable groups contained in one molecule
  • examples of the linking group consisting of 9 or more atoms linking any two radically polymerizable groups contained in one molecule include —CO—, —O—, —NH—, and divalent to tetravalent fatty acids.
  • a linking group having a valence of 2 or more selected from the group consisting of an aromatic group, a bivalent to hexavalent aromatic group, and combinations thereof (usually having a valence corresponding to the number of functional groups), -CO-, -O- and a divalent linking group selected from the group consisting of a divalent aliphatic group and a combination thereof are more preferable.
  • the aliphatic group and the aromatic group may have a substituent.
  • the number of atoms between any two radically polymerizable groups contained in one molecule of a bifunctional or lower radical polymerizable monomer and / or a trifunctional or higher functional radical polymerizable monomer is the number of atoms of the linking group. If the amount is too large, the releasability is lowered, and therefore the divalent linking group is preferably 9 to 100 atoms, more preferably 10 to 80 atoms, and particularly preferably 12 to 50 atoms.
  • the number of atoms between any two radically polymerizable groups contained in one molecule is the number of atoms between radically polymerizable ethylenically unsaturated groups. Specifically, as in the following example, Be counted.
  • At least one of a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer preferably has a polyoxyalkylene partial structure represented by the following general formula (1).
  • General formula (1) (In general formula (1), R 21 represents a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150.)
  • Examples of the alkyl group represented by R 21 include straight-chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, An isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like can be mentioned.
  • R 21 is particularly preferably a hydrogen atom.
  • a is preferably 1 or 2, and particularly preferably 1.
  • l is preferably an integer of 2 to 50, more preferably an integer of 2 to 25, and particularly preferably an integer of 2 to 10.
  • Monomers connected by divalent or higher valent linking groups in which the number of atoms between any two radically polymerizable groups contained in one molecule is 9 atoms or more are all difunctional radical polymerizations. It is preferably a reactive monomer, and more preferably a bifunctional radically polymerizable monomer. Furthermore, the bifunctional or lower radical polymerizable monomer preferably has a polyoxyalkylene partial structure represented by the general formula (1), and the bifunctional radical polymerizable monomer is represented by the general formula (1). More preferably, it has a polyoxyalkylene partial structure.
  • the bifunctional or lower radical polymerizable monomer is particularly preferably a bifunctional monomer represented by the following general formula (2).
  • General formula (2) (In the general formula (2), R 21 , R 22 and R 23 each represent a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150.
  • X 1 , X 2 , Y 1 and Y 2 are each composed of a single bond, or —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represents a divalent linking group selected from the group.)
  • Examples of the alkyl group represented by R 21 , R 22 and R 23 include straight-chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and each includes a methyl group, an ethyl group, a propyl group, an octyl group, Examples include isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
  • R 21 is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
  • R 22 and R 23 are each particularly preferably a hydrogen atom or a methyl group.
  • a and l are respectively synonymous with a and l in General formula (1), and their preferable range is also the same.
  • X 1 and X 2 are each selected from the group consisting of a single bond, or —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represents a divalent linking group.
  • Specific examples of X 1 and X 2 include the following L1 to L18, respectively. In the following example, the left side is bonded to Y 1 or Y 2 , and the right side is bonded to an ethylenically unsaturated bond.
  • the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
  • an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
  • These groups preferably have no substituent.
  • the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
  • Y 1 and Y 2 are each selected from the group consisting of a single bond, or —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represents a divalent linking group.
  • Either Y 1 or Y 2 preferably has a divalent aromatic group or a polyoxyalkylene structure, and particularly preferably has a divalent aromatic group and a polyoxyalkylene structure.
  • the divalent aromatic group is preferably composed of one or two or more benzene rings, and more preferably a phenylene group.
  • the radical polymerizable monomer having 2 or less functional groups and / or the radical polymerizable monomer having 3 or more functional groups may be composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom and a nitrogen atom. Preferably, it is comprised only from a carbon atom, an oxygen atom, and a hydrogen atom.
  • the ratio (mass ratio) of the bifunctional or lower radical polymerizable monomer and the trifunctional or higher radical polymerizable monomer is preferably 95/5 to 20/80, more preferably 85/15 to 20/80. It is preferably 80/20 to 20/80, more preferably 80/20 to 40/60, and particularly preferably 80/20 to 50/50.
  • NK ester A-TMP-3EO, NK ester AD-TMP, NK ester A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.
  • divinylbenzene manufactured by Wako Pure Chemical Industries, Ltd.
  • light acrylate TMP -A manufactured by Kyoeisha Chemical Co., Ltd.
  • triallyl isocyanurate manufactured by Tokyo Chemical Industry Co., Ltd.
  • the content of the polymerizable monomer is preferably 20 to 100% by mass, more preferably 30 to 95% by mass with respect to the total solid content of the adhesive layer precursor, from the viewpoint of good adhesive strength and peelability. More preferably, it is 90% by mass. Only one type of polymerizable monomer may be used, or two or more types may be used. When there are two or more kinds of polymerizable monomers, the total is preferably in the above range.
  • the polymerizable monomer and / or polymerizable oligomer in the present invention is particularly preferably a polymerizable compound having a fluorine atom and / or a silicon atom.
  • the polymerizable compound having a fluorine atom and / or silicon atom is preferably a radical polymerizable monomer and / or polymerizable oligomer in which one or more fluorine atoms or silicon atoms are contained in one molecule, and one molecule of fluorine atoms
  • a polymerizable monomer and / or polymerizable oligomer having a group generally referred to as a perfluoro group contained in two or more thereof is particularly preferable.
  • the radically polymerizable compound having a fluorine atom and / or a silicon atom has a radically polymerizable functional group, and the radically polymerizable functional group is not particularly limited, but an unsaturated group (such as an ethylenically unsaturated bond group). Preferably).
  • the radically polymerizable compound having a fluorine atom and / or a silicon atom preferably has two or more radically polymerizable functional groups, so that the laminated body is subjected to a high-temperature process with respect to the treated member.
  • the peelability of the temporary support can be further improved.
  • the polymerizable monomer and / or polymerizable oligomer having a fluorine atom can be selected from known monomers, and is preferably a crosslinking agent having a polymerizable group as a crosslinkable group.
  • crosslinkable group examples include a silyl group having a hydroxyl group or a hydrolyzable group (eg, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) acryloyl group, allyl group, Vinyloxy groups, etc.), ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, mercapto groups, ⁇ -ketoester groups, Hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like.
  • silyl group having a hydroxyl group or a hydrolyzable group eg, alkoxy
  • the radically polymerizable monomer and / or polymerizable oligomer having a fluorine atom is preferably a compound that can be represented by the following general formula (1).
  • Formula (I): Rf ⁇ -LY ⁇ n (In the formula, Rf represents a chain or cyclic n-valent group containing at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom, and n represents an integer of 2 or more.
  • L represents a single bond or a divalent linking group, and Y represents a polymerizable group.)
  • Y is a polymerizable group, for example, a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), a reactive unsaturated double bond.
  • Y represents a radical polymerizable group, and more preferably a group having a reactive unsaturated double bond.
  • T preferably represents a radical polymerizable functional group represented by the following general formula (9).
  • R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • the dotted line represents a bond to a group linked to L.
  • alkyl group examples are preferably alkyl groups having 1 to 8 carbon atoms.
  • the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
  • L represents a single bond or a divalent linking group.
  • the divalent linking group a divalent aliphatic group, a divalent aromatic group, —O—, —S—, —CO—, —N (R) —, or a combination of two or more thereof can be obtained.
  • R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Rf represents a chain or cyclic n-valent group which contains at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom.
  • Rf may be a linear or branched polymer structure having a repeating unit having a fluorine atom.
  • the radically polymerizable monomer having a fluorine atom may be at least one selected from compounds represented by the following structural formulas (1), (2), (3), (4) and (5). preferable.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents —C p H 2p —, —C (C p H 2p + 1 ) H—, —CH 2 C ( C p H 2p + 1 ) H— or —CH 2 CH 2 O—, where R f is —C n F 2n + 1 , — (CF 2 ) n H, —C n F 2n + 1 —CF 3, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, or, -N (C p H 2p + 1) represents the SO 2 C n F 2n + 1 .
  • p is an integer of 1 ⁇ 10
  • n is an integer of 1 ⁇ 16
  • CF 2 CFOR g.
  • Structural formula (2) (In the structural formula (2), R g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
  • R 3 and R 4 represent a hydrogen atom or a methyl group.
  • R 5 and R 6 represent —C q H 2q —, —C (C q H 2q + 1 ) H— , —CH 2 C (C q H 2q + 1 ) H— or —CH 2 CH 2 O—,
  • R j represents —C t F 2t , q is an integer of 1 to 10, and t is 1 to 16 Is an integer.
  • Examples of the monomer represented by the structural formula (1) include CF 3 (CF 2 ) 5 CH 2 CH 2 OCOCH ⁇ CH 2 , CF 3 CH 2 OCOCH ⁇ CH 2 , CF 3 (CF 2 ) 4.
  • CH 2 CH 2 OCOC (CH 3 ) CH 2, C 7 F 15 CON (C 2 H 5)
  • radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom an oligomer having a repeating unit having a fluorine atom and a repeating unit having a radical polymerizable functional group can also be preferably used.
  • the repeating unit having a fluorine atom is preferably selected from at least one repeating unit represented by the following formulas (6), (7) and (10).
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, and R 1 , R 2 , R 3 , At least one of R 4 is a fluorine atom or a monovalent organic group having a fluorine atom.
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group
  • Y 1 represents a single bond, —CO—, — It represents a divalent linking group selected from the group consisting of O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.
  • R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group
  • Y 2 and Y 3 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • Rf represents a divalent organic group having a fluorine atom.
  • the monovalent organic group having a fluorine atom in formula (6) and formula (7) is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
  • a fluorine-containing alkyl group having 1 to 15 carbon atoms is particularly preferred.
  • This fluorine-containing alkyl group is a straight chain (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.
  • branched structures for example, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like, and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these).
  • An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , — CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
  • the divalent organic group having a fluorine atom in the formula (10) is not particularly limited, but is preferably a fluorine-containing alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Fifteen fluorine-containing alkylene groups are particularly preferred.
  • This fluorine-containing alkylene group is a straight chain (for example, —CF 2 CF 2 —, —CH 2 (CF 2 ) 4 —, —CH 2 (CF 2 ) 8 CF 2 —, —CH 2 CH 2 (CF 2 ) 4 -, Etc.), branched structures (eg, —CH (CF 3 ) CF 2 —, —CH 2 CF (CF 3 ) CF 2 —, —CH (CH 3 ) CF 2 CF 2 —, —CH (CH 3 ) (CF 2 ) 5 CF 2- and the like) and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl, perfluorocyclopentyl, or substituted therewith A linking group having an alkyl group, etc.) or an ether bond (for example, —CH 2 OCH 2 CF 2 CF 2 —, —CH 2 CH 2 OCH 2 C 4 F 8 —,
  • the monovalent organic group in the formulas (6), (7), and (10) is preferably an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms. At least one or more selected from atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms Examples include organic groups composed of elements. More specific examples include organic groups composed of the following structures singly or in combination. The monovalent organic group may further have a substituent.
  • substituents that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group.
  • the organic group may contain an ether bond, an ester bond, or a ureido bond.
  • the monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
  • the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
  • a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-ethylhexyl group, A methylhexyl group, a cyclopentyl group, etc. are mentioned.
  • alkenyl group and an alkenyl group having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group.
  • the alkynyl group is preferably an alkynyl group having 3 to 10 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethylsilylethynyl group.
  • the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.
  • an alkyl group or an aryl group is preferable.
  • the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms.
  • the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
  • the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
  • an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
  • the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
  • the content of the repeating unit having a fluorine atom is preferably 2 mol% to 98 mol%, preferably 10 mol% to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. Is more preferable.
  • repeating unit having a radical polymerizable functional group a repeating unit represented by the following formula (8) is preferable.
  • R 801 to R 803 each independently represents a hydrogen atom, an alkyl group, or a halogen atom.
  • Y 8 represents a single bond, or —CO—, —O—, — NH— represents a divalent linking group selected from the group consisting of a divalent aliphatic group, a divalent aromatic group, and combinations thereof, and T represents a structure having a radical polymerizable functional group.
  • the alkyl group as R 801 to R 803 is preferably an alkyl group having 1 to 6 carbon atoms.
  • T preferably represents a radical polymerizable functional group represented by the general formula (9).
  • R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • the dotted line represents a bond to a group linked to Y 8.
  • alkyl group examples are preferably alkyl groups having 1 to 8 carbon atoms.
  • the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
  • Y 8 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. To express. Specific examples of comprising the combination Y 8 below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the formula (9).
  • the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
  • an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
  • the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
  • the content of the repeating unit having a radical polymerizable functional group is preferably 2 mol% to 98 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom, and is preferably 10 mol% to 90 mol%. It is more preferable that
  • the weight average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a fluorine atom as measured by gel permeation chromatography (GPC) is preferably 2000 to 20000, more preferably 2000 to 15000, and more preferably 2000 to 10,000. Most preferred.
  • the content of the radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom is not particularly limited, preferably The total solid content of the adhesive layer precursor is preferably 0.01% by mass or more and 20% by mass or less. If it is less than 0.01% by mass, the peelability tends to be insufficient. On the other hand, when it exceeds 20 mass%, there exists a tendency for adhesiveness to fall.
  • the radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom may be only one type or two or more types. When there are two or more kinds of polymerizable monomers, the total is preferably in the above range.
  • the radically polymerizable monomer and / or polymerizable oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer.
  • at least one terminal of a polydimethylsiloxane bond is a (meth) acryloyl group or a styryl group.
  • a compound having a (meth) acryloyl group is preferable.
  • the number average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a silicon atom as measured by gel permeation chromatography is preferably 1,000 to 10,000.
  • the number average molecular weight in terms of polystyrene by a gel permeation chromatography method of a radically polymerizable oligomer having a silicon atom is less than 1,000 or 10,000 or more, properties such as releasability due to a silicon atom are hardly expressed.
  • the radically polymerizable monomer having a silicon atom in the present invention it is preferable to use a compound represented by the general formula (11) or (12).
  • R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group.
  • Z 11 , Z 12 , and Z 13 each independently represents a radically polymerizable group,
  • L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group, and
  • n and m each independently represents 0 or more. Represents an integer.
  • R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group.
  • the alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, n-propyl group. Group, isopropyl group and the like.
  • An alkoxy group means —OR 20 , wherein R 20 represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group And a butoxy group.
  • An alkoxycarbonyl group means —C ( ⁇ O) R 21 , where R 21 represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specifically includes methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl.
  • R 21 represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specifically includes methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl.
  • the aryl group include a phenyl group, a tolyl group, and a naphthyl group, which may have a substituent, such as phenylmethyl (benzyl) group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl. Groups and the like.
  • L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group.
  • the divalent linking group represents a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. .
  • N and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, and more preferably an integer of 0 to 50.
  • Z 11 , Z 12 , and Z 13 each independently represent a radical polymerizable group, and a functional group represented by any one of the following general formulas (i) to (iii) is particularly preferable.
  • R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group.
  • X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —, R 104 represents a hydrogen atom or a monovalent organic group.
  • R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group.
  • R 101 preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity.
  • R 102 and R 103 are each independently preferably a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, or optionally substituted alkyl.
  • aryl group which may have a substituent alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent Represents an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, among which a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.
  • X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —
  • R 104 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include an alkyl group which may have a substituent.
  • R 104 is preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.
  • substituents examples include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, A nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.
  • R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group.
  • Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —.
  • R 206 represents a hydrogen atom or a monovalent organic group.
  • R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group.
  • R 201 to R 205 each independently represents a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent.
  • An aryl group that may have, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent It is preferably a good arylamino group, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group, having a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent. It is more preferably an alkyl group which may be substituted or an aryl group which may have a substituent.
  • Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —.
  • R 206 has the same meaning as R 104 in formula (i), and preferred examples thereof are also the same.
  • R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group.
  • Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or a substituent.
  • R 304 has the same meaning as R 104 in formula (i).
  • R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group.
  • R 301 is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group because of high radical reactivity.
  • R 302 and R 303 are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent.
  • An alkyl group that may have a substituent or an aryl group that may have a substituent is more preferable because of high radical reactivity.
  • Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or an optionally substituted phenylene group.
  • R 304 has the same meaning as R 104 in the general formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and An isopropyl group is preferable because of high radical reactivity.
  • the content of the radically polymerizable monomer and / or polymerizable oligomer having a silicon atom is the total solid content of the adhesive precursor. It is preferable that it is 0.01 mass% or more and 20 mass% or less with respect to a minute. If it is less than 0.01% by mass, the peelability tends to decrease. On the other hand, when it exceeds 20 mass%, there exists a tendency for adhesiveness to fall.
  • Examples of the radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom or a silicon atom include RS-75, RS-72-K, RS-76-E manufactured by DIC Corporation, and OPTOOL manufactured by Daikin Industries, Ltd. DAC-HP, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164, X-22-164C, X-22 manufactured by Shin-Etsu Chemical Co., Ltd. -164E, EBECRYL350, EBECRYL1360 manufactured by Daicel-Cytec, Inc., TEGORad2700 manufactured by Degussa, and the like.
  • the adhesive layer precursor of the present invention is a radical polymerization initiator, that is, (b-2) a compound that generates radicals upon irradiation with actinic rays or radiation (photoirradiation) (photoradical initiator (photoradical polymerization initiator)). Or (b-3) a compound that generates radicals by heat (thermal radical initiator (thermal radical polymerization initiator)).
  • the radical polymerizable monomer or oligomer is irradiated with light or heated to cause a curing reaction due to radicals, and the polymerization rate of the adhesive layer precursor can be adjusted, thereby improving adhesion. Can be adjusted.
  • photo radical initiator As a photo radical initiator, what is known as a polymerization initiator described below can be used, for example.
  • the photoradical initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) in a reactive compound having a polymerizable group as the polymerizable monomer.
  • known polymerization initiators It can be selected appropriately. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
  • the polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).
  • halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group
  • Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo Compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like.
  • halogenated hydrocarbon compound having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-258241, compound described in JP-A-5-281728, compound described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.
  • Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) ) -1,3,4-oxadiazole, 2-trichlor
  • photo radical initiators other than the above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, 9-phenylacridine, etc.) Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (eg, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1 -Pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-di
  • ketone compound examples include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenones (eg, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexyl) Amino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzof Non, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone,
  • hydroxyacetophenone compounds As the photoradical initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used.
  • acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • More preferable examples of the photo radical initiator include oxime compounds.
  • Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • oxime ester compounds examples include J.M. C. S. Perkin II (1979) p. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • oxime ester compounds other than those described above compounds described in JP-T-2009-519904 in which oxime is linked to carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in Japanese Patent Application Laid-Open No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used. .
  • cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744.
  • cyclic oxime compounds in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
  • the compounds described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because high sensitivity can be achieved by regenerating the active radical from the polymerization inert radical. it can.
  • an oxime compound having a specific substituent as disclosed in JP 2007-26997A and an oxime compound having a thioaryl group as disclosed in JP 2009-191061 A can be mentioned.
  • a known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer manufactured by Varian) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.
  • photo radical initiators from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, trimethyl compounds, Selected from the group consisting of allylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 3-aryl substituted coumarin compound are preferred.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, ⁇ -aminoketones
  • Most preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, and most preferred are oxime compounds.
  • the content of the photo radical initiator is 0.1% by mass or more and 50% by mass or less based on the total solid content of the adhesive layer precursor. Is preferable, 0.1 mass% or more and 30 mass% or less is more preferable, and 0.1 mass% or more and 20 mass% or less is further more preferable. Only one type of photo radical initiator may be used, or two or more types may be used. When there are two or more types of photo radical initiators, the total is preferably in the above range.
  • Thermal radical initiator As the thermal radical initiator, a known thermal radical generator can be used.
  • the thermal radical initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable monomer.
  • the adhesiveness that is, tackiness and tackiness
  • the adhesive layer precursor may be lowered in advance as will be described in detail later. it can.
  • the adhesive layer precursor in the adhesive support is irradiated with heat after temporary adhesion between the member to be processed and the adhesive support, the reactivity having a crosslinkable group by heat The crosslinking reaction in the compound proceeds.
  • the adhesive layer becomes tougher, and cohesive failure of the adhesive layer precursor, which is likely to occur when mechanically or chemically treating the member to be treated, can be suppressed. That is, the adhesiveness in the adhesive layer precursor can be improved.
  • Preferable thermal radical initiators include compounds that generate radicals upon irradiation with actinic rays or radiation as described above, and compounds having a thermal decomposition point of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C.
  • Thermal radical initiators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens Examples thereof include a compound having a bond and an azo compound. Among these, organic peroxides or azo compounds are more preferable, and organic peroxides are particularly preferable. Specifically, compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be mentioned. In a commercial item, perbutyl Z (made by NOF Corporation) can be used conveniently.
  • the adhesive layer precursor in the present invention contains (b-3) a thermal radical polymerization initiator as a radical polymerization initiator (more preferably, (b-2) a photoradical polymerization initiator and (b-3) )
  • a thermal radical polymerization initiator as a radical polymerization initiator
  • the adhesiveness at high temperatures for example, 100 ° C.
  • the adhesive layer precursor in the present invention preferably contains (b-2) a photoradical polymerization initiator. Moreover, the adhesive layer precursor in the present invention may contain one kind of radical polymerization initiator or two or more kinds.
  • the content of the thermal radical initiator is preferably 0.1% by mass or more and 50% by mass or less based on the total solid content of the adhesive layer precursor, More preferably, it is 0.1 mass% or more and 30 mass% or less, More preferably, it is 0.1 mass% or more and 20 mass% or less. Only one type of thermal radical initiator may be used, or two or more types may be used. When there are two or more thermal radical initiators, the total is preferably in the above range.
  • the adhesive layer precursor of the present invention may have a polymer compound as necessary in order to adjust the coating property.
  • the coating property means the uniformity of the film thickness after coating and the film forming property after coating.
  • any polymer compound can be used.
  • hydrocarbon resin, polystyrene resin for example, acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene copolymer (AS resin), methyl methacrylate / styrene copolymer (MS resin) are included.
  • Novolac resin Novolac resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyimide resin, polyethylene resin, polypropylene, polyvinyl chloride resin, polyvinyl acetate resin, Teflon (registered trademark) ), (Meth) acrylic resin (for example, polymethyl methacrylate), polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, polyethylene terephthalate resin, poly E double sulfide resins, polysulfone resins, polyethersulfone resins, polyarylate resins, polyether ether ketone resin, and synthetic resins such as polyamide-imide resins, and natural resins such as natural rubber.
  • Novolac resin Novolac resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane
  • hydrocarbon resin, ABS resin, AS resin, MS resin, polyurethane resin, novolac resin, and polyimide resin are preferable, hydrocarbon resin and MS resin are more preferable, and acrylic resin, ABS resin, AS resin, and MS resin are more preferable. Further preferred. In this invention, you may use a binder in combination of 2 or more type as needed.
  • any hydrocarbon resin can be used.
  • the hydrocarbon resin in the present invention basically means a resin composed of only carbon atoms and hydrogen atoms, but if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, when a functional group other than a hydrocarbon group is directly bonded to the main chain, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, or a polyvinylpyrrolidone resin, to a hydrocarbon resin consisting of only carbon atoms and hydrogen atoms. It is included in the hydrocarbon resin in the invention, and in this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is 30 mol% or more based on the total repeating unit of the resin. Is preferred.
  • hydrocarbon resins examples include polystyrene resin, terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, and hydrogenated rosin ester.
  • the hydrocarbon resin is preferably a polystyrene resin, a terpene resin, a rosin, a petroleum resin, a hydrogenated rosin, a polymerized rosin, an olefin polymer, or a cycloolefin polymer, and a polystyrene resin, a terpene resin, a rosin, an olefin polymer, Or it is more preferably a cycloolefin polymer, more preferably a polystyrene resin, terpene resin, rosin, olefin polymer, polystyrene resin, or cycloolefin polymer, polystyrene resin, terpene resin, rosin, cycloolefin polymer, Alternatively, an olefin polymer is more preferably a polystyrene resin or a cycloolefin monomer polymer.
  • polystyrene resin examples include polystyrene, styrene / acrylonitrile resin, acrylonitrile / butadiene / styrene resin, and methyl methacrylate / styrene resin.
  • a methyl methacrylate / styrene resin is preferable. Since the heat resistance with respect to the high temperature process of a semiconductor substrate is calculated
  • methyl methacrylate / styrene resin Commercial products of methyl methacrylate / styrene resin include Estyrene MS-200NT, Estyrene MS-300, Estyrene MS-500, Estyrene MS-600 (Nippon Steel & Sumikin Chemical Co., Ltd.), Sebian MAS10, MAS30 (Daicel Polymer Co., Ltd.) Can be particularly preferably used.
  • cycloolefin polymers examples include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers.
  • Preferred examples of the cycloolefin polymer include addition (co) polymers containing at least one repeating unit represented by the following general formula (II), and at least one repeating unit represented by the general formula (I).
  • An addition (co) polymer further comprising a species or more is mentioned.
  • Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).
  • m represents an integer of 0 to 4.
  • R 1 to R 6 each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • X 1 to X 3 and Y 1 to Y 3 are each a hydrogen atom, or a carbon group having 1 to 10 carbon atoms.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), and Z is a carbon atom Represents a hydrogen group or a hydrocarbon group substituted with halogen, W represents SiR 18 p D 3-p (R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, Represents OCOR 18 or —OR 18 , and p represents an integer of 0 to 3. n represents an integer of 0 to 10.
  • Norbornene-based polymers are disclosed in JP-A-10-7732, JP-T 2002-504184, US2004 / 229157A1 or WO2004 / 070463A1.
  • the norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, a norbornene-based polycyclic unsaturated compound and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene can also be subjected to addition polymerization.
  • This norbornene polymer is marketed by Mitsui Chemicals, Inc.
  • Tg glass transition temperatures
  • APL8008T Tg70 ° C
  • APL6013T Tg125 ° C
  • APL6015T Tg145 ° C
  • Pellets such as TOPAS 8007, 5013, 6013, 6015, etc. are available from Polyplastics. Further, Appear 3000 is sold by Ferrania.
  • hydrides of norbornene polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, and JP-A-2003-1159767.
  • it can be produced by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization and then hydrogenation.
  • R 5 and R 6 are preferably hydrogen atoms or methyl groups
  • X 3 and Y 3 are preferably hydrogen atoms, and other groups are appropriately selected.
  • This norbornene polymer is sold under the trade name Arton G or Arton F by JSR Co., Ltd., and Zeonor ZF14, ZF16, Zeonex 250, Nippon Zeon Co., Ltd., These are commercially available under the trade names 280 and 480R, and these can be used.
  • the polystyrene equivalent weight average molecular weight of the polymer compound by gel permeation chromatography (GPC) method is preferably 10,000 to 1,000,000, preferably 50,000 to 500,000, More preferably, it is 100,000 to 300,000.
  • the content of the polymer compound is preferably 5% by mass or more based on the total solid content of the adhesive layer precursor of the present invention. More preferably, it is more preferably 20% by mass or more.
  • the content of the polymer compound is preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass with respect to the total solid content of the adhesive layer precursor of the present invention. More preferably, it is more preferably 40% by mass or less. Only one type of polymer compound may be used, or two or more types may be used. When there are two or more kinds of polymer compounds, the total is preferably within the above range.
  • the content ratio (mass ratio) of the polymerizable monomer and the polymer compound (radical polymerizable monomer / polymer compound) is preferably 100/0 to 10/90, and preferably 100/0 to 20/80. It is more preferable that the ratio is 100/0 to 30/70.
  • the adhesive precursor layer of the present invention preferably contains a polymer compound having a non-polymerizable fluorine atom.
  • a polymer compound having a non-polymerizable fluorine atom a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used.
  • tetrafluoroethylene hexafluoropropene
  • tetrafluoroethylene oxide hexafluoropropene oxide
  • perfluoroalkyl vinyl ether perfluorotrifluoroethylene
  • vinylidene fluoride perfluoroalkyl group-containing (meth) acrylic acid ester
  • examples thereof include at least one fluorine-containing resin selected from a copolymer of one or more functional monomers and chlorotrifluoroethylene.
  • the polymer compound having a non-polymerizable fluorine atom is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic ester.
  • the perfluoroalkyl group-containing (meth) acrylic acid ester is preferably a compound represented by the following formula (101).
  • R 101 , R 102 , and R 103 each independently represent a hydrogen atom, an alkyl group, or a halogen atom.
  • Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • Rf is a fluorine atom or a monovalent organic group having at least one fluorine atom.
  • examples of the alkyl group represented by R 101 , R 102 , R 103 are preferably alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Examples include octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
  • Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 101 to R 103 are preferably a hydrogen atom or a methyl group.
  • Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • the divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Y 101 is preferably an aliphatic group having a divalent linear structure.
  • the monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to Fifteen fluorine-containing alkyl groups are particularly preferred.
  • This fluorine-containing alkyl group is a straight chain ⁇ for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.
  • a branched structure ⁇ eg, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like ⁇ and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these).
  • An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , —CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
  • the perfluoroalkyl group-containing (meth) acrylic resin specifically has a repeating unit represented by the following formula (102).
  • R 101 , R 102 , R 103 , Y 101 , and Rf are each synonymous with General Formula (101), and preferred embodiments are also synonymous.
  • a copolymer component can be selected in addition to the perfluoroalkyl group-containing (meth) acrylic acid ester from the viewpoint of peelability.
  • the radical polymerizable compound capable of forming a copolymer component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, and acrylonitriles. And radical polymerizable compounds selected from methacrylonitriles and the like.
  • acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms), such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic Butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerynuri Tall monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (for example, phenyl Methacrylic acid esters (eg, methyl methacrylate, ethyl
  • (meth) acrylic acid esters having a hydrocarbon group having 1 to 24 carbon atoms are particularly preferred, for example, methyl (meth) acrylate, butyl , 2-ethylhexyl, lauryl, su Allyl, include such glycidyl ester, 2-ethylhexyl, lauryl, higher alcohol (meth) acrylate stearyl, especially acrylate.
  • polymer compounds having non-polymerizable fluorine atoms those commercially available include Teflon (registered trademark) (DuPont), Tefzel (DuPont), Fullon (Asahi Glass), Halar (SolvaySolexis) , Fluororesins such as Hyler (SolvaySolexis), Lumiflon (Asahi Glass), Afras (Asahi Glass), Cefral Soft (Central Glass), Cefral Coat (Central Glass), Vuitton (DuPont), Kalrez (DuPont), Fluoro rubbers with trade names such as SIFEL (Shin-Etsu Chemical Co., Ltd.), various fluorines including perfluoropolyether oils such as Krytox (DuPont Co., Ltd.), Fomblin (Daito Tech Co., Ltd.), and Demnum (Daikin Kogyo Co., Ltd.) Oil, Daifree FB series (
  • the weight average molecular weight in terms of polystyrene by a gel permeation chromatography (GPC) method of the polymer compound having a non-polymerizable fluorine atom is preferably 2000 to 100,000, more preferably 2000 to 50,000, and more preferably 2000 to 10,000. Most preferably it is.
  • the polymer compound having a non-polymerizable fluorine atom is particularly effective when the adhesive layer precursor has a radical polymerizable compound having a fluorine atom. It is most preferable to use a combination of polymer compounds having non-polymerizable fluorine atoms.
  • the ratio (mass ratio) of the radically polymerizable compound having fluorine atoms and the polymer compound having non-polymerizable fluorine atoms in the adhesive layer precursor is preferably 5:95 to 50:50. 10:90 to 40:60 is more preferable, and 15:85 to 30:70 is preferable.
  • the content of the non-polymerizable polymer compound having a fluorine atom is preferably 1 to 99% by mass, preferably 3 to 95% by mass with respect to the total solid content of the adhesive layer precursor, from the viewpoint of good releasability. % Is more preferable, and 5 to 90% by mass is more preferable.
  • the adhesive layer precursor in the present invention preferably contains a chain transfer agent.
  • the chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684.
  • As the chain transfer agent for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals.
  • thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc. are preferably used as the temporary adhesive. be able to.
  • the preferred content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass relative to the total solid content of the adhesive layer precursor. 1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably within the above range.
  • a small amount of a polymerization inhibitor is added to the adhesive layer precursor in the present invention to prevent unnecessary thermal polymerization of the polymer compound and the radical polymerizable monomer during the production or storage of the adhesive layer precursor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and N-nitroso-N-phenylhydroxylamine aluminum salt.
  • the addition amount of the polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the adhesive layer precursor. Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more polymerization inhibitors, the total is preferably in the above range.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the adhesive layer precursor in the present invention, and the adhesive layer precursor in the drying process after coating. It may be unevenly distributed on the surface of the body.
  • the addition amount of the higher fatty acid derivative is preferably about 0.1 to about 10% by mass with respect to the total solid content of the adhesive layer precursor. Only one type of higher fatty acid derivative or the like may be used. When two or more types of higher fatty acid derivatives are used, the total is preferably within the above range.
  • Solvent When the adhesive layer precursor in the present invention is layered by coating, it is preferable to blend a solvent. Any known solvent can be used without limitation as long as an adhesive layer can be formed.
  • organic solvents examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate.
  • Alkyl oxyacetates eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)
  • alkyl 3-oxypropionate Esters eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
  • Oxypropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic Carbonization
  • hydrogens include toluene, xylene, anisole, limonene and the like.
  • solvents are preferably mixed in two or more types from the viewpoint of improving the coated surface.
  • It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
  • the content of the solvent in the adhesive layer precursor forming composition is 5 in terms of the total solid content of the adhesive layer precursor forming composition from the viewpoint of applicability.
  • the amount is preferably ⁇ 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass.
  • One type of solvent may be sufficient and two or more types may be sufficient. When there are two or more solvents, the total is preferably in the above range.
  • surfactant Various surfactants may be added to the adhesive layer precursor in the present invention from the viewpoint of further improving applicability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved. it can. That is, in the case of forming a film using a coating solution containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating solution. The coating property to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, manufactured by BASF) 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Rusupasu 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
  • glycerol trimethylolpropane
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the adhesive layer precursor has a surfactant
  • the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably based on the total solid content of the adhesive layer precursor. Is 0.005% by mass to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
  • the adhesive layer precursor in the present invention is various additives, for example, a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, an oxidation as long as the effects of the present invention are not impaired.
  • An inhibitor, an ultraviolet absorber, an aggregation inhibitor and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the adhesive layer precursor.
  • a composition for forming an adhesive layer precursor (for example, an adhesive layer precursor coating solution) is applied to a conventionally known spin coating method, spray method, roller coating method. Then, it can be formed by drying (baking) using a flow coating method, a doctor coating method, a dipping method or the like. Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
  • the thicknesses of the adhesive layer precursor and the adhesive layer are each preferably 1 to 500 ⁇ m, more preferably 1 to 100 ⁇ m, and even more preferably 1 to 10 ⁇ m.
  • the storage elastic modulus at 25 ° C. of the adhesive layer precursor is preferably 1 M to 10 GPa, more preferably 10 M to 10 GPa, and further preferably 100 M to 10 GPa.
  • the elastic modulus can be measured by, for example, a viscoelasticity measuring device Rheosol-G1000 (manufactured by UBM).
  • the laminate of the present invention has (A) a support (also referred to as a carrier substrate).
  • the material of the support is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and the like. In view of the fact that a widely used electrostatic chuck can be used, a silicon substrate is preferable.
  • the thickness of the support is, for example, in the range of 300 ⁇ m to 5 mm, but is not particularly limited.
  • the laminate of the present invention has (C) a protective layer.
  • the protective layer By providing the protective layer, unevenness when polished can be suppressed.
  • a well-known thing can be used for a protective layer without a restriction
  • a known compound can be used without limitation as long as it is intended to protect the substrate to be treated.
  • Synthetic resins natural resins such as rosin and natural rubber, and hydrocarbon resins can be preferably used.
  • ZEONEX480R made by Nippon Zeon Co., Ltd.
  • the softening point of the protective layer is preferably 170 ° C. or higher and 250 ° C. or lower, and more preferably 200 ° C. or higher and 250 ° C. or lower. More preferred are a polyethersulfone resin, polycarbonate resin, polystyrene resin, hydrocarbon resin, and polyetheretherketone resin having a softening point of 170 ° C. or higher and 250 ° C. or lower, and a softening point of 170 ° C. or higher and 250 ° C. or lower. Most preferred are polyethersulfone resins, polycarbonate resins, polystyrene resins and polyetheretherketone resins.
  • the softening point of the protective layer is preferably lower than the softening point of the adhesive layer precursor and the adhesive layer.
  • the difference between the softening point of the protective layer and the softening point of the adhesive layer precursor is preferably 10 ° C to 200 ° C, more preferably 30 ° C to 200 ° C.
  • the protective layer can contain a compound that can be contained in the adhesive layer precursor as necessary within a range not impairing the effects of the present invention.
  • the protective layer-forming composition (protective layer coating solution) is applied using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. Then, it can be formed by drying (baking). Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
  • the protective layer coating solution preferably contains the resin and solvent.
  • the thickness of the protective layer is preferably 1 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and further preferably 20 to 150 ⁇ m. When having a structure on the surface of the device wafer, the thickness is preferably equal to or greater than the structure.
  • the storage elastic modulus of the protective layer at 25 ° C. is preferably 10 M to 1 GPa, more preferably 100 M to 5 GPa, and even more preferably 1000 M to 3 GPa.
  • the storage elastic modulus of the protective layer is preferably lower than the storage elastic modulus of the adhesive layer precursor, and the value of [storage elastic modulus of protective layer] / [storage elastic modulus of adhesive layer precursor] is 0.9 to 0.01 is preferable, 0.8 to 0.05 is more preferable, and 0.5 to 0.1 is most preferable.
  • the protective layer of the present invention preferably contains a non-polymerizable polymer compound having a fluorine atom.
  • the preferred embodiment of the non-polymerizable polymer compound having a fluorine atom is the same as that described in the non-polymerizable polymer compound having a fluorine atom contained in the above-mentioned adhesive layer precursor, and is preferred. The range is the same.
  • the content of the polymer compound having non-polymerizable fluorine atoms is preferably 0.01 to 99% by mass, preferably 0.03 to 99% by mass with respect to the total solid content of the protective layer, from the viewpoint of good releasability. 50% by mass is more preferable, and 0.05 to 10% by mass is further preferable.
  • the non-polymerizable polymer compound having a fluorine atom is particularly effective in improving the peelability when the adhesive layer precursor has a radical polymerizable compound having a fluorine atom. Most preferably, it is used in combination with a non-polymerizable polymer compound having a fluorine atom.
  • the non-polymerizable polymer compound having a fluorine atom is preferably contained in at least one of the protective layer and the adhesive layer precursor, and may be contained in both layers. From the viewpoint of releasability, it is preferably contained in any one layer of the protective layer or the adhesive layer precursor, and included in the protective layer in order to form an adhesive layer having a softening point of 250 ° C. or higher of the present invention. Most preferably.
  • the ratio (mass ratio) of the radical polymerizable compound having a fluorine atom in the adhesive layer precursor and the polymer compound having a non-polymerizable fluorine atom in the protective layer is 5:95 to 5:95. It is preferably 10:90 to 90:10, more preferably 15:85 to 30:70.
  • the laminate of the present invention has (D) a device wafer.
  • a known device wafer can be used without limitation, and examples thereof include a MEMS and a sensor device.
  • the device wafer preferably has a structure on the surface.
  • the structure is preferably a structure having a height of 1 ⁇ m to 150 ⁇ m, and a metal structure (metal bump) having a height of 1 ⁇ m to 150 ⁇ m. It is preferable to have (also called).
  • the height of the structure is preferably 5 to 100 ⁇ m.
  • the device wafer preferably has a film thickness of 500 ⁇ m or more, preferably 600 ⁇ m or more, and more preferably 700 ⁇ m or more. Although details will be described later, the device wafer is preferably thinned to a thickness of less than 500 ⁇ m by subjecting the surface opposite to the surface in contact with the protective layer to mechanical or chemical treatment. A more preferable film thickness is 400 ⁇ m or less, and a more preferable film thickness is 300 ⁇ m or less.
  • the present invention relates to a protective layer forming composition containing a resin and a solvent, and a kit containing an adhesive layer precursor or an adhesive layer forming composition containing a solvent and a polymerizable monomer. It becomes possible to produce the laminate of the present invention by applying the composition for forming an adhesive layer precursor on a support, forming the adhesive layer precursor, and then applying the composition for forming a protective layer. .
  • the composition for forming a protective layer may be applied on a device and cured.
  • the respective compositions and preferred ranges of the adhesive layer precursor or the adhesive layer forming composition and the protective layer forming composition are the same as those described in the paragraphs of the adhesive layer precursor and the protective layer. .
  • the manufacturing method of the semiconductor manufacturing apparatus includes the step of bonding the first surface of the member to be processed and the substrate through the protective layer and the adhesive layer precursor of the present invention, and the first surface of the member to be processed.
  • the second surface opposite to the first surface is subjected to mechanical or chemical treatment to obtain a treated member, and the adhesive layer precursor or a cured product of the adhesive layer precursor (adhesive) Layer) and the treated member.
  • the method for manufacturing a semiconductor device includes the first surface of the member to be processed after the step of bonding the first surface of the member to be processed and the substrate through the protective layer and the adhesive layer precursor.
  • the adhesive layer precursor is heated at a temperature of 150 ° C. to 300 ° C.
  • the laminate of the present invention is suitable for use in a use environment of 250 ° C. or higher.
  • the laminate of the present invention is characterized by having (B) an adhesive layer, (C) a protective layer, and (D) a device wafer in this order on (A) a support.
  • Such a laminate can be produced by a method of bonding (B) a method of bonding (A) a support having an adhesive layer precursor and (C) a device wafer having a protective layer (D).
  • the adhesive layer precursor is formed by polymerizing the polymerizable monomer and / or polymerizable oligomer in the adhesive layer precursor forming composition by irradiating the adhesive layer precursor forming composition with actinic rays, radiation or heat. By adjusting the rate to 10 to 70%, it is converted into an adhesive layer precursor.
  • the heating temperature is preferably 50 ° C. to 220 ° C., more preferably 100 to 210 ° C., and further preferably 160 to 200 ° C.
  • the polymerization rate of the polymerizable monomer and / or polymerizable oligomer in the adhesive layer precursor is adjusted to 50 to 100% by a further step of irradiating actinic rays, radiation or heat. And by making it an adhesive bond layer, adhesiveness and easy peelability can be improved.
  • the heating temperature is preferably 150 ° C. to 300 ° C., more preferably 170 to 250 ° C., and further preferably 180 to 220 ° C.
  • the production method of the layered product of the present invention and the manufacturing method of a semiconductor device are not limited to the following.
  • FIG. 1A, FIG. 1B, FIG. 1C, FIG. 1D, FIG. 1E, and FIG. 1F are schematic cross-sectional views illustrating temporary bonding between an adhesive support and a device wafer, respectively, and a device wafer temporarily bonded to the adhesive support
  • an adhesive support precursor 100 in which an adhesive layer precursor 11 is provided on a support 12 is prepared.
  • the adhesive support precursor 100 includes a polymerizable monomer and / or a polymerizable oligomer.
  • the adhesive layer precursor forming composition 11 is prepared by adjusting the polymerization rate of the polymerizable monomer to 10 to 70% by the step of irradiating actinic rays, radiation or heat. It becomes the layer precursor 13. Moreover, it is preferable that the storage elastic modulus in 25 degreeC of an adhesive bond layer precursor is 10 MPA or more and less than 1 GPa. By adjusting within this range, it is possible to achieve both strong adhesion at the time of thinning the device wafer described later and easy peelability at the time of separation of the Debye wafer.
  • the monomer polymerization rate can be controlled by adjusting the content of the photoinitiator and thermal initiator, and the amount of actinic light, radiation, or heat energy.
  • FT-IR Fourier transform infrared spectroscopy
  • the peak area before irradiation with actinic rays, radiation, or heat can be calculated as 0%, and the state in which the peak completely disappears can be calculated as 100%.
  • the Fourier transform infrared spectrometer for example, EXCALIBUR FTS-3000 manufactured by DIGILAB can be used.
  • the protective layer mentioned later on the support body 12 can form by applying (preferably apply
  • the device wafer 60 (member to be processed) has a plurality of structures (device chips) 62 provided on the surface 61 a of the silicon substrate 61.
  • the thickness of the silicon substrate 61 is in the range of 200 to 1200 ⁇ m, for example.
  • the device chip 62 is preferably a metal structure, for example, and the height is in the range of 10 to 100 ⁇ m.
  • the protective layer 71 When the protective layer 71 is provided on the surface 61a, it can be formed by applying (preferably coating) the surface of the protective layer and then drying (baking). Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
  • the protective layer 71 preferably completely covers the device chip 62.
  • the protective layer 71 is preferably represented by the formula X + 100 ⁇ Y> X.
  • the protective layer 71 completely covers the device chip 62 in this way is that a thin device wafer TTV (Total Thickness) obtained by thinning the device wafer 60 temporarily bonded by the adhesive support 100 ′.
  • TTV Total Thickness
  • This is effective when it is desired to further reduce the variation (that is, when it is desired to further improve the flatness of the thin device wafer). That is, when the device wafer 60 temporarily bonded by the adhesive support 100 is thinned, the uneven shape of the device wafer 60 formed by the plurality of device chips 62 is transferred to the back surface 61b ′ of the thin device wafer 60 ′. Tend to become a factor that increases TTV.
  • the protective layer 71 is provided on the surface 61a, the protective layer 71 is pressed against the adhesive layer precursor 13 of the adhesive support 100 ′. As a result, the protective layer 71 and the adhesive layer precursor 13 are bonded, and the adhesive support 100 ′ and the device wafer 60 are temporarily bonded. Thereafter, if necessary, the adhesive body between the adhesive support 100 ′ and the device wafer 60 is heated (irradiated with heat) so that the adhesive layer precursor has a stronger adhesive layer. Also good.
  • the anchor effect at the interface between the adhesive support and the member to be processed is promoted, and cohesive failure of the adhesive layer that is likely to occur when the device wafer 60 is subjected to mechanical or chemical processing described later is performed. Since it can suppress, it will raise the adhesiveness of adhesive support body 100 ', and also the ease of peeling at the time of isolation
  • separation of a Debye wafer can also be improved by improving the elasticity modulus of an adhesive layer.
  • the heating temperature is preferably 150 ° C. to 300 ° C., more preferably 170 ° C. to 250 ° C., and further preferably 180 ° C. to 220 ° C.
  • the heating time is preferably 20 seconds to 10 minutes, more preferably 30 seconds to 5 minutes, and further preferably 40 seconds to 3 minutes.
  • the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment, specifically, thinning treatment such as gliding or chemical mechanical polishing (CMP).
  • the thickness of the silicon substrate 61 is reduced (for example, a thickness of 1 to 200 ⁇ m) to obtain a thin device wafer 60 ′.
  • a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b ′ of the thin device wafer 60 ′ after the thinning process, and the silicon is penetrated into the through hole. You may perform the process which forms an electrode (not shown) as needed.
  • the surface 61a of the thin device wafer 60 ′ is detached from the adhesive layer of the adhesive support 100 ′.
  • the method of detachment is not particularly limited, but it is preferable that the separation is performed by pulling up from the end of the thin device wafer 60 ′ in the direction perpendicular to the device wafer without any treatment.
  • the stripping solution water and a solvent (organic solvent) can be used.
  • the organic solvent which melt
  • the organic solvent include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons. (Methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents.
  • Polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol,
  • the stripping solution may contain an alkali, an acid, and a surfactant.
  • the blending amount is preferably 0.1 to 5.0% by mass of the stripping solution.
  • a form in which two or more organic solvents and water, two or more alkalis, an acid, and a surfactant are mixed is also preferable.
  • alkali examples include tribasic sodium phosphate, tribasic potassium phosphate, tribasic ammonium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, and ammonium carbonate.
  • Inorganic alkali agents such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, monomethylamine, Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanol Min, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, may be used an organic alkali agent such as tetramethylammonium hydroxide. These alkali agents can be used alone or in combination of two or more.
  • Acids include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid, boric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid
  • Organic acids such as formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid can be used.
  • the surfactant an anionic, cationic, nonionic or zwitterionic surfactant can be used.
  • the content of the surfactant is preferably 1 to 20% by mass and more preferably 1 to 10% by mass with respect to the total amount of the alkaline aqueous solution.
  • anionic surfactant examples include, but are not limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid salts, Alkylnaphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid Monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef oil, sulfate esters of fatty acid alkyl
  • the cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkyl imidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
  • the nonionic surfactant is not particularly limited, but is a polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid.
  • Ethylene oxide adduct polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block Copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer , Fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines.
  • those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol ethylene oxide adduct is more preferable.
  • Zwitterionic surfactants include, but are not limited to, amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaines, and amino acids such as sodium alkylamino fatty acids.
  • alkyldimethylamine oxide which may have a substituent alkylcarboxybetaine which may have a substituent
  • alkylsulfobetaine which may have a substituent
  • the compound represented by the formula (2) in paragraph [0256] of JP-A-2008-203359, the formula (I) and the formula (II) in paragraph [0028] of JP-A-2008-276166 are disclosed.
  • a compound represented by the formula (VI), and compounds represented by paragraph numbers [0022] to [0029] of JP-A-2009-47927 can be used.
  • additives such as an antifoaming agent and a water softening agent can be contained as required.
  • a thin device wafer can be obtained by removing the protective layer 71 on the device wafer surface 61a.
  • the method for removing the protective layer 71 include a method for removing the protective layer 71 in a film state, a method for dissolving and removing it by dissolving in an aqueous solution or an organic solvent, and a method for decomposing and vaporizing by irradiation with actinic rays, radiation, or heat.
  • a method of dissolving and removing by dissolving in an organic solvent can be preferably used.
  • the aqueous solution or the organic solvent any solution that can dissolve and remove the protective layer can be used.
  • the above-described stripping solution that can dissolve and remove the protective layer can be preferably used. Is the same.
  • the thin device wafer 60 ′ is detached from the adhesive support 100 ′, various known processes are performed on the thin device wafer 60 ′ as necessary to obtain a semiconductor device having the thin device wafer 60 ′. To manufacture.
  • the support can be regenerated by removing the adhesive layer on the support.
  • a method for removing the adhesive layer as it is in the form of a film, it is physically removed by spraying with a brush, ultrasonic waves, ice particles, aerosol, a method of dissolving and removing by dissolving in an aqueous solution or an organic solvent, activity
  • a chemical removal method such as a method of decomposing and vaporizing by irradiation with light, radiation, or heat can be mentioned, and conventionally known cleaning methods can be used depending on the support.
  • a silicon substrate is used, a conventionally known silicon wafer cleaning method can be used.
  • acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, organic acids, bases such as tetramethylammonium, ammonia, organic bases, oxidizing agents such as hydrogen peroxide, or Examples thereof include a mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide solution, a mixture of sulfuric acid and hydrogen peroxide solution, a mixture of hydrofluoric acid and hydrogen peroxide solution, and a mixture of hydrofluoric acid and ammonium fluoride.
  • the substrate cleaning liquid preferably contains an acid having a pKa of less than 0 and hydrogen peroxide.
  • the acid having a pKa of less than 0 is selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid and sulfuric acid, or organic acids such as alkylsulfonic acid and arylsulfonic acid.
  • inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid and sulfuric acid, or organic acids such as alkylsulfonic acid and arylsulfonic acid.
  • an inorganic acid is preferable, and sulfuric acid is most preferable.
  • the hydrogen peroxide As the hydrogen peroxide, 30 w / v% hydrogen peroxide water can be preferably used, and the mixing ratio of the strong acid and 30 w / v% hydrogen peroxide water is preferably 0.1: 1 to 100: 1, and 1: 1. ⁇ 10: 1 is more preferred, and 3: 1 to 5: 1 is most preferred.
  • FIG. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the conventional adhesive support and the device wafer.
  • an adhesive support in which an adhesive layer 11 ′ formed of a conventional temporary adhesive is provided on the support 12 as an adhesive support.
  • the adhesive support 100 ′ and the device wafer are temporarily bonded in the same manner as described with reference to FIGS. 1A and 1B, and the silicon substrate is thinned on the device wafer.
  • the thin device wafer 60 ′ is peeled from the adhesive support 100 ′.
  • the conventional temporary adhesive it is difficult to easily release the temporary support for the processed member without temporarily damaging the processed member with high adhesive force and damaging the processed member.
  • a conventional temporary adhesive having high adhesiveness if a conventional temporary adhesive having high adhesiveness is adopted, the temporary bonding between the device wafer and the support tends to be too strong. Become. Therefore, in order to release this excessively strong temporary adhesion, for example, as shown in FIG. 2, a tape (for example, dicing tape) is attached to the back surface 61b ′ of the thin device wafer 60 ′, and the adhesive support 100 ′ is thin.
  • the device chip 62 When the device wafer 60 ′ is peeled off, the device chip 62 is easily detached from the device chip 62 provided with the structure (bump) 63, and the device chip 62 is easily damaged.
  • a conventional temporary adhesive having low adhesiveness when adopted, temporary support to the processed member can be easily released, but the temporary adhesion between the device wafer and the carrier substrate is too weak in the first place. A problem that the wafer cannot be reliably supported by the carrier substrate is likely to occur.
  • the adhesive layer formed by the adhesive layer precursor of the present invention exhibits sufficient adhesiveness and can easily release the temporary adhesion between the device wafer 60 and the adhesive support 100 ′. That is, according to the laminate of the present invention, the device wafer 60 can be temporarily supported with high adhesive force, and the temporary support for the thin device wafer 60 ′ can be easily released without damaging the thin device wafer 60 ′.
  • the method for forming a laminated body and the method for manufacturing a semiconductor device of the present invention are not limited to the above-described embodiments, and appropriate modifications and improvements can be made.
  • the adhesive layer formed from the adhesive layer precursor in the present invention constitutes an adhesive support by being provided on the support before temporary bonding of the device wafer.
  • a member to be processed such as a device wafer, may be temporarily bonded to a member to be processed, which is then provided with an adhesive layer.
  • the adhesive layer precursor and the adhesive layer have a single layer structure, but the adhesive layer precursor and the adhesive layer may have a multilayer structure.
  • a method for forming an adhesive layer having a multilayer structure before irradiating actinic light, radiation or heat, a method of applying a temporary adhesive in a stepwise manner by the above-mentioned conventionally known method, or actinic light, radiation or heat is used. And a method of applying a temporary adhesive by a conventionally known method described above.
  • the silicon substrate is exemplified as the member to be processed supported by the adhesive support.
  • the present invention is not limited to this, and in the semiconductor device manufacturing method, mechanical or chemical Any member to be processed that can be subjected to various processing may be used.
  • the member to be processed can include a compound semiconductor substrate.
  • the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate. Can be mentioned.
  • the silicon substrate thinning process and the silicon through electrode forming process are exemplified as the mechanical or chemical process for the silicon substrate supported by the adhesive support.
  • the present invention is not limited to these, and any processing necessary in the method for manufacturing a semiconductor device can be used.
  • the shape, dimensions, number, arrangement location, and the like of the device chip on the device wafer are arbitrary as long as the present invention can be achieved and are not limited.
  • EXCALIBUR FTS-3000 Fourier transform infrared spectrometer
  • ⁇ Adhesive layer precursor forming composition Polymerizable monomer or oligomer (b-1) parts by mass listed in the table below Polymerizable monomer or oligomer (b-1 ′) parts by mass listed in the table below Photoradical polymerization initiator (b-2) Table below Parts by mass / thermal radical polymerization initiator (b-3) described in Table 4 parts by mass / polymer compound (b-4) described in the following table parts by mass / polymerization inhibitor (p-methoxyphenol, Tokyo) (Made by Kasei Co., Ltd.) 0.008 parts by mass / surfactant (PF6320, manufactured by OMNOVA) 0.032 parts by mass / solvent (propylene glycol monopropyl ether acetate) 94.96 parts by mass
  • B-4-1 Estyrene MS600 (methyl methacrylate / styrene copolymer resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
  • B-4-2) Polymethyl methacrylate (manufactured by Aldrich, Mw: 12 million)
  • a protective layer forming composition described in the following table was applied to a 200 mm Si wafer with a Cu bump having a height of 10 ⁇ m using a spin coater, and then once or twice under the conditions described in the following table. Baking was performed separately to form a wafer provided with a protective layer having a thickness of 20 ⁇ m.
  • composition of composition for forming protective layer Resin component parts by mass listed in the following table / solvent parts by mass listed in the following table
  • a laminate having an adhesive layer precursor, a protective layer, and a member to be processed was obtained. Furthermore, heating was performed at 200 ° C. for 3 minutes under normal pressure, and the adhesive layer precursor was used as an adhesive layer to obtain an adhesive test piece.
  • ⁇ TTV Total Thickness Variation>
  • a grinder DFG8560 manufactured by DISCO Corporation
  • the bonded wafer was thinned on the back side with respect to the bonded surface of the processed member, and the film thickness of the processed member was reduced to 100 ⁇ m.
  • the layer thickness of the to-be-processed member was measured using the semiconductor substrate surface test
  • inspection apparatus SemDex300
  • the difference of the minimum value and the maximum value of thickness was calculated
  • B Difference between minimum and maximum values exceeds 5 ⁇ m
  • an adhesive layer precursor, (C) a protective layer, and (D) a device wafer are provided in this order on (A) a support, and (B) the adhesive layer precursor is (B-1)
  • Examples containing a polymerizable monomer or oligomer and having a polymerization rate of 10 to 70% not only give good results with respect to adhesiveness and peelability, but also have excellent TTV and detergency. I understood.
  • the comparative example 1 whose polymerization rate of a polymerizable monomer is less than 10% is inferior to an Example in peelability.
  • the comparative example 2 in which the polymerization rate of a polymerizable monomer exceeds 70% is inferior to an Example in adhesive force.
  • Comparative Examples 3 to 4 which did not have any one of the adhesive layer precursor and the protective layer were inferior in adhesive strength and TTV to the examples. Further, it was found that the peelability was further improved when the adhesive layer precursor had a radical polymerizable monomer having three or more functional groups and / or a radical polymerizable monomer having a fluorine atom (Examples 8, 10 to 12, 14-30, 33). Furthermore, it can be seen that when the radically polymerizable compound having a fluorine atom is contained in the adhesive layer precursor and the nonpolymerizable compound having a fluorine atom is further contained in the adhesive layer precursor or the protective layer, the releasability is further improved. It was. (Examples 35, 36, 39 to 48))
  • Adhesive Layer Precursor Composition 12 Support (Carrier Substrate) 13 Adhesive layer precursor 60 Device wafer 60 'Thin device wafer 61' Silicon substrate 61a Silicon substrate surface 61b Silicon substrate back surface 61b 'Thin device wafer back surface 62 Device chip 63 Bump 71 Protective layer 100, 100' Adhesive support body

Abstract

Provided is a laminate that, when a member-to-be-treated is mechanically or chemically treated, can temporarily support the member-to-be-treated by means of high adhesive force and can easily release the temporary support of the member-to-be-treated without doing damage to the member-to-be-treated. Also provided are a composition for formation of a protective layer, an adhesive layer precursor or a composition for formation of an adhesive layer, and a kit for the laminate. A laminate that has, in order upon a support body (A), an adhesive layer precursor (B), a protective layer (C), and a device wafer (D). The adhesive layer precursor (B) contains a polymerizable monomer and/or a polymerizable oligomer (b-1), and the polymerization rate of the polymerizable monomer and/or the polymerizable oligomer is 10%-70%.

Description

積層体およびその応用Laminate and its application
　本発明は、積層体、保護層形成用組成物、接着剤層前駆体または接着剤層形成用組成物、およびそのキットに関する。より詳細には、半導体装置製造用仮接着剤を用いた接着性支持体に仮接合した積層体、それに用いる保護層形成用組成物、接着剤層前駆体または接着剤層形成用組成物、および前記保護層形成用組成物と接着剤層前駆体または接着剤層形成用組成物を含むキットに関する。 The present invention relates to a laminate, a protective layer forming composition, an adhesive layer precursor or an adhesive layer forming composition, and a kit thereof. More specifically, a laminate temporarily bonded to an adhesive support using a temporary adhesive for manufacturing a semiconductor device, a protective layer forming composition used therefor, an adhesive layer precursor or an adhesive layer forming composition, and The present invention relates to a kit comprising the protective layer forming composition and an adhesive layer precursor or an adhesive layer forming composition.
　従来、ＩＣ（集積回路）やＬＳＩ（大規模集積回路）などの半導体デバイスの製造プロセスにおいては、通常、半導体シリコンウエハ上に多数のＩＣチップが形成され、ダイシングにより個片化される。
　電子機器の更なる小型化および高性能化のニーズに伴い、電子機器に搭載されるＩＣチップについても更なる小型化および高集積化が求められているが、シリコン基板の面方向における集積回路の高集積化は限界に近づいている。 Conventionally, in a manufacturing process of a semiconductor device such as an IC (integrated circuit) or an LSI (large scale integrated circuit), a large number of IC chips are usually formed on a semiconductor silicon wafer and separated into pieces by dicing.
With the need for further miniaturization and higher performance of electronic equipment, further miniaturization and higher integration are required for IC chips mounted on electronic equipment. High integration is approaching its limit.
　ＩＣチップ内の集積回路から、ＩＣチップの外部端子への電気的な接続方法としては、従来より、ワイヤーボンディング法が広く知られているが、ＩＣチップの小型化を図るべく、近年、シリコン基板に貫通孔を設け、外部端子としての金属プラグを貫通孔内を貫通するように集積回路に接続する方法（いわゆる、シリコン貫通電極（ＴＳＶ）を形成する方法）が知られている。しかしながら、シリコン貫通電極を形成する方法のみでは、上記した近年のＩＣチップに対する更なる高集積化のニーズに充分応えられるものではない。 As an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known. However, in recent years, in order to reduce the size of the IC chip, a silicon substrate is used. A method is known in which a through-hole is provided in the semiconductor device and a metal plug as an external terminal is connected to an integrated circuit so as to pass through the through-hole (so-called silicon through electrode (TSV) forming method). However, only the method of forming the through silicon vias cannot sufficiently meet the above-described needs for higher integration of the recent IC chip.
　以上を鑑み、ＩＣチップ内の集積回路を多層化することにより、シリコン基板の単位面積当たりの集積度を向上させる技術が知られている。しかしながら、集積回路の多層化は、ＩＣチップの厚みを増大させるため、ＩＣチップを構成する部材の薄型化が必要である。このような部材の薄型化としては、例えば、シリコン基板の薄型化が検討されており、ＩＣチップの小型化につながるのみならず、シリコン貫通電極の製造におけるシリコン基板の貫通孔製造工程を省力化できることから、有望視されている。 In view of the above, a technique for improving the degree of integration per unit area of a silicon substrate by multilayering integrated circuits in an IC chip is known. However, since the multilayered integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the members constituting the IC chip. For example, the thinning of the silicon substrate is being considered as the thinning of such a member, which not only leads to the miniaturization of the IC chip, but also saves labor in the through hole manufacturing process of the silicon substrate in the manufacture of the silicon through electrode. Because it is possible, it is considered promising.
　半導体デバイスの製造プロセスに用いられる、半導体シリコンウエハとしては、約７００～９００μｍの厚さを有するものが広く知られているが、近年、ＩＣチップの小型化等を目的に、半導体シリコンウエハの厚さを２００μｍ以下となるまで薄くすることが試みられている。
　しかしながら、厚さ２００μｍ以下の半導体シリコンウエハは非常に薄く、ひいては、これを基材とする半導体デバイス製造用部材も非常に薄いため、このような部材に対して更なる処理を施したり、あるいは、このような部材を単に移動したりする場合等において、部材を安定的に、かつ、損傷を与えることなく支持することは困難である。 A semiconductor silicon wafer having a thickness of about 700 to 900 μm is widely known as a semiconductor silicon wafer used in a semiconductor device manufacturing process. However, in recent years, the thickness of a semiconductor silicon wafer has been reduced for the purpose of miniaturizing an IC chip. Attempts have been made to reduce the thickness to 200 μm or less.
However, since the semiconductor silicon wafer having a thickness of 200 μm or less is very thin, and the semiconductor device manufacturing member based on this is also very thin, such a member can be further processed, or When such a member is simply moved, it is difficult to support the member stably and without causing damage.
　上記のような問題を解決すべく、表面にデバイスが設けられた薄型化前の半導体ウエハと加工用支持基板とをシリコーン粘着剤により仮接着し、半導体ウエハの裏面を研削して薄型化した後に、半導体ウエハを穿孔してシリコン貫通電極を設け、その後、半導体ウエハから加工用支持基板を脱離させる技術が知られている（特許文献１参照）。この技術によれば、半導体ウエハの裏面研削時の耐研削抵抗、異方性ドライエッチング工程などにおける耐熱性、メッキやエッチング時の耐薬品性、最終的な加工用支持基板とのスムースな剥離と低披着体汚染性を同時に達成することが可能であるとされている。 To solve the above problems, after pre-thinning the semiconductor wafer before thinning with the device provided on the surface and the processing support substrate with a silicone adhesive, grinding the back of the semiconductor wafer to make it thin A technique is known in which a semiconductor wafer is drilled to provide a silicon through electrode, and then a processing support substrate is detached from the semiconductor wafer (see Patent Document 1). According to this technology, resistance to grinding during back grinding of semiconductor wafers, heat resistance in anisotropic dry etching processes, chemical resistance during plating and etching, smooth separation from the final support substrate for processing, It is said that it is possible to simultaneously achieve low plastid contamination.
　また、ウエハの支持方法としては、ウエハを支持層システムにより支持する方法であって、ウエハと支持層システムとの間に、プラズマ堆積法により得られるプラズマポリマー層を分離層として介装させて、支持層システムと分離層との間の接着結合を、ウエハと分離層との間の接合結合より大きくなるようにし、ウエハを支持層システムから脱離する際に、ウエハが分離層から容易に脱離するように構成した技術も知られている（特許文献２参照）。 Further, as a method for supporting the wafer, the wafer is supported by a support layer system, and a plasma polymer layer obtained by a plasma deposition method is interposed as a separation layer between the wafer and the support layer system. The adhesive bond between the support layer system and the separation layer is made larger than the bond bond between the wafer and the separation layer, so that when the wafer is detached from the support layer system, the wafer is easily detached from the separation layer. A technique configured to be separated is also known (see Patent Document 2).
　また、ポリエーテルスルホンと粘性付与剤を使用して、仮接着を行い、加熱により仮接着を解除する技術が知られている（特許文献３参照）。
　また、カルボン酸類とアミン類からなる混合物により、仮接着を行い、加熱により仮接着を解除する技術も知られている（特許文献４参照）。
　また、セルロースポリマー類等からなる接合層を加温した状態で、デバイスウエハと支持基板を圧着することで接着させて、加温して横方向にスライドすることによりデバイスウエハを支持基板から脱離する技術が知られている（特許文献５参照）。 Moreover, the technique which performs temporary adhesion | attachment using a polyether sulfone and a viscosity imparting agent, and cancels | releases temporary adhesion by heating is known (refer patent document 3).
There is also known a technique in which temporary adhesion is performed with a mixture of carboxylic acids and amines and the temporary adhesion is released by heating (see Patent Document 4).
In addition, the device wafer and the support substrate are bonded together by pressure bonding with the bonding layer made of cellulose polymers heated, and the device wafer is detached from the support substrate by heating and sliding in the lateral direction. The technique which performs is known (refer patent document 5).
　また、シンジオタクチック１，２－ポリブタジエンと光重合開始剤からなり、放射線の照射により接着力が変化する粘着フィルムが知られている（特許文献６参照）。
　さらに、ポリカーボネート類からなる接着剤により、支持基板と半導体ウエハとを仮接着し、半導体ウエハに対して処理を行った後、照射線を照射し、次いで、加熱することにより、処理済の半導体ウエハを支持基板から脱離する技術が知られている（特許文献７参照）。 Further, a pressure-sensitive adhesive film made of syndiotactic 1,2-polybutadiene and a photopolymerization initiator and having an adhesive force that changes by irradiation with radiation is known (see Patent Document 6).
Further, the support substrate and the semiconductor wafer are temporarily bonded with an adhesive made of polycarbonate, the semiconductor wafer is processed, irradiated with irradiation radiation, and then heated, thereby processing the processed semiconductor wafer. A technique for detaching the substrate from the support substrate is known (see Patent Document 7).
　また、軟化点の異なる２層で、支持基板と半導体ウエハを仮接着し、半導体ウエハに対して処理を行った後、加温して横方向にスライドすることで支持基板と半導体ウエハを脱離する技術が知られている。（特許文献８参照）。 In addition, the support substrate and the semiconductor wafer are temporarily bonded with two layers having different softening points, and after processing the semiconductor wafer, the support substrate and the semiconductor wafer are detached by heating and sliding laterally. The technology to do is known. (See Patent Document 8).
特開２０１１－１１９４２７号公報JP 2011-119427 A 特表２００９－５２８６８８号公報Special table 2009-528688 特開２０１１－２２５８１４号公報JP 2011-225814 A 特開２０１１－０５２１４２号公報Japanese Unexamined Patent Publication No. 2011-052142 特表２０１０－５０６４０６号公報Special table 2010-506406 gazette 特開２００７－０４５９３９号公報JP 2007-045939 A 米国特許公開２０１１／０３１８９３８号明細書US Patent Publication No. 2011/0318938 米国特許公報２０１２／００３４４３７号明細書US Patent Publication 2012/0034437
　ところで、デバイスが設けられた半導体ウエハの表面（すなわち、デバイスウエハのデバイス面）と支持基板（キャリア基板）とを、特許文献１等で知られている粘着剤からなる層を介して仮接着する場合には、半導体ウエハを安定的に支持するべく、粘着剤層には一定の強さの粘着度が要求される。
　そのため、半導体ウエハのデバイス面の全面と支持体とを粘着剤層を介して仮接着する場合においては、半導体ウエハと支持体との仮接着を充分なものとし、半導体ウエハを安定的に、かつ、損傷を与えることなく支持しようとする程、反面、半導体ウエハと支持体との仮接着が強すぎることにより、支持体から半導体ウエハを脱離する際に、デバイスが破損したり、半導体ウエハからデバイスが脱離してしまうという不具合が生じやすい。 By the way, the surface of the semiconductor wafer on which the device is provided (that is, the device surface of the device wafer) and the support substrate (carrier substrate) are temporarily bonded via a layer made of an adhesive known in Patent Document 1 or the like. In some cases, the adhesive layer is required to have a certain degree of adhesion to stably support the semiconductor wafer.
Therefore, in the case of temporarily bonding the entire device surface of the semiconductor wafer and the support through the adhesive layer, the temporary bonding between the semiconductor wafer and the support is sufficient, and the semiconductor wafer is stably and However, the temporary adhesion between the semiconductor wafer and the support is too strong, so that the device may be damaged or detached from the semiconductor wafer. There is a tendency for the device to be detached.
　また、特許文献２のように、ウエハと支持層システムとの接着が強くなりすぎることを抑制すべく、ウエハと支持層システムとの間に、分離層としてのプラズマポリマー層を、プラズマ堆積法により形成する方法は、（１）通常、プラズマ堆積法を実施するための設備コストは大きい；（２）プラズマ堆積法による層形成は、プラズマ装置内の真空化やモノマーの堆積に時間を要する；および（３）プラズマポリマー層からなる分離層を設けても、加工に供されるウエハを支持する場合においては、ウエハと分離層との接着結合を充分なものとしながら、反面、ウエハの支持を解除する場合においては、ウエハが容易に分離層から脱離するような接着結合にコントロールすることは容易ではない；等の問題がある。 Further, as in Patent Document 2, in order to suppress the adhesion between the wafer and the support layer system from becoming too strong, a plasma polymer layer as a separation layer is formed between the wafer and the support layer system by a plasma deposition method. The forming method is (1) the equipment cost for carrying out the plasma deposition method is usually high; (2) the layer formation by the plasma deposition method requires time for vacuuming and monomer deposition in the plasma apparatus; and (3) Even when a separation layer composed of a plasma polymer layer is provided, when supporting a wafer to be processed, the wafer is released from support while the adhesive bond between the wafer and the separation layer is sufficient. In such a case, it is not easy to control the adhesive bond so that the wafer is easily detached from the separation layer;
　また、特許文献３、４、５、８記載のように、加熱により仮接着を解除する方法では、半導体ウエハを脱離する際にデバイスが破損する不具合が生じやすい。 Further, as described in Patent Documents 3, 4, 5, and 8, the method of releasing temporary adhesion by heating tends to cause a problem that the device is damaged when the semiconductor wafer is detached.
　また、特許文献６、７のように、照射線を照射して仮接着を解除する方法では、照射線を透過する支持体を使用する必要がある。 Also, as disclosed in Patent Documents 6 and 7, in the method of releasing the temporary adhesion by irradiating the irradiation line, it is necessary to use a support that transmits the irradiation line.
　さらに、特許文献８のように、半導体ウエハ側の接合層の軟化点が基板側の接合層の軟化点よりも２０℃以上大きい場合は、剥離後に基板側の接合層が半導体ウエハ側の接合層に転写し、半導体ウエハの洗浄性が低下する問題が発生する。 Further, as in Patent Document 8, when the softening point of the bonding layer on the semiconductor wafer side is 20 ° C. or higher than the softening point of the bonding layer on the substrate side, the bonding layer on the substrate side after peeling is the bonding layer on the semiconductor wafer side This causes a problem that the cleaning performance of the semiconductor wafer is lowered.
　本発明は、上記背景を鑑みてなされたものであり、その目的は、披処理部材（半導体ウエハなど）に機械的または化学的な処理を施す際に、高い接着力により披処理部材を仮支持でき、さらには真空、高温でのプロセスを経た後においても、処理済部材に損傷を与えることなく、処理済部材に対する仮支持を容易に（高い剥離性で以って）解除できる、積層体、保護層形成用組成物、接着剤層前駆体または接着剤層形成用組成物、およびそのキットを提供することにある。 The present invention has been made in view of the above background, and its purpose is to temporarily support a processing member with a high adhesive force when mechanically or chemically processing the processing member (such as a semiconductor wafer). A laminate that can be easily released (with high peelability) from the temporary support to the treated member without damaging the treated member even after undergoing a vacuum and high temperature process, The object is to provide a protective layer forming composition, an adhesive layer precursor or an adhesive layer forming composition, and a kit thereof.
　本発明者らは、上記課題を解決すべく鋭意検討した結果、（Ａ）支持体上に、（Ｂ）接着剤層前駆体、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有し、前記（Ｂ）（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含み、かつ、重合性モノマーおよび／または重合性オリゴマーの重合率が１０～７０％である積層体を使用したところ、高い接着力によりデバイスウエハと支持体を仮支持できるとともに、デバイスウエハの仮支持を容易に解除できることを見出し、本発明を完成するに至った。
　いかなる理論にも拘泥されるものではないが、本発明の積層体では、重合性モノマーおよび／または重合性オリゴマーの重合体によって、保護層と接着剤前駆体（重合性モノマーおよび／または重合性オリゴマーの重合体と重合性モノマーおよび／または重合性オリゴマーの混合物）界面で適度なアンカー効果が働くこと、および接着後さらに重合を進行させることで接着剤層の弾性率を高く設定できるため、ウエハ薄化時の接着性と薄化後の剥離性を両立できている。
　以上の見解に基づき、接着性が高く剥離容易な接着性層を形成できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the present inventors have (B) an adhesive layer precursor, (C) a protective layer, and (D) a device wafer in this order on a support. When the laminate (B) (b-1) containing a polymerizable monomer and / or polymerizable oligomer and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70% is used, The present inventors have found that the device wafer and the support can be temporarily supported by a high adhesive force, and the temporary support of the device wafer can be easily released, and the present invention has been completed.
Without being bound by any theory, in the laminate of the present invention, a protective layer and an adhesive precursor (polymerizable monomer and / or polymerizable oligomer) are formed by a polymer of polymerizable monomer and / or polymerizable oligomer. A mixture of a polymer and a polymerizable monomer and / or a polymerizable oligomer) Since an appropriate anchoring effect works at the interface and further the polymerization proceeds after bonding, the elastic modulus of the adhesive layer can be set high, so that the wafer thickness Both the adhesiveness at the time of forming and the peelability after thinning can be achieved.
Based on the above view, the present inventors have found that an adhesive layer having high adhesiveness and can be easily peeled can be formed, and the present invention has been completed.
　具体的には、下記手段＜１＞により、より好ましくは＜２＞～＜２３＞により、上記課題は解決された。
＜１＞（Ａ）支持体上に、（Ｂ）接着剤層前駆体、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有し、（Ｂ）接着剤層前駆体が、（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含み、かつ、重合性モノマーおよび／または重合性オリゴマーの重合率が１０～７０％である、積層体。
＜２＞（ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、３官能以上のラジカル重合性モノマーを少なくとも１種含む、＜１＞に記載の積層体。
＜３＞（ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、フッ素原子および／またはケイ素原子を有するラジカル重合性化合物を少なくとも１種含む、＜１＞または＜２＞に記載の積層体。
＜４＞（ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、２官能以下のラジカル重合性モノマーおよび３官能以上のラジカル重合性モノマーを含む、＜１＞～＜３＞のいずれかに記載の積層体。
＜５＞接着剤層前駆体が、さらに（ｂ－２）光ラジカル開始剤を含有する、＜１＞～＜４＞のいずれかに記載の積層体。
＜６＞接着剤層前駆体が、さらに（ｂ－３）熱ラジカル開始剤を含有する、＜１＞～＜４＞のいずれかに記載の積層体。
＜７＞接着剤層前駆体が、さらに（ｂ－４）高分子化合物を含有する、＜１＞～＜６＞のいずれかに記載の積層体。
＜８＞（Ａ）支持体上に、（Ｂ２）接着剤層、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有し、（Ｂ２)接着剤層が接着剤層前駆体の硬化物であり、接着剤層前駆体が（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含み、かつ、重合性モノマーおよび／または重合性オリゴマーの重合率が１０～７０％である、積層体。
＜９＞（Ｃ）保護層の軟化点が１７０℃以上２５０℃以下である、＜１＞～＜８＞のいずれかに記載の積層体。
＜１０＞（Ｃ）保護層が、熱可塑性樹脂である、＜１＞～＜９＞のいずれかに記載の積層体。
＜１１＞（Ｃ）保護層が、ポリエーテルスルホン樹脂、ポリイミド樹脂、ポリエステル樹脂、ポリベンズイミダゾール樹脂、ポリアミドイミド樹脂、ポリカーボネート樹脂、ポリスチレン樹脂およびポリエーテルエーテルケトン樹脂から選ばれる少なくとも１種の熱可塑性樹脂を含む、＜１＞～＜１０＞のいずれかに記載の積層体。
＜１２＞（Ｄ）デバイスウエハが、表面上に高さ１μｍ以上１５０μｍ以下の構造体を有する、＜１＞～＜１１＞のいずれかに記載の積層体。
＜１３＞＜１＞～＜１２＞のいずれかに記載の積層体の保護層を製造するための保護層形成用組成物であって、樹脂と溶剤を含む保護層形成用組成物。
＜１４＞樹脂の軟化点が１７０℃以上２５０℃以下である、＜１３＞に記載の保護層形成用組成物。
＜１５＞＜１＞～＜７＞および＜９＞～＜１２＞のいずれかに記載の積層体の接着剤層前駆体または＜８＞に記載の接着剤層を製造するための組成物であって、溶剤と（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含む、組成物。
＜１６＞（ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、３官能以上のラジカル重合性モノマーを少なくとも１種含む、＜１５＞に記載の組成物。
＜１７＞（ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、フッ素原子および／またはケイ素原子を有するラジカル重合性化合物を少なくとも１種含む、＜１５＞または＜１６＞に記載の組成物。
＜１８＞（ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、２官能以下のラジカル重合性モノマーおよび３官能以上のラジカル重合性モノマーを含む、＜１５＞～＜１７＞のいずれかに記載の組成物。
＜１９＞さらに（ｂ－２）光ラジカル開始剤を含有する、＜１５＞～＜１８＞のいずれかに記載の組成物。
＜２０＞さらに（ｂ－２）熱ラジカル開始剤を含む、＜１５＞～＜１８＞のいずれかに記載の組成物。
＜２１＞さらに（ｂ－４）高分子化合物を含む、＜１５＞～＜２０＞のいずれかに記載の組成物。
＜２２＞樹脂と溶剤を含む保護層形成用組成物と、溶剤と重合性モノマーおよび／または重合性オリゴマーを含む接着剤層前駆体または接着剤層形成用組成物を含むキット。
＜２３＞キットが、＜１＞～＜１２＞のいずれかに記載の積層体を製造するためのキットである、＜２２＞に記載のキット。 Specifically, the above problem has been solved by the following means <1>, more preferably <2> to <23>.
<1> (B) Adhesive layer precursor, (C) Protective layer, (D) Device wafer in this order on (A) support, (B) Adhesive layer precursor is (b- 1) A laminate comprising a polymerizable monomer and / or polymerizable oligomer, and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70%.
<2> (b-1) The laminate according to <1>, wherein the polymerizable monomer and / or polymerizable oligomer includes at least one radically polymerizable monomer having three or more functions.
<3> (b-1) The laminate according to <1> or <2>, wherein the polymerizable monomer and / or polymerizable oligomer includes at least one radical polymerizable compound having a fluorine atom and / or a silicon atom. .
<4> (b-1) The polymerizable monomer and / or the polymerizable oligomer includes any one of <1> to <3>, including a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer. The laminated body of description.
<5> The laminate according to any one of <1> to <4>, wherein the adhesive layer precursor further contains (b-2) a photoradical initiator.
<6> The laminate according to any one of <1> to <4>, wherein the adhesive layer precursor further contains (b-3) a thermal radical initiator.
<7> The laminate according to any one of <1> to <6>, wherein the adhesive layer precursor further contains (b-4) a polymer compound.
<8> (A) On the support, (B2) adhesive layer, (C) protective layer, (D) device wafer in this order, (B2) cured product of adhesive layer precursor And the adhesive layer precursor contains (b-1) a polymerizable monomer and / or polymerizable oligomer, and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70%. .
<9> (C) The laminate according to any one of <1> to <8>, wherein the softening point of the protective layer is 170 ° C. or higher and 250 ° C. or lower.
<10> (C) The laminate according to any one of <1> to <9>, wherein the protective layer is a thermoplastic resin.
<11> (C) The protective layer is at least one thermoplastic selected from polyethersulfone resin, polyimide resin, polyester resin, polybenzimidazole resin, polyamideimide resin, polycarbonate resin, polystyrene resin and polyetheretherketone resin. The laminate according to any one of <1> to <10>, comprising a resin.
<12> (D) The laminate according to any one of <1> to <11>, wherein the device wafer has a structure having a height of 1 μm to 150 μm on the surface.
<13> A protective layer forming composition for producing the protective layer of the laminate according to any one of <1> to <12>, comprising a resin and a solvent.
<14> The composition for forming a protective layer according to <13>, wherein the softening point of the resin is 170 ° C. or higher and 250 ° C. or lower.
<15> A composition for producing the adhesive layer precursor of the laminate according to any one of <1> to <7> and <9> to <12> or the adhesive layer according to <8>. A composition comprising a solvent and (b-1) a polymerizable monomer and / or a polymerizable oligomer.
<16> (b-1) The composition according to <15>, wherein the polymerizable monomer and / or polymerizable oligomer comprises at least one trifunctional or higher functional radical polymerizable monomer.
<17> (b-1) The composition according to <15> or <16>, wherein the polymerizable monomer and / or polymerizable oligomer contains at least one radical polymerizable compound having a fluorine atom and / or a silicon atom. .
<18> (b-1) The polymerizable monomer and / or the polymerizable oligomer includes any one of <15> to <17>, including a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer. The composition as described.
<19> The composition according to any one of <15> to <18>, further comprising (b-2) a photoradical initiator.
<20> The composition according to any one of <15> to <18>, further comprising (b-2) a thermal radical initiator.
<21> The composition according to any one of <15> to <20>, further comprising (b-4) a polymer compound.
<22> A kit comprising a protective layer forming composition containing a resin and a solvent, and an adhesive layer precursor or an adhesive layer forming composition containing a solvent and a polymerizable monomer and / or a polymerizable oligomer.
<23> The kit according to <22>, wherein the kit is a kit for producing the laminate according to any one of <1> to <12>.
　本発明によれば、被処理部材に機械的または化学的な処理を施す際に、高い接着力により被処理部材を仮支持できるとともに、処理済部材に損傷を与えることなく、処理済部材に対する仮支持を容易に解除できる、積層体、保護層形成用組成物、接着剤層前駆体または接着剤層形成用組成物、およびそのキットを提供可能になった。 According to the present invention, when performing mechanical or chemical treatment on a member to be treated, the member to be treated can be temporarily supported by a high adhesive force, and the treated member can be temporarily treated without damaging the treated member. It has become possible to provide a laminate, a protective layer forming composition, an adhesive layer precursor or an adhesive layer forming composition, and a kit thereof that can be easily released from support.
図１Ａ、図１Ｂ、１Ｃ、１Ｄ、１Ｅ、１Ｆは、それぞれ、支持体とデバイスウエハとの仮接着を説明する概略断面図、支持体に仮接着されたデバイスウエハが薄型化された状態、支持体とデバイスウエハを剥離した状態、および支持体とデバイスウエハの表面の洗浄後の状態を示す概略断面図である。1A, 1B, 1C, 1D, 1E, and 1F are schematic cross-sectional views illustrating temporary bonding between a support and a device wafer, a state in which a device wafer temporarily bonded to the support is thinned, and support, respectively. It is a schematic sectional drawing which shows the state after peeling the body and the device wafer, and the state after washing | cleaning of the surface of a support body and a device wafer. 図２は、接着性支持体とデバイスウエハとの仮接着状態の解除を説明する概略断面図である。FIG. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the adhesive support and the device wafer.
　以下、本発明の実施形態を詳細に説明する。
　本明細書に於ける基（原子団）の表記に於いて、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書中における「活性光線」または「放射線」は、例えば、可視光線、紫外線、遠紫外線、電子線、Ｘ線等を含むものを意味する。また、本発明において「光」とは、活性光線または放射線を意味している。
　また、本明細書中における「露光」とは、特に断らない限り、水銀灯、紫外線、エキシマレーザーに代表される遠紫外線、Ｘ線、ＥＵＶ光等による露光のみならず、電子線およびイオンビーム等の粒子線による描画をも意味している。
　なお、本明細書において、“（メタ）アクリレート”はアクリレートおよびメタアクリレートを表し、“（メタ）アクリルはアクリルおよびメタアクリルを表し、“（メタ）アクリロイル”は、アクリロイルおよびメタクリロイルを表す。また、本明細書中において、“単量体”と“モノマー”とは同義である。本発明における単量体は、オリゴマーおよびポリマーと区別され、質量平均分子量が２，０００以下の化合物をいう。
　なお、以下に説明する実施の形態において、既に参照した図面において説明した部材等については、図中に同一符号あるいは相当符号を付すことにより説明を簡略化あるいは省略化する。 Hereinafter, embodiments of the present invention will be described in detail.
In the description of a group (atomic group) in this specification, the description which does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
“Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like. In the present invention, “light” means actinic rays or radiation.
In addition, the term “exposure” in the present specification is not limited to exposure by far-ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc. It also means drawing with particle beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous.The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a mass average molecular weight of 2,000 or less.
In the embodiments described below, the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.
積層体：
　本発明の積層体は、（Ａ）支持体上に、（Ｂ）接着剤層前駆体、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有し、前記（Ｂ）接着剤層前駆体が、（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含み、かつ、重合性モノマーおよび／または重合性オリゴマーの重合率が１０～７０％であることを特徴とする。
　また、本発明の積層体は、前記積層体をさらに硬化させた積層体にも関する。すなわち、（Ａ）支持体上に、（Ｂ２）接着剤層、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有し、前記（Ｂ２)接着剤層が（Ｂ）接着剤層前駆体の硬化物である。
　本発明の積層体は、２５０℃以上の環境で使用することもできる点で価値が高い。
　本発明の積層体によれば、披処理部材に機械的または化学的な処理を施す際に、高い接着力により披処理部材を仮支持できるとともに、処理済部材に損傷を与えることなく、処理済部材に対する仮支持を解除できる。
　本発明の積層体は、シリコン貫通電極形成用であることが好ましい。シリコン貫通電極の形成については後に詳述する。 Laminate:
The laminate of the present invention has (B) an adhesive layer precursor, (B) an adhesive layer precursor, (C) a protective layer, and (D) a device wafer in this order. (B-1) includes a polymerizable monomer and / or polymerizable oligomer, and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70%.
The laminate of the present invention also relates to a laminate obtained by further curing the laminate. That is, (B) adhesive layer, (C) protective layer, and (D) device wafer are provided in this order on (A) support, and (B2) adhesive layer is (B) adhesive layer precursor. It is a cured product.
The laminate of the present invention is highly valuable in that it can be used in an environment of 250 ° C. or higher.
According to the laminate of the present invention, when performing mechanical or chemical treatment on the treatment member, the treatment member can be temporarily supported by a high adhesive force, and the treated member is treated without damage. Temporary support for the member can be released.
The laminate of the present invention is preferably used for forming a silicon through electrode. The formation of the through silicon via will be described in detail later.
　以下、本発明の積層体が含有し得る各成分について詳細に説明する。 Hereinafter, each component that the laminate of the present invention may contain will be described in detail.
＜（Ｂ）接着剤層前駆体＞
　本発明の積層体は、（Ｂ）接着剤層前駆体を有し、接着剤層前駆体は、（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含み、かつ、重合性モノマーおよび／または重合性オリゴマーの重合率が１０～７０％である。以下、接着剤層を形成する接着剤層前駆体に含まれる成分について説明する。 <(B) Adhesive layer precursor>
The laminate of the present invention has (B) an adhesive layer precursor, and the adhesive layer precursor includes (b-1) a polymerizable monomer and / or a polymerizable oligomer, and the polymerizable monomer and / or Alternatively, the polymerization rate of the polymerizable oligomer is 10 to 70%. Hereinafter, components contained in the adhesive layer precursor forming the adhesive layer will be described.
＜＜接着剤層前駆体＞＞
（（ｂ－１）重合性モノマーおよび／または重合性オリゴマー）
　接着剤層前駆体には、（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを有する。
　重合性モノマーとしては、任意のものを使用でき、以下で説明するラジカル重合性モノマーおよび／または重合性オリゴマーの中から、任意に選択することができる。
　接着性と剥離性の観点から、２官能以上の重合性モノマーを少なくとも１種含むことが好ましく、３官能以上の重合性モノマーを少なくとも１種含むことがより好ましい。さらに、接着剤前駆体の適切な硬さと柔らかさの両立の観点から、２官能以下の重合性モノマーおよび３官能以上の重合性モノマーの混合物を含むことがさらに好ましい。
　また、重合性モノマーおよび／または重合性オリゴマーが、フッ素原子および／またはシリコン原子を含むことが好ましく、少なくともフッ素原子を含むことがより好ましい。本発明では、（ｂ－１）重合性モノマーおよび／または重合性オリゴマーのうち、５質量％以上がフッ素原子を含む重合性化合物であることが好ましく、１０質量％以上がフッ素原子を含む重合性化合物であることが好ましく、２０質量％以上がフッ素原子を含む重合性化合物であることがより好ましい。 << Adhesive layer precursor >>
((B-1) polymerizable monomer and / or polymerizable oligomer)
The adhesive layer precursor has (b-1) a polymerizable monomer and / or a polymerizable oligomer.
Arbitrary things can be used as a polymerizable monomer and it can select arbitrarily from the radically polymerizable monomer and / or polymerizable oligomer which are demonstrated below.
From the viewpoint of adhesiveness and peelability, it is preferable to include at least one bifunctional or higher polymerizable monomer, and more preferable to include at least one trifunctional or higher polymerizable monomer. Furthermore, it is more preferable to include a mixture of a bifunctional or lower polymerizable monomer and a trifunctional or higher polymerizable monomer from the viewpoint of achieving both appropriate hardness and softness of the adhesive precursor.
Further, the polymerizable monomer and / or polymerizable oligomer preferably contains a fluorine atom and / or a silicon atom, and more preferably contains at least a fluorine atom. In the present invention, (b-1) the polymerizable monomer and / or polymerizable oligomer is preferably a polymerizable compound in which 5% by mass or more contains a fluorine atom, and 10% by mass or more is a polymerizable compound containing a fluorine atom. It is preferably a compound, and more preferably 20% by mass or more is a polymerizable compound containing a fluorine atom.
　接着剤層前駆体中の重合性モノマーおよび／または重合性オリゴマーの重合率は、１０～７０％であり、２０～６０％が好ましく、２５～５０％がより好ましい。このように、接着剤の半硬化層で保護層を設けたデバイスウエハと貼り合わせることにより、適度なアンカー硬化と弾性率を高めることが可能となる。 The polymerization rate of the polymerizable monomer and / or polymerizable oligomer in the adhesive layer precursor is 10 to 70%, preferably 20 to 60%, more preferably 25 to 50%. Thus, it becomes possible to raise moderate anchor hardening and an elasticity modulus by bonding with the device wafer which provided the protective layer with the semi-hardened layer of the adhesive agent.
　重合性モノマーおよび／または重合性オリゴマーの重合率を１０～７０％に調整する方法としては、重合性モノマーおよび／または重合性オリゴマーを含む組成物（接着剤層前駆体形成用組成物）を５０～３００℃で加熱する方法、活性光線もしくは放射線を照射する方法および重合開始剤の選択等が挙げられる。
　接着剤層前駆体形成用組成物を５０～３００℃で加熱する方法における加熱温度は５０～３００℃が好ましく、１００～２００℃がより好ましく、１４０～１７０℃がさらに好ましい。加熱時間は、３０秒～１０分が好ましく、１～７分がより好ましく、２～５分がさらに好ましい。
　活性光線もしくは放射線を照射する方法は、例えばＵＶ露光装置を用いて接着剤層前駆体形成用組成物を露光することで重合性モノマーおよび／または重合性オリゴマーを重合させる。露光量は、１００～５０００ｍＪ／ｃｍ2が好ましく、３００～３０００ｍＪ／ｃｍ2がより好ましく、４００～１５００ｍＪ／ｃｍ2がさらに好ましい。 As a method for adjusting the polymerization rate of the polymerizable monomer and / or polymerizable oligomer to 10 to 70%, a composition containing the polymerizable monomer and / or polymerizable oligomer (composition for forming an adhesive layer precursor) is 50. Examples thereof include a method of heating at ˜300 ° C., a method of irradiating actinic rays or radiation, and selection of a polymerization initiator.
The heating temperature in the method of heating the adhesive layer precursor forming composition at 50 to 300 ° C. is preferably 50 to 300 ° C., more preferably 100 to 200 ° C., and further preferably 140 to 170 ° C. The heating time is preferably 30 seconds to 10 minutes, more preferably 1 to 7 minutes, and further preferably 2 to 5 minutes.
In the method of irradiating actinic rays or radiation, for example, the polymerizable monomer and / or polymerizable oligomer is polymerized by exposing the composition for forming an adhesive layer precursor using a UV exposure apparatus. Exposure is preferably 100 ~ 5000mJ / cm 2, more preferably 300 ~ 3000mJ / cm 2, more preferably 400 ~ 1500mJ / cm 2.
　重合性モノマーおよび／または重合性オリゴマーの重合率は、例えば、重合性モノマーおよび／または重合性オリゴマーの重合前後のＩＲ測定を行い、８００～８２０ｃｍ-1付近のピーク面積の減少率から測定することができる。 The polymerization rate of the polymerizable monomer and / or polymerizable oligomer should be measured, for example, by performing IR measurement before and after polymerization of the polymerizable monomer and / or polymerizable oligomer, and from the reduction rate of the peak area in the vicinity of 800 to 820 cm −1. Can do.
　重合性モノマーおよび／または重合性オリゴマーは重合性基を有する化合物を意味するが、重合性基として、ラジカル重合性基であることが好ましい。すなわち重合性モノマーおよび／または重合性オリゴマーとしてはラジカル重合性モノマーおよび／または重合性オリゴマーであることが好ましい。本発明におけるラジカル重合性モノマーおよび／または重合性オリゴマーの官能基数は、１分子中におけるラジカル重合性基の数を意味する。ラジカル重合性基とは、典型的には、活性光線若しくは放射線の照射、または、ラジカルの作用により、重合することが可能な基である。
　なお、重合性モノマーは、高分子化合物とは異なる化合物である。重合性モノマーは、典型的には、低分子化合物であり、分子量２０００以下の低分子化合物であることが好ましく、１５００以下の低分子化合物であることがより好ましく、分子量９００以下の低分子化合物であることがさらに好ましい。なお、分子量は、通常、１００以上である。また重合性オリゴマーとは、典型的には比較的低い分子量の重合体であり、１０個から１００個のモノマーが結合した重合体であることが好ましい。分子量としては、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によるポリスチレン換算の重量平均分子量が、２０００～２００００であることが好ましく、２０００～１５０００がより好ましく、２０００～１００００であることが最も好ましい。 A polymerizable monomer and / or a polymerizable oligomer means a compound having a polymerizable group, and a radical polymerizable group is preferable as the polymerizable group. That is, the polymerizable monomer and / or polymerizable oligomer is preferably a radical polymerizable monomer and / or polymerizable oligomer. The number of functional groups of the radical polymerizable monomer and / or polymerizable oligomer in the present invention means the number of radical polymerizable groups in one molecule. The radical polymerizable group is typically a group that can be polymerized by irradiation with actinic rays or radiation, or by the action of radicals.
The polymerizable monomer is a compound different from the polymer compound. The polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably it is. The molecular weight is usually 100 or more. The polymerizable oligomer is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 monomers are bonded. Regarding the molecular weight, the polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) method is preferably 2000 to 20000, more preferably 2000 to 15000, and most preferably 2000 to 10,000.
　重合性基は、例えば、付加重合反応し得る官能基であることが好ましく、付加重合反応し得る官能基としては、エチレン性不飽和結合基が挙げられる。エチレン性不飽和結合基としては、スチリル基、（メタ）アクリロイル基およびアリル基が好ましく、（メタ）アクリロイル基がさらに好ましい。すなわち、本発明で用いるラジカル重合性モノマーは、（メタ）アクリレートモノマーであることが好ましく、アクリレートモノマーであることがさらに好ましい。 The polymerizable group is preferably, for example, a functional group that can undergo an addition polymerization reaction, and examples of the functional group that can undergo an addition polymerization reaction include an ethylenically unsaturated bond group. As the ethylenically unsaturated bond group, a styryl group, a (meth) acryloyl group and an allyl group are preferable, and a (meth) acryloyl group is more preferable. That is, the radical polymerizable monomer used in the present invention is preferably a (meth) acrylate monomer, and more preferably an acrylate monomer.
　ラジカル重合性モノマーとしては、例えば、モノマー、プレポリマー、すなわち２量体、３量体およびオリゴマー、またはそれらの混合物並びにそれらの多量体などの化学的形態のいずれであってもよい。 The radical polymerizable monomer may be any of chemical forms such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, a mixture thereof, and a multimer thereof.
　より具体的には、モノマーおよびそのプレポリマーの例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類、並びにこれらの多量体が挙げられ、好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル、および不飽和カルボン酸と多価アミン化合物とのアミド類、並びにこれらの多量体である。また、ヒドロキシル基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、さらに、ハロゲン基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。 More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, amides of unsaturated carboxylic acids and polyhydric amine compounds, and multimers thereof. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
　多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、アクリル酸エステルとして、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、１，３－ブタンジオールジアクリレート、テトラメチレングリコールジアクリレート、プロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリメチロールエタントリアクリレート、ヘキサンジオールジアクリレート、１，４－シクロヘキサンジオールジアクリレート、テトラエチレングリコールジアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールジアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラアクリレート、ソルビトールトリアクリレート、ソルビトールテトラアクリレート、ソルビトールペンタアクリレート、ソルビトールヘキサアクリレート、トリ（アクリロイルオキシエチル）イソシアヌレート、イソシアヌール酸エチレンオキシド（ＥＯ）変性トリアクリレート、ポリエステルアクリレートオリゴマー等がある。 Specific examples of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide (EO) modified tri Examples include acrylates and polyester acrylate oligomers.
　メタクリル酸エステルとしては、テトラメチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、エチレングリコールジメタクリレート、１，３－ブタンジオールジメタクリレート、ヘキサンジオールジメタクリレート、ペンタエリスリトールジメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールジメタクリレート、ジペンタエリスリトールヘキサメタクリレート、ソルビトールトリメタクリレート、ソルビトールテトラメタクリレート、ビス〔ｐ－（３－メタクリルオキシ－２－ヒドロキシプロポキシ）フェニル〕ジメチルメタン、ビス－〔ｐ－（メタクリルオキシエトキシ）フェニル〕ジメチルメタン等がある。 Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.
　イタコン酸エステルとしては、エチレングリコールジイタコネート、プロピレングリコールジイタコネート、１，３－ブタンジオールジイタコネート、１，４－ブタンジオールジイタコネート、テトラメチレングリコールジイタコネート、ペンタエリスリトールジイタコネート、ソルビトールテトライタコネート等がある。 Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
　クロトン酸エステルとしては、エチレングリコールジクロトネート、テトラメチレングリコールジクロトネート、ペンタエリスリトールジクロトネート、ソルビトールテトラジクロトネート等がある。 Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
　イソクロトン酸エステルとしては、エチレングリコールジイソクロトネート、ペンタエリスリトールジイソクロトネート、ソルビトールテトライソクロトネート等がある。 Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
　マレイン酸エステルとしては、エチレングリコールジマレート、トリエチレングリコールジマレート、ペンタエリスリトールジマレート、ソルビトールテトラマレート等がある。 Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
　その他のエステルの例として、例えば、特公昭４６－２７９２６号公報、特公昭５１－４７３３４号公報、特開昭５７－１９６２３１号公報記載の脂肪族アルコール系エステル類や、特開昭５９－５２４０号公報、特開昭５９－５２４１号公報、特開平２－２２６１４９号公報記載の芳香族系骨格を有するもの、特開平１－１６５６１３号公報記載のアミノ基を含有するもの等も好適に用いられる。 Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Those having an aromatic skeleton described in JP-A-59-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613 are also preferably used.
　また、多価アミン化合物と不飽和カルボン酸とのアミドのモノマーの具体例としては、メチレンビス－アクリルアミド、メチレンビス－メタクリルアミド、１，６－ヘキサメチレンビス－アクリルアミド、１，６－ヘキサメチレンビス－メタクリルアミド、ジエチレントリアミントリスアクリルアミド、キシリレンビスアクリルアミド、キシリレンビスメタクリルアミド等がある。 Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
　その他の好ましいアミド系モノマーの例としては、特公昭５４－２１７２６号公報記載のシクロへキシレン構造を有するものをあげることができる。 Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
　また、イソシアネートと水酸基の付加反応を用いて製造されるウレタン系付加重合性モノマーも好適であり、そのような具体例としては、例えば、特公昭４８－４１７０８号公報に記載されている１分子に２個以上のイソシアネート基を有するポリイソシアネート化合物に、下記一般式（Ａ）で示される水酸基を含有するビニルモノマーを付加させた１分子中に２個以上の重合性ビニル基を含有するビニルウレタン化合物等が挙げられる。
　ＣＨ2＝Ｃ（Ｒ4）ＣＯＯＣＨ2ＣＨ（Ｒ5）ＯＨ　　　　　　　（Ａ）
（ただし、Ｒ4およびＲ5は、ＨまたはＣＨ3を示す。）
　また、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。 In addition, urethane-based addition-polymerizable monomers produced using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Etc.
CH 2 = C (R 4) COOCH 2 CH (R 5) OH (A)
(However, R 4 and R 5 represent H or CH 3. )
Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.
　また、ラジカル重合性モノマーとしては、特開２００９－２８８７０５号公報の段落番号００９５～段落番号０１０８に記載されている化合物を本発明においても好適に用いることができる。 As the radical polymerizable monomer, compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.
　また、前記ラジカル重合性モノマーとしては、少なくとも１個の付加重合可能なエチレン基を有する、常圧下で１００℃以上の沸点を持つエチレン性不飽和基を持つ化合物も好ましい。その例としては、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、等の単官能のアクリレートやメタアクリレート；ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイロキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後（メタ）アクリレート化したもの、特公昭４８－４１７０８号、特公昭５０－６０３４号、特開昭５１－３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタアクリレートおよびこれらの混合物を挙げることができる。
　多官能カルボン酸にグリシジル（メタ）アクリレート等の環状エーテル基とエチレン性不飽和基を有する化合物を反応させ得られる多官能（メタ）アクリレートなども挙げることができる。
　また、その他の好ましいラジカル重合性モノマーとして、特開２０１０－１６０４１８号公報、特開２０１０－１２９８２５号公報、特許第４３６４２１６号等に記載される、フルオレン環を有し、エチレン性重合性基を２官能以上有する化合物、カルド樹脂も使用することが可能である。
　さらに、ラジカル重合性モノマーのその他の例としては、特公昭４６－４３９４６号公報、特公平１－４０３３７号公報、特公平１－４０３３６号公報記載の特定の不飽和化合物や、特開平２－２５４９３号公報記載のビニルホスホン酸系化合物等もあげることができる。また、ある場合には、特開昭６１－２２０４８号公報記載のペルフルオロアルキル基を含有する構造が好適に使用される。さらに日本接着協会誌　ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に光硬化性モノマーおよびオリゴマーとして紹介されているものも使用することができる。 The radical polymerizable monomer is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Further, as other preferable radical polymerizable monomers, those having a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. It is also possible to use a compound having a functionality or higher, a cardo resin.
Other examples of the radical polymerizable monomer include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid-based compounds described in the Japanese Patent Publication. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.
　また、常圧下で１００℃以上の沸点を有し、少なくとも一つの付加重合可能なエチレン性不飽和基を持つ化合物としては、特開２００８－２９２９７０号公報の段落番号０２５４～０２５７に記載の化合物も好適である。 Examples of the compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group include the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. Is preferred.
　上記のほか、下記一般式（ＭＯ－１）～（ＭＯ－５）で表される、ラジカル重合性モノマーも好適に用いることができる。なお、式中、Ｔがオキシアルキレン基の場合には、炭素原子側の末端がＲに結合する。 In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　前記一般式において、ｎは０～１４の整数であり、ｍは１～８の整数である。一分子内に複数存在するＲ、Ｔ、は、各々同一であっても、異なっていてもよい。
　上記一般式（ＭＯ－１）～（ＭＯ－５）で表されるラジカル重合性モノマーの各々において、複数のＲの内の少なくとも１つは、－ＯＣ（＝Ｏ）ＣＨ＝ＣＨ2、または、－ＯＣ（＝Ｏ）Ｃ（ＣＨ3）＝ＣＨ2で表される基を表す。
　上記一般式（ＭＯ－１）～（ＭＯ－５）で表される、ラジカル重合性モノマーの具体例としては、特開２００７－２６９７７９号公報の段落番号０２４８～０２５１に記載されている化合物を本発明においても好適に用いることができる。 In the above general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH 2 , or A group represented by —OC (═O) C (CH 3 ) ═CH 2 is represented.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.
　また、特開平１０－６２９８６号公報において一般式（１）および（２）としてその具体例と共に記載の、前記多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も、ラジカル重合性モノマーとして用いることができる。 In addition, compounds described in JP-A No. 10-62986 as general formulas (1) and (2) together with specific examples thereof are compounds obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol and then (meth) acrylated. Can be used as a radical polymerizable monomer.
　中でも、ラジカル重合性モノマーとしては、ジペンタエリスリトールトリアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬株式会社製）、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬株式会社製）ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬株式会社製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬株式会社製）、およびこれらの（メタ）アクリロイル基がエチレングリコール、プロピレングリコール残基を介している構造が好ましい。これらのオリゴマータイプも使用できる。 Among them, as radical polymerizable monomers, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (commercially available) KAYARAD D-310 (commercially available from Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues. These oligomer types can also be used.
　ラジカル重合性モノマーとしては、多官能モノマーであって、カルボキシル基、スルホン酸基、リン酸基等の酸基を有していても良い。従って、エチレン性化合物が、上記のように混合物である場合のように未反応のカルボキシル基を有するものであれば、これをそのまま利用することができるが、必要において、上述のエチレン性化合物のヒドロキシル基に非芳香族カルボン酸無水物を反応させて酸基を導入しても良い。この場合、使用される非芳香族カルボン酸無水物の具体例としては、無水テトラヒドロフタル酸、アルキル化無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、アルキル化無水ヘキサヒドロフタル酸、無水コハク酸、無水マレイン酸が挙げられる。 The radical polymerizable monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.
　本発明における接着剤層前駆体としては、酸基を有するモノマーを有していてもよい。
　本発明において、酸基を有するモノマーとしては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルであり、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシル基に非芳香族カルボン酸無水物を反応させて酸基を持たせた多官能モノマーが好ましく、特に好ましくは、このエステルにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトールおよび／またはジペンタエリスリトールであるものである。市販品としては、例えば、東亞合成株式会社製の多塩基酸変性アクリルオリゴマーとして、Ｍ－５１０、Ｍ－５２０などが挙げられる。 The adhesive layer precursor in the present invention may have a monomer having an acid group.
In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
　本発明では、必要に応じてモノマーとして酸基を有しない多官能モノマーと酸基を有する多官能モノマーを併用しても良い。
　酸基を有する多官能モノマーの好ましい酸価としては、０．１～４０ｍｇ－ＫＯＨ／ｇであり、特に好ましくは５～３０ｍｇ－ＫＯＨ／ｇである。多官能モノマーの酸価が低すぎると現像溶解特性が落ち、高すぎると製造や取扱いが困難になり光重合性能が落ち、画素の表面平滑性等の硬化性が劣るものとなる傾向にある。従って、異なる酸基の多官能モノマーを２種以上併用する場合、或いは酸基を有しない多官能モノマーを併用する場合、全体の多官能モノマーとしての酸基が上記範囲に入るように調整することが好ましい。
　また、ラジカル重合性モノマーとして、カプロラクトン構造を有する多官能性単量体を含有することが好ましい。
　カプロラクトン構造を有する多官能性単量体としては、その分子内にカプロラクトン構造を有する限り特に限定されるものではないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、（メタ）アクリル酸およびε－カプロラクトンをエステル化することにより得られる、ε－カプロラクトン変性多官能（メタ）アクリレートを挙げることができる。なかでも下記一般式（Ｂ）で表されるカプロラクトン構造を有する多官能性単量体が好ましい。 In this invention, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.
Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a radically polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone-modified polyfunctionality obtained by esterifying polyhydric alcohols such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Especially, the polyfunctional monomer which has a caprolactone structure represented with the following general formula (B) is preferable.
一般式（Ｂ）
Figure JPOXMLDOC01-appb-C000003
 General formula (B)
Figure JPOXMLDOC01-appb-C000003
（式中、６個のＲは全てが下記一般式（Ｃ）で表される基であるか、または６個のＲのうち１～５個が下記一般式（Ｃ）で表される基であり、残余が下記一般式（Ｄ）で表される基である。） (In the formula, all six Rs are groups represented by the following general formula (C), or 1 to 5 of the six Rs are groups represented by the following general formula (C). And the remainder is a group represented by the following general formula (D).)
一般式（Ｃ）
Figure JPOXMLDOC01-appb-C000004
 General formula (C)
Figure JPOXMLDOC01-appb-C000004
（式中、Ｒ1は水素原子またはメチル基を示し、ｍは１または２の数を示し、「＊」は結合手であることを示す。） (In the formula, R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)
　一般式（Ｄ）
Figure JPOXMLDOC01-appb-C000005
 Formula (D)
Figure JPOXMLDOC01-appb-C000005
（式中、Ｒ1は水素原子またはメチル基を示し、「＊」は結合手であることを示す。）
　このようなカプロラクトン構造を有する多官能性単量体は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０（上記一般式（Ｂ）～（Ｄ）においてｍ＝１、一般式（Ｃ）で表される基の数＝２、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－３０（同式、ｍ＝１、一般式（Ｃ）で表される基の数＝３、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－６０（同式、ｍ＝１、一般式（Ｃ）で表される基の数＝６、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－１２０（同式においてｍ＝２、一般式（Ｃ）で表される基の数＝６、Ｒ1が全て水素原子である化合物）等を挙げることができる。
　本発明において、カプロラクトン構造を有する多官能性単量体は、単独でまたは２種以上を混合して使用することができる。 (In the formula, R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = 1, the number of groups represented by the general formula (C) = 2, a compound in which R 1 is all hydrogen atoms, DPCA-30 (same formula, m = 1, the group represented by the general formula (C) Number = 3, compound in which R 1 is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by general formula (C) = 6, compound in which R 1 is all hydrogen atoms) ), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by the general formula (C) = 6, and all R 1 are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.
　また、多官能モノマーとしては、下記一般式（ｉ）または（ｉｉ）で表される化合物の群から選択される少なくとも１種であることも好ましい。 The polyfunctional monomer is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　前記一般式（ｉ）および（ｉｉ）中、Ｅは、各々独立に、－（（ＣＨ2）ｙＣＨ2Ｏ）－、または－（（ＣＨ2）ｙＣＨ（ＣＨ3）Ｏ）－を表し、ｙは、各々独立に０～１０の整数を表し、Ｘは、各々独立に、（メタ）アクリロイル基、水素原子、またはカルボキシル基を表す。
　前記一般式（ｉ）中、（メタ）アクリロイル基の合計は３個または４個であり、ｍは各々独立に０～１０の整数を表し、各ｍの合計は０～４０の整数である。但し、各ｍの合計が０の場合、Ｘのうちいずれか１つはカルボキシル基である。
　前記一般式（ｉｉ）中、（メタ）アクリロイル基の合計は５個または６個であり、ｎは各々独立に０～１０の整数を表し、各ｎの合計は０～６０の整数である。但し、各ｎの合計が０の場合、Ｘのうちいずれか１つはカルボキシル基である。 In the general formulas (i) and (ii), each E independently represents — ((CH 2 ) yCH 2 O) — or — ((CH 2 ) yCH (CH 3 ) O) —, y Each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (i), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group.
In the general formula (ii), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.
　前記一般式（ｉ）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が特に好ましい。
　前記一般式（ｉｉ）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。
また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が特に好ましい。 In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
　また、一般式（ｉ）または一般式（ｉｉ）中の－（（ＣＨ2）ｙＣＨ2Ｏ）－または－（（ＣＨ2）ｙＣＨ（ＣＨ3）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In addition, — ((CH 2 ) yCH 2 O) — or — ((CH 2 ) yCH (CH 3 ) O) — in the general formula (i) or the general formula (ii) has an oxygen atom side terminal of X The form which couple | bonds with is preferable.
　特に、一般式（ｉｉ）において、６個のＸ全てがアクリロイル基である形態が好ましい。 In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.
　前記一般式（ｉ）または（ｉｉ）で表される化合物は、従来公知の工程である、ペンタエリスリト－ルまたはジペンタエリスリト－ルにエチレンオキシドまたはプロピレンオキシドを開環付加反応により開環骨格を結合する工程と、開環骨格の末端水酸基に、例えば（メタ）アクリロイルクロライドを反応させて（メタ）アクリロイル基を導入する工程と、から合成することができる。各工程は良く知られた工程であり、当業者は容易に一般式（ｉ）または（ｉｉ）で表される化合物を合成することができる。 The compound represented by the general formula (i) or (ii) is a ring-opening skeleton obtained by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).
　前記一般式（ｉ）、（ｉｉ）で表される化合物の中でも、ペンタエリスリトール誘導体および／またはジペンタエリスリトール誘導体がより好ましい。
　具体的には、下記式（ａ）～（ｆ）で表される化合物（以下、「例示化合物（ａ）～（ｆ）」ともいう。）が挙げられ、中でも、例示化合物（ａ）、（ｂ）、（ｅ）、（ｆ）が好ましい。 Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（ｉ）、（ｉｉ）で表されるラジカル重合性モノマーの市販品としては、例えばサートマー社製のエチレンオキシ鎖を４個有する４官能アクリレートであるＳＲ－４９４、日本化薬株式会社製のペンチレンオキシ鎖を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個有する３官能アクリレートであるＴＰＡ－３３０などが挙げられる。 Examples of commercially available radical polymerizable monomers represented by the general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
　また、ラジカル重合性モノマーとしては、特公昭４８－４１７０８号、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。さらに、重合性モノマーとして、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する付加重合性モノマー類を用いることもできる。
　ラジカル重合性モノマーの市販品としては、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（山陽国策パルプ社製）、ＵＡ－７２００」(新中村化学社製、ＤＰＨＡ－４０Ｈ（日本化薬社製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社製）、ブレンマーＰＭＥ４００（日油（株）社製））などが挙げられる。 Examples of the radical polymerizable monomer include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable monomers. Monomers can also be used.
Commercially available products of radically polymerizable monomers include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha), Bremer PME400 (manufactured by NOF Corporation)) and the like.
　本発明における重合性モノマーは、２官能以下のラジカル重合性モノマーおよび３官能以上のラジカル重合性モノマーについて、それぞれ、１種単独で用いてもよいし、２種以上を併用することが好ましく、三次元架橋構造を有するという点から、３官能以上のラジカル重合性モノマーを少なくとも１種含むこと、および２官能以下のラジカル重合性モノマーおよび、３官能以上のラジカル重合性モノマーの混合物であることが好ましい。 The polymerizable monomer in the present invention may be used singly or in combination of two or more types for the bifunctional or lower radical polymerizable monomer and the trifunctional or higher radical polymerizable monomer. From the viewpoint of having an original cross-linked structure, it is preferable to include at least one trifunctional or higher functional radical polymerizable monomer and to be a mixture of a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer. .
　ラジカル重合性モノマーとしては、２５０℃の高温プロセス後の易剥離性の観点から、１、３－アダマンチルジメタノールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレートを少なくとも一つ有することが好ましい。 As the radically polymerizable monomer, 1,3-adamantyl dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified di ( (Meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di It is preferable to have at least one of pentaerythritol hexa (meth) acrylate and tetramethylolmethane tetra (meth) acrylate.
　また、２官能以下のラジカル重合性モノマーおよび３官能以上のラジカル重合性モノマーの少なくとも１種が、１つの分子内に含まれている任意の２つのラジカル重合性基の間の原子数がいずれも９原子以上であることが、接着性と易剥離性の観点から好ましい。すなわち、１つの分子中に３つ以上の重合性基を有する場合、どの２つの重合性基間の原子数も９原子以上離れていることを意味する。
　１つの分子内に含まれている任意の２つのラジカル重合性基の間を連結する９原子以上からなる連結基としては、－ＣＯ－、－Ｏ－、－ＮＨ－、２～４価の脂肪族基、２～６価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価以上の連結基（通常、官能基の数に対応する価数となる）が例示され、－ＣＯ－、－Ｏ－、および２価の脂肪族基およびそれらの組み合わせからなる群より選ばれる２価の連結基がより好ましい。ここで、脂肪族基および芳香族基は置換基を有していても良い。
　２官能以下のラジカル重合性モノマーおよび／または３官能以上のラジカル重合性モノマーの１つの分子内に含まれている任意の２つのラジカル重合性基の間の原子数は、連結基の原子数が多すぎると剥離性が低下するため、２価の連結基としては、９～１００原子が好ましく、１０～８０原子がより好ましく、１２～５０原子であることが特に好ましい。１つの分子内に含まれている任意の２つのラジカル重合性基の間の原子数は、ラジカル重合可能なエチレン性不飽和基間の原子数であり、具体的には以下の例のように数えられる。
Figure JPOXMLDOC01-appb-C000009
 In addition, the number of atoms between any two radically polymerizable groups in which at least one of a radically polymerizable monomer having a functionality of 2 or less and a radically polymerizable monomer having a functionality of 3 or more are contained in one molecule are both It is preferably 9 atoms or more from the viewpoints of adhesiveness and easy peelability. That is, when it has three or more polymerizable groups in one molecule, it means that the number of atoms between any two polymerizable groups is 9 atoms or more apart.
Examples of the linking group consisting of 9 or more atoms linking any two radically polymerizable groups contained in one molecule include —CO—, —O—, —NH—, and divalent to tetravalent fatty acids. A linking group having a valence of 2 or more selected from the group consisting of an aromatic group, a bivalent to hexavalent aromatic group, and combinations thereof (usually having a valence corresponding to the number of functional groups), -CO-, -O- and a divalent linking group selected from the group consisting of a divalent aliphatic group and a combination thereof are more preferable. Here, the aliphatic group and the aromatic group may have a substituent.
The number of atoms between any two radically polymerizable groups contained in one molecule of a bifunctional or lower radical polymerizable monomer and / or a trifunctional or higher functional radical polymerizable monomer is the number of atoms of the linking group. If the amount is too large, the releasability is lowered, and therefore the divalent linking group is preferably 9 to 100 atoms, more preferably 10 to 80 atoms, and particularly preferably 12 to 50 atoms. The number of atoms between any two radically polymerizable groups contained in one molecule is the number of atoms between radically polymerizable ethylenically unsaturated groups. Specifically, as in the following example, Be counted.
Figure JPOXMLDOC01-appb-C000009
　２官能以下のラジカル重合性モノマーおよび３官能以上のラジカル重合性モノマーの少なくとも１種は下記一般式（１）で表されるポリオキシアルキレン部分構造を有することが好ましい。
一般式（１）
Figure JPOXMLDOC01-appb-C000010
 （一般式（１）中、Ｒ21は、水素原子またはアルキル基を表す。ａは、１～５の整数を表す。ｌは、２～１５０の整数を表す。） At least one of a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer preferably has a polyoxyalkylene partial structure represented by the following general formula (1).
General formula (1)
Figure JPOXMLDOC01-appb-C000010
 (In general formula (1), R 21 represents a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150.)
　Ｒ21で表されるアルキル基としては、炭素数１～１０の、直鎖、分岐または環状アルキル基が例示され、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。
　Ｒ21としては、水素原子が特に好ましい。
　ａは、１または２が好ましく、１が特に好ましい。
　ｌは、２～５０の整数が好ましく、２～２５の整数がより好ましく、２～１０の整数が特に好ましい。 Examples of the alkyl group represented by R 21 include straight-chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, An isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like can be mentioned.
R 21 is particularly preferably a hydrogen atom.
a is preferably 1 or 2, and particularly preferably 1.
l is preferably an integer of 2 to 50, more preferably an integer of 2 to 25, and particularly preferably an integer of 2 to 10.
　１つの分子内に含まれている任意の２つのラジカル重合性基の間の原子数がいずれも９原子以上からなる２価以上の連結基で連結されているモノマーは、２官能以下のラジカル重合性モノマーであることが好ましく、２官能のラジカル重合性モノマーであることがさらに好ましい。さらに、２官能以下のラジカル重合性モノマーが一般式（１）で表されるポリオキシアルキレン部分構造を有していることが好ましく、２官能のラジカル重合性モノマーが一般式（１）で表されるポリオキシアルキレン部分構造を有していることがさらに好ましい。 Monomers connected by divalent or higher valent linking groups in which the number of atoms between any two radically polymerizable groups contained in one molecule is 9 atoms or more are all difunctional radical polymerizations. It is preferably a reactive monomer, and more preferably a bifunctional radically polymerizable monomer. Furthermore, the bifunctional or lower radical polymerizable monomer preferably has a polyoxyalkylene partial structure represented by the general formula (1), and the bifunctional radical polymerizable monomer is represented by the general formula (1). More preferably, it has a polyoxyalkylene partial structure.
　さらには、２官能以下のラジカル重合性モノマーとしては、下記一般式（２）で表される２官能モノマーであることが特に好ましい。
一般式（２）
Figure JPOXMLDOC01-appb-C000011
 （一般式（２）中、Ｒ21、Ｒ22およびＲ23は、それぞれ、水素原子またはアルキル基を表す。ａは、１～５の整数を表す。ｌは、２～１５０の整数を表す。Ｘ1、Ｘ2、Ｙ1およびＹ2はそれぞれ、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。） Furthermore, the bifunctional or lower radical polymerizable monomer is particularly preferably a bifunctional monomer represented by the following general formula (2).
General formula (2)
Figure JPOXMLDOC01-appb-C000011
 (In the general formula (2), R 21 , R 22 and R 23 each represent a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150. X 1 , X 2 , Y 1 and Y 2 are each composed of a single bond, or —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represents a divalent linking group selected from the group.)
　Ｒ21、Ｒ22およびＲ23で表されるアルキル基としては、炭素数１～１０の、直鎖、分岐または環状アルキル基が例示され、それぞれ、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。
　Ｒ21としては、水素原子またはメチル基が好ましく、水素原子が特に好ましい。
　Ｒ22およびＲ23としては、それぞれ、水素原子またはメチル基が特に好ましい。
　ａおよびｌは、それぞれ、一般式（１）におけるａおよびｌと同義であり、好ましい範囲も同様である。 Examples of the alkyl group represented by R 21 , R 22 and R 23 include straight-chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and each includes a methyl group, an ethyl group, a propyl group, an octyl group, Examples include isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
R 21 is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
R 22 and R 23 are each particularly preferably a hydrogen atom or a methyl group.
a and l are respectively synonymous with a and l in General formula (1), and their preferable range is also the same.
　Ｘ1およびＸ2としては、それぞれ、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。
　Ｘ1およびＸ2の具体例としては、それぞれ、以下のＬ１～Ｌ１８が挙げられる。下記例において左側がＹ1またはＹ2に結合し、右側がエチレン性不飽和結合に結合する。 X 1 and X 2 are each selected from the group consisting of a single bond, or —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represents a divalent linking group.
Specific examples of X 1 and X 2 include the following L1 to L18, respectively. In the following example, the left side is bonded to Y 1 or Y 2 , and the right side is bonded to an ethylenically unsaturated bond.
Ｌ１：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ２：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ３：－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ５：－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ６：－ＣＯ－ＮＨ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ７：－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ８：－２価の芳香族基－Ｏ－ＣＯ－
Ｌ９：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１０：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１１：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１２：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１３：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１５：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１６：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１７：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１８：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－ L1: -CO-NH-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
L2: —CO—NH-divalent aliphatic group —O—CO—
L3: —CO-2 valent aliphatic group —O—CO—
L4: —CO—O-2 valent aliphatic group —O—CO—
L5: -valent aliphatic group -O-CO-
L6: —CO—NH-divalent aromatic group —O—CO—
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 divalent aromatic group -O-CO-NH-2 divalent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
　ここで２価の脂肪族基とは、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基またはポリアルキレンオキシ基を意味する。なかでもアルキレン基、置換アルキレン基、アルケニレン基、および置換アルケニレン基が好ましく、アルキレン基および置換アルキレン基がさらに好ましい。これらの基は置換基を有さない方が好ましい。
　２価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。２価の脂肪族基の炭素原子数は、１～２０であることが好ましく、１～１５であることがより好ましく、１～１２であることがさらに好ましく、１～１０であることがさらにまた好ましく、１～８であることがよりさらに好ましく、１～４であることが特に好ましい。
　２価の脂肪族基の置換基の例としては、ハロゲン原子（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、アリールアミノ基およびジアリールアミノ基等が挙げられる。 Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable. These groups preferably have no substituent.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
　２価の芳香族基の例としては、フェニレン基、置換フェニレン基、ナフタレン基および置換ナフタレン基が挙げられ、フェニレン基が好ましい。２価の芳香族基の置換基の例としては、上記２価の脂肪族基の置換基の例に加えて、アルキル基が挙げられる。 Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
　Ｙ1およびＹ2としては、それぞれ、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｙ1、Ｙ2のいずれかが、２価の芳香族基、またはポリオキシアルキレン構造を有することが好ましく、２価の芳香族基およびポリオキシアルキレン構造を有することが特に好ましい。２価の芳香族基は１つまたは２以上のベンゼン環から構成されていることが好ましく、フェニレン基であることがより好ましい。 Y 1 and Y 2 are each selected from the group consisting of a single bond, or —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represents a divalent linking group. Either Y 1 or Y 2 preferably has a divalent aromatic group or a polyoxyalkylene structure, and particularly preferably has a divalent aromatic group and a polyoxyalkylene structure. The divalent aromatic group is preferably composed of one or two or more benzene rings, and more preferably a phenylene group.
　さらに本発明では、２官能以下のラジカル重合性モノマーおよび／または３官能以上のラジカル重合性モノマーが、炭素原子、酸素原子、水素原子および窒素原子から選択される原子のみから構成されていることが好ましく、炭素原子、酸素原子および水素原子のみから構成されていることがより好ましい。 Furthermore, in the present invention, the radical polymerizable monomer having 2 or less functional groups and / or the radical polymerizable monomer having 3 or more functional groups may be composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom and a nitrogen atom. Preferably, it is comprised only from a carbon atom, an oxygen atom, and a hydrogen atom.
　分子内の最も近いラジカル重合性基が、少なくとも９原子からなる２価の連結基で連結されているラジカル重合性モノマーとしては、具体的に以下の構造で表されるラジカル重合性モノマーが挙げられるがこれらに限定されない。
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
 （Ｍｅはメチル基を表す。） Specific examples of the radical polymerizable monomer in which the closest radical polymerizable group in the molecule is linked by a divalent linking group consisting of at least 9 atoms include radical polymerizable monomers represented by the following structures. However, it is not limited to these.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
 (Me represents a methyl group.)
　２官能以下のラジカル重合性モノマーと３官能以上のラジカル重合性モノマーの比率（質量比）は、９５／５～２０／８０であることが好ましく、８５／１５～２０／８０であることがより好ましく、８０／２０～２０／８０であることがさらに好ましく、８０／２０～４０／６０であることがよりさらに好ましく、８０／２０～５０／５０が特に好ましい。 The ratio (mass ratio) of the bifunctional or lower radical polymerizable monomer and the trifunctional or higher radical polymerizable monomer is preferably 95/5 to 20/80, more preferably 85/15 to 20/80. It is preferably 80/20 to 20/80, more preferably 80/20 to 40/60, and particularly preferably 80/20 to 50/50.
　２官能以下のラジカル重合性モノマーおよび３官能以上のラジカル重合性モノマーの市販品としては、ブレンマーＰＭＥ４００（日油（株）社製））、ＮＫエステル　Ａ－ＢＰＥ－４、ＮＫエステル　Ａ－ＢＰＥ－１０、ＮＫエステル　Ａ－ＴＭＰ－３ＥＯ、ＮＫエステル　ＡＤ－ＴＭＰ、ＮＫエステル　Ａ－ＤＰＨ（新中村化学工業（株）社製）、ジビニルベンゼン（和光純薬工業（株）社製）、ライトアクリレート　ＴＭＰ－Ａ（共栄社化学（株）社製）、イソシアヌル酸トリアリル（東京化成工業（株）社製）などが挙げられる。 Commercially available products of a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer include BREMMER PME400 (manufactured by NOF Corporation), NK ester A-BPE-4, NK ester A-BPE- 10. NK ester A-TMP-3EO, NK ester AD-TMP, NK ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.), divinylbenzene (manufactured by Wako Pure Chemical Industries, Ltd.), light acrylate TMP -A (manufactured by Kyoeisha Chemical Co., Ltd.), triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
　重合性モノマーの含有量は、良好な接着強度と剥離性の観点から、接着剤層前駆体の全固形分に対して、２０～１００質量％が好ましく、３０～９５質量％がより好ましく、５０～９０質量％がさらに好ましい。重合性モノマーは１種類のみでもよいし、２種類以上であってもよい。重合性モノマーが２種類以上の場合は、その合計が上記範囲であることが好ましい。 The content of the polymerizable monomer is preferably 20 to 100% by mass, more preferably 30 to 95% by mass with respect to the total solid content of the adhesive layer precursor, from the viewpoint of good adhesive strength and peelability. More preferably, it is 90% by mass. Only one type of polymerizable monomer may be used, or two or more types may be used. When there are two or more kinds of polymerizable monomers, the total is preferably in the above range.
［フッ素原子またはケイ素原子を有する重合性モノマーおよび／または重合性オリゴマー］
　本発明における重合性モノマーおよび／または重合性オリゴマーは、フッ素原子および／またはケイ素原子を有する重合性化合物であることが特に好ましい。フッ素原子および／またはケイ素原子を有する重合性化合物は、フッ素原子またはケイ素原子が一分子中に１個以上含まれるラジカル重合性モノマーおよび／または重合性オリゴマーであることが好ましく、フッ素原子が一分子中に２個以上含まれる、一般的にパーフルオロ基と呼ばれる基を有している重合性モノマーおよび／または重合性オリゴマーであることが特に好ましい。 [Polymerizable monomer and / or polymerizable oligomer having fluorine atom or silicon atom]
The polymerizable monomer and / or polymerizable oligomer in the present invention is particularly preferably a polymerizable compound having a fluorine atom and / or a silicon atom. The polymerizable compound having a fluorine atom and / or silicon atom is preferably a radical polymerizable monomer and / or polymerizable oligomer in which one or more fluorine atoms or silicon atoms are contained in one molecule, and one molecule of fluorine atoms A polymerizable monomer and / or polymerizable oligomer having a group generally referred to as a perfluoro group contained in two or more thereof is particularly preferable.
　フッ素原子および／またはケイ素原子を有するラジカル重合性化合物は、ラジカル重合性官能基を有するものであり、ラジカル重合性官能基としては、特に制限されないが、不飽和基（エチレン性不飽和結合基など）あることが好ましい。 The radically polymerizable compound having a fluorine atom and / or a silicon atom has a radically polymerizable functional group, and the radically polymerizable functional group is not particularly limited, but an unsaturated group (such as an ethylenically unsaturated bond group). Preferably).
　フッ素原子および／またはケイ素原子を有するラジカル重合性化合物は、２個以上のラジカル重合性官能基を有することが好ましく、これにより、積層体の、高温でのプロセスを経た後の、処理済部材に対する仮支持の剥離性をより向上できる。 The radically polymerizable compound having a fluorine atom and / or a silicon atom preferably has two or more radically polymerizable functional groups, so that the laminated body is subjected to a high-temperature process with respect to the treated member. The peelability of the temporary support can be further improved.
［［フッ素原子を有する重合性モノマーおよび／または重合性オリゴマー］］
　フッ素原子を有する重合性モノマーおよび／または重合性オリゴマーは、公知のモノマーから選択することができ、重合性基を架橋性基とする架橋剤であることが好ましい。架橋性基としては例えば、水酸基又は加水分解可能な基を有するシリル基（例えばアルコキシシリル基、アシルオキシシリル基等）、反応性不飽和二重結合を有する基（（メタ）アクリロイル基、アリル基、ビニルオキシ基等）、開環重合反応性基（エポキシ基、オキセタニル基、オキサゾリル基等）、活性水素原子を有する基（たとえば水酸基、カルボキシル基、アミノ基、カルバモイル基、メルカプト基、β－ケトエステル基、ヒドロシリル基、シラノール基等）、酸無水物、求核剤によって置換され得る基（活性ハロゲン原子、スルホン酸エステル等）等が挙げられる。 [[Polymerizable monomer and / or polymerizable oligomer having a fluorine atom]]
The polymerizable monomer and / or polymerizable oligomer having a fluorine atom can be selected from known monomers, and is preferably a crosslinking agent having a polymerizable group as a crosslinkable group. Examples of the crosslinkable group include a silyl group having a hydroxyl group or a hydrolyzable group (eg, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) acryloyl group, allyl group, Vinyloxy groups, etc.), ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, mercapto groups, β-ketoester groups, Hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like.
　フッ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーは、以下の一般式（１）で表すことができる化合物が好ましい。
一般式（Ｉ） ： Ｒｆ｛－Ｌ－Ｙ｝ｎ
（式中、Ｒｆは少なくとも炭素原子及びフッ素原子を含み、酸素原子及び水素原子のうちいずれかを含んでも良い、鎖状又は環状のｎ価の基を表し、ｎは２以上の整数を表す。Ｌは単結合又は二価の連結基を表す。Ｙは重合性基を表す。） The radically polymerizable monomer and / or polymerizable oligomer having a fluorine atom is preferably a compound that can be represented by the following general formula (1).
Formula (I): Rf {-LY} n
(In the formula, Rf represents a chain or cyclic n-valent group containing at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom, and n represents an integer of 2 or more. L represents a single bond or a divalent linking group, and Y represents a polymerizable group.)
　上記一般式（Ｉ）において、Ｙは重合性基であり、例えば、水酸基又は加水分解可能な基を有するシリル基（例えば、アルコキシシリル基、アシルオキシシリル基等）、反応性不飽和二重結合を有する基（（メタ）アクリロイル基、アリル基、ビニルオキシ基等）、開環重合反応性基（エポキシ基、オキセタニル基、オキサゾリル基等）、活性水素原子を有する基（たとえば水酸基、カルボキシル基、アミノ基、カルバモイル基、メルカプト基、β－ケトエステル基、ヒドロシリル基、シラノール基等）、酸無水物、求核剤によって置換され得る基（活性ハロゲン原子、スルホン酸エステル等）等が好ましい。 In the above general formula (I), Y is a polymerizable group, for example, a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), a reactive unsaturated double bond. Groups having (meth) acryloyl groups, allyl groups, vinyloxy groups, etc., ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups) Carbamoyl group, mercapto group, β-ketoester group, hydrosilyl group, silanol group, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like are preferable.
　より好ましくは、Ｙは、ラジカル重合性基を表し、反応性不飽和二重結合を有する基が更に好ましい。具体的には、Ｔは下記一般式（９）で表されるラジカル重合性官能基を表すことが好ましい。 More preferably, Y represents a radical polymerizable group, and more preferably a group having a reactive unsaturated double bond. Specifically, T preferably represents a radical polymerizable functional group represented by the following general formula (9).
Figure JPOXMLDOC01-appb-C000014
 （一般式（９）中、Ｒ901～Ｒ903は、それぞれ独立して、水素原子、アルキル基又はアリール基を表す。点線は、Lへ連結する基への結合を表す。）
Figure JPOXMLDOC01-appb-C000014
 (In the general formula (9), R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group. The dotted line represents a bond to a group linked to L.)
　アルキル基の例は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。Ｒ901～Ｒ903はとしては、なかでも、水素原子またはメチル基が好ましい。 Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples thereof include 2-methylhexyl group and cyclopentyl group. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
　Ｌは単結合又は二価の連結基を表す。二価の連結基としては、２価の脂肪族基、２価の芳香族基、－Ｏ－、－Ｓ－、－CO－、－Ｎ（Ｒ）－、及びこれらを２種以上組み合わせて得られる２価の連結基を表す。ただし、前記Ｒは水素原子又は炭素数１～５のアルキル基を表す。
Ｌがアルキレン基又はアリーレン基を有する場合、アルキレン基及びアリーレン基はハロゲン原子で置換されていることが好ましく、フッ素原子で置換されていることがより好ましい。 L represents a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group, a divalent aromatic group, —O—, —S—, —CO—, —N (R) —, or a combination of two or more thereof can be obtained. Represents a divalent linking group. R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
When L has an alkylene group or an arylene group, the alkylene group and the arylene group are preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.
　Ｒｆは、少なくとも炭素原子及びフッ素原子を含み、酸素原子及び水素原子のうちいずれかを含んでも良い、鎖状又は環状のｎ価の基を表す。Ｒｆは、フッ素原子を有する繰り返し単位を有する線状または分岐状の高分子構造であってもよい。 Rf represents a chain or cyclic n-valent group which contains at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom. Rf may be a linear or branched polymer structure having a repeating unit having a fluorine atom.
　このようなフッ素原子を有するモノマーとしては、特開２０１１－４８３５８号公報の段落番号００１９～００３３に記載の化合物も好ましく使用でき、これらの内容は本願明細書に組み込まれる。 As such a monomer having a fluorine atom, the compounds described in paragraph numbers 0019 to 0033 of JP2011-48358A can also be preferably used, and the contents thereof are incorporated in the present specification.
　また、フッ素原子を有するラジカル重合性モノマーは、下記構造式（１）、（２）、（３）、（４）及び（５）で表される化合物から選択される少なくとも１種であることも好ましい。 The radically polymerizable monomer having a fluorine atom may be at least one selected from compounds represented by the following structural formulas (1), (2), (3), (4) and (5). preferable.
　ＣＨ2＝ＣＲ1ＣＯＯＲ2Ｒf　・・・構造式（１）
（構造式（１）中、Ｒ1は、水素原子、またはメチル基を表す。Ｒ2は、－ＣpＨ2p－、－Ｃ（ＣpＨ2p+1）Ｈ－、－ＣＨ2Ｃ（ＣpＨ2p+1）Ｈ－、または－ＣＨ2ＣＨ2Ｏ－を表す。Ｒfは、－ＣnＦ2n+1、－（ＣＦ2）nＨ、－ＣnＦ2n+1－ＣＦ3、－（ＣＦ2）pＯＣnＨ2nＣiＦ2i+1、－（ＣＦ2）pＯＣmＨ2mＣiＦ2iＨ、－Ｎ（ＣpＨ2p+1）ＣＯＣnＦ2n+1、または、－Ｎ（ＣpＨ2p+1）ＳＯ2ＣnＦ2n+1を表す。ただし、ｐは１～１０の整数、ｎは１～１６の整数、ｍは０～１０の整数、ｉは０～１６の整数をそれぞれ表す。） CH 2 = CR 1 COOR 2 R f ··· structural formula (1)
(In the structural formula (1), R 1 represents a hydrogen atom or a methyl group. R 2 represents —C p H 2p —, —C (C p H 2p + 1 ) H—, —CH 2 C ( C p H 2p + 1 ) H— or —CH 2 CH 2 O—, where R f is —C n F 2n + 1 , — (CF 2 ) n H, —C n F 2n + 1 —CF 3, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, or, -N (C p H 2p + 1) represents the SO 2 C n F 2n + 1 . Here, p is an integer of 1 ~ 10, n is an integer of 1 ~ 16, m is 0 to 10 integer I represents an integer of 0 to 16, respectively.)
　ＣＦ2＝ＣＦＯＲg・・・構造式（２）
（構造式（２）中、Ｒgは、炭素数１～２０のフルオロアルキル基を表す。） CF 2 = CFOR g. Structural formula (2)
(In the structural formula (2), R g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
　ＣＨ2＝ＣＨＲg・・・構造式（３）
（構造式（３）中、Ｒgは、炭素数１～２０のフルオロアルキル基を表す。） CH 2 = CHR g ... Structural formula (3)
(In the structural formula (3), R g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
　ＣＨ2＝ＣＲ3ＣＯＯＲ5ＲjＲ6ＯＣＯＣＲ4＝ＣＨ2・・・構造式（４）
（構造式（４）中、Ｒ3およびＲ4は、水素原子、またはメチル基を表す。Ｒ5およびＲ6は、－ＣqＨ2q－、－Ｃ（ＣqＨ2q+1）Ｈ－、－ＣＨ2Ｃ（ＣqＨ2q+1）Ｈ－または－ＣＨ2ＣＨ2Ｏ－、Ｒjは－ＣtＦ2tを表す。ｑは１～１０の整数であり、ｔは１～１６の整数である。） CH 2 = CR 3 COOR 5 R j R 6 OCOCR 4 = CH 2 ··· structural formula (4)
(In the structural formula (4), R 3 and R 4 represent a hydrogen atom or a methyl group. R 5 and R 6 represent —C q H 2q —, —C (C q H 2q + 1 ) H— , —CH 2 C (C q H 2q + 1 ) H— or —CH 2 CH 2 O—, R j represents —C t F 2t , q is an integer of 1 to 10, and t is 1 to 16 Is an integer.)
　ＣＨ2＝ＣＨＲ7ＣＯＯＣＨ2（ＣＨ2Ｒk）ＣＨＯＣＯＣＲ8＝ＣＨ2・・・構造式（５）
（構造式（５）中、Ｒ7およびＲ8は、水素原子、またはメチル基を表す。Ｒkは－ＣｙＦ2y+1である。ｙは１～１６の整数である。） CH 2 = CHR 7 COOCH 2 (CH 2 R k ) CHOCOCR 8 = CH 2. Structural formula (5)
(In the structural formula (5), R 7 and R 8 represent a hydrogen atom or a methyl group. R k is —CyF 2y + 1. Y is an integer of 1 to 16.)
　前記構造式（１）で表される単量体としては、例えば、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＦ3ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＦ3（ＣＦ2）4ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、Ｃ7Ｆ15ＣＯＮ（Ｃ2Ｈ5）ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）7ＳＯ2Ｎ（ＣＨ2）ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＦ2（ＣＦ2）7ＳＯ2Ｎ（Ｃ3Ｈ7）ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｃ2Ｆ5ＳＯ2Ｎ（Ｃ3Ｈ7）ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、（ＣＦ3）2ＣＦ（ＣＦ2）6（ＣＨ2）3ＯＣＯＣＨ＝ＣＨ2、（ＣＦ3）2ＣＦ（ＣＦ2）10（ＣＨ2）3ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）4ＣＨ（ＣＨ3）ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3ＣＨ2ＯＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｃ2Ｆ5（ＣＨ2ＣＨ2Ｏ）2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、（ＣＦ3）2ＣＦＯ（ＣＨ2）5ＯＣＯＣＨ＝ＣＨ2、ＣＦ3（ＣＦ2）4ＯＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、Ｃ2Ｆ5ＣＯＮ（Ｃ2Ｈ5）ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＦ3（ＣＦ2）2ＣＯＮ（ＣＨ3）ＣＨ（ＣＨ3）ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｈ（ＣＦ2）6Ｃ（Ｃ2Ｈ5）ＯＣＯＣ（ＣＨ3）＝ＣＨ2、Ｈ（ＣＦ2）8ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｈ（ＣＦ2）4ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｈ（ＣＦ2）ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）7ＳＯ2Ｎ（ＣＨ3）ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）7ＳＯ2Ｎ（ＣＨ3）（ＣＨ2）10ＯＣＯＣＨ＝ＣＨ2、Ｃ2Ｆ5ＳＯ2Ｎ（Ｃ2Ｈ5）ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）7ＳＯ2Ｎ（ＣＨ3）（ＣＨ2）4ＯＣＯＣＨ＝ＣＨ2、Ｃ2Ｆ5ＳＯ2Ｎ（Ｃ2Ｈ5）Ｃ（Ｃ2Ｈ5）ＨＣＨ2ＯＣＯＣＨ＝ＣＨ2、等が挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。 Examples of the monomer represented by the structural formula (1) include CF 3 (CF 2 ) 5 CH 2 CH 2 OCOCH═CH 2 , CF 3 CH 2 OCOCH═CH 2 , CF 3 (CF 2 ) 4. CH 2 CH 2 OCOC (CH 3 ) = CH 2, C 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 2) CH 2 CH 2 OCOCH═CH 2 , CF 2 (CF 2 ) 7 SO 2 N (C 3 H 7 ) CH 2 CH 2 OCOCH═CH 2 , C 2 F 5 SO 2 N (C 3 H 7 ) CH 2 CH 2 OCOC (CH 3 ) ═CH 2 , (CF 3 ) 2 CF (CF 2 ) 6 (CH 2 ) 3 OCOCH═CH 2 , (CF 3 ) 2 CF (CF 2 ) 10 (CH 2 ) 3 OCOC (CH 3 ) = CH 2, CF 3 ( CF 2) 4 CH (CH 3) OCOC (CH 3) = CH 2, CF 3 CH 2 OCH 2 H 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH = CH 2, (CF 3) 2 CFO (CH 2) 5 OCOCH = CH 2, CF 3 (CF 2) 4 OCH 2 CH 2 OCOC (CH 3 ) = CH 2 , C 2 F 5 CON (C 2 H 5 ) CH 2 OCOCH═CH 2 , CF 3 (CF 2 ) 2 CON (CH 3 ) CH (CH 3 ) CH 2 OCOCH = CH 2, H (CF 2 ) 6 C (C 2 H 5) OCOC (CH 3) = CH 2, H (CF 2) 8 CH 2 OCOCH = CH 2, H (CF 2) 4 CH 2 OCOCH = CH 2 , H (CF 2 ) CH 2 OCOC (CH 3 ) ═CH 2 , CF 3 (CF 2 ) 7 SO 2 N (CH 3 ) CH 2 CH 2 OCOC (CH 3 ) ═CH 2 , CF 3 (CF 2 7 SO 2 N (CH 3 ) (CH 2 ) 10 OCOCH═CH 2 , C 2 F 5 SO 2 N (C 2 H 5) ) CH 2 CH 2 OCOC (CH 3 ) ═CH 2 , CF 3 (CF 2 ) 7 SO 2 N (CH 3 ) (CH 2 ) 4 OCOCH═CH 2 , C 2 F 5 SO 2 N (C 2 H 5 ) C (C 2 H 5 ) HCH 2 OCOCH═CH 2 , and the like. These may be used individually by 1 type and may use 2 or more types together.
　前記構造式（２）または（３）で表されるフルオロアルキル化オレフィンとしては、例えば、Ｃ3Ｆ7ＣＨ＝ＣＨ2、Ｃ4Ｆ9ＣＨ＝ＣＨ2、Ｃ10Ｆ21ＣＨ＝ＣＨ2、Ｃ3Ｆ7ＯＣＦ＝ＣＦ2、Ｃ7Ｆ15ＯＣＦ＝ＣＦ2、Ｃ8Ｆ17ＯＣＦ＝ＣＦ2、などが挙げられる。 Examples of the fluoroalkylated olefin represented by the structural formula (2) or (3) include C 3 F 7 CH═CH 2 , C 4 F 9 CH═CH 2 , C 10 F 21 CH═CH 2 , C 3 F 7 OCF = CF 2 , C 7 F 15 OCF = CF 2, C 8 F 17 OCF = CF 2, and the like.
　前記構造式（４）または（５）で表される単量体としては、例えば、ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）3ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）6ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ（ＣＨ2Ｃ8Ｆ17）ＯＣＯＣＨ＝ＣＨ2、などが挙げられる。 Examples of the monomer represented by the structural formula (4) or (5), for example, CH 2 = CHCOOCH 2 (CF 2) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 (CF 2) 6 CH 2 OCOCH═CH 2 , CH 2 = CHCOOCH 2 CH (CH 2 C 8 F 17 ) OCOCH═CH 2 , and the like.
　また、フッ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーとしては、フッ素原子を有する繰り返し単位と、ラジカル重合性官能基を有する繰り返し単位とを有するオリゴマーも好ましく使用できる。 Further, as the radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom, an oligomer having a repeating unit having a fluorine atom and a repeating unit having a radical polymerizable functional group can also be preferably used.
　フッ素原子を有する繰り返し単位としては、下記式（６）、（７）および（１０）で表される繰り返し単位の少なくとも１種から選択されることが好ましい。
Figure JPOXMLDOC01-appb-C000015
 The repeating unit having a fluorine atom is preferably selected from at least one repeating unit represented by the following formulas (6), (7) and (10).
Figure JPOXMLDOC01-appb-C000015
　式（６）中、Ｒ1、Ｒ2、Ｒ3、およびＲ4は、それぞれ独立して水素原子、ハロゲン原子、水酸基、又は１価の有機基を表し、Ｒ1、Ｒ2、Ｒ3、及び、Ｒ4の内の少なくとも一つは、フッ素原子、又は、フッ素原子を有する１価の有機基である。
　式（７）中、Ｒ5、Ｒ6、Ｒ7は、それぞれ独立して水素原子、ハロゲン原子、水酸基、又は１価の有機基を表し、Ｙ１は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｒｆは、フッ素原子、又は、フッ素原子を有する１価の有機基を表す。
　式（１０）中、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12、Ｒ13は、それぞれ独立して水素原子、ハロゲン原子、水酸基、又は１価の有機基を表し、Ｙ2およびＹ3は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｒｆは、フッ素原子を有する２価の有機基を表す。 In formula (6), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, and R 1 , R 2 , R 3 , At least one of R 4 is a fluorine atom or a monovalent organic group having a fluorine atom.
In formula (7), R 5 , R 6 and R 7 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and Y 1 represents a single bond, —CO—, — It represents a divalent linking group selected from the group consisting of O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.
In the formula (10), R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, Y 2 and Y 3 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. . Rf represents a divalent organic group having a fluorine atom.
　式（６）及び式（７）中のフッ素原子を有する１価の有機基としては、特に限定はないが、炭素数１～３０の含フッ素アルキル基が好ましく、炭素数１～２０がより好ましく、炭素数１～１５の含フッ素アルキル基が特に好ましい。この含フッ素アルキル基は、直鎖（例えば－ＣＦ2ＣＦ3、－ＣＨ2（ＣＦ2）4Ｈ、－ＣＨ2（ＣＦ2）8ＣＦ3、－ＣＨ2ＣＨ2（ＣＦ2）4Ｈ等）であっても、分岐構造（例えば－ＣＨ（ＣＦ3）2、－ＣＨ2ＣＦ（ＣＦ3）2、－ＣＨ（ＣＨ3）ＣＦ2ＣＦ3、－ＣＨ（ＣＨ3）（ＣＦ2）5ＣＦ2Ｈ等）を有していてもよく、また脂環式構造（好ましくは５員環又は６員環、例えばペルフルオロシクロへキシル基、ペルフルオロシクロペンチル基又はこれらで置換されたアルキル基等）を有していてもよく、エーテル結合（例えば、－ＣＨ2ＯＣＨ2ＣＦ2ＣＦ3、－ＣＨ2ＣＨ2ＯＣＨ2Ｃ4Ｆ8Ｈ、－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2Ｃ8Ｆ17、－ＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2Ｈ等）を有していてもよい。また、ペルフルオロアルキル基であってもよい。 The monovalent organic group having a fluorine atom in formula (6) and formula (7) is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. A fluorine-containing alkyl group having 1 to 15 carbon atoms is particularly preferred. This fluorine-containing alkyl group is a straight chain (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc. ) Even in branched structures (for example, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like, and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these). An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , — CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
　式（１０）中のフッ素原子を有する２価の有機基としては、特に限定はないが、炭素数１～３０の含フッ素アルキレン基が好ましく、炭素数１～２０がより好ましく、炭素数１～１５の含フッ素アルキレン基が特に好ましい。この含フッ素アルキレン基は、直鎖（例えば－ＣＦ2ＣＦ2－、－ＣＨ2（ＣＦ2）4－、－ＣＨ2（ＣＦ2）8ＣＦ2－、－ＣＨ2ＣＨ2（ＣＦ2）4－等）であっても、分岐構造（例えば－ＣＨ（ＣＦ3）ＣＦ2－、－ＣＨ2ＣＦ（ＣＦ3）ＣＦ2－、－ＣＨ（ＣＨ3）ＣＦ2ＣＦ2－、－ＣＨ（ＣＨ3）（ＣＦ2）5ＣＦ2－等）を有していてもよく、また脂環式構造（好ましくは５員環又は６員環、例えばペルフルオロシクロへキシル基、ペルフルオロシクロペンチル基又はこれらで置換されたアルキル基等）を有する連結基でもよく、エーテル結合（例えば－ＣＨ2ＯＣＨ2ＣＦ2ＣＦ2－、－ＣＨ2ＣＨ2ＯＣＨ2Ｃ4Ｆ8－、－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2Ｃ8Ｆ16－、－ＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2－、－ＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2－、ポリパーフルオロアルキレンエーテル鎖等）を有していてもよい。また、ペルフルオロアルキレン基であってもよい。 The divalent organic group having a fluorine atom in the formula (10) is not particularly limited, but is preferably a fluorine-containing alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Fifteen fluorine-containing alkylene groups are particularly preferred. This fluorine-containing alkylene group is a straight chain (for example, —CF 2 CF 2 —, —CH 2 (CF 2 ) 4 —, —CH 2 (CF 2 ) 8 CF 2 —, —CH 2 CH 2 (CF 2 ) 4 -, Etc.), branched structures (eg, —CH (CF 3 ) CF 2 —, —CH 2 CF (CF 3 ) CF 2 —, —CH (CH 3 ) CF 2 CF 2 —, —CH (CH 3 ) (CF 2 ) 5 CF 2- and the like) and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl, perfluorocyclopentyl, or substituted therewith A linking group having an alkyl group, etc.) or an ether bond (for example, —CH 2 OCH 2 CF 2 CF 2 —, —CH 2 CH 2 OCH 2 C 4 F 8 —, —CH 2 CH 2 OCH 2 CH 2 C 8 F 16 —, —CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 —, —C H 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 —, polyperfluoroalkylene ether chain, etc.). Further, it may be a perfluoroalkylene group.
　式（６）、（７）、（１０）中の１価の有機基は、３～１０価の非金属原子から構成される有機基であることが好ましく、例えば、１から６０個までの炭素原子、０個から１０個までの窒素原子、０個から５０個までの酸素原子、１個から１００個までの水素原子、及び０個から２０個までの硫黄原子から選ばれる少なくとも１種以上の元素から構成される有機基が挙げられる。
　より具体的な例としては、下記の構造が単独又は複数組み合わさって構成される有機基を挙げることができる。
　１価の有機基は、更に置換基を有してもよく、導入可能な置換基としては、例えば、ハロゲン原子、ヒドロキシ基、カルボキシ基、スルホナト基、ニトロ基、シアノ基、アミド基、アミノ基、アルキル基、アルケニル基、アルキニル基、アリール基、置換オキシ基、置換スルホニル基、置換カルボニル基、置換スルフィニル基、スルホ基、ホスホノ基、ホスホナト基、シリル基、複素環基、等が挙げられる。また有機基は、エーテル結合、エステル結合、ウレイド結合を含んでいてもよい。 The monovalent organic group in the formulas (6), (7), and (10) is preferably an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms. At least one or more selected from atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms Examples include organic groups composed of elements.
More specific examples include organic groups composed of the following structures singly or in combination.
The monovalent organic group may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group. , Alkyl group, alkenyl group, alkynyl group, aryl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonato group, silyl group, heterocyclic group, and the like. The organic group may contain an ether bond, an ester bond, or a ureido bond.
　１価の有機基は、アルキル基、アルケニル基、アルキニル基、アリール基が好ましい。アルキル基は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アルケニル基、炭素数２～２０のアルケニル基であることが好ましく、例えば、ビニル基、アリル基、プレニル基、ゲラニル基、オレイル基等が挙げられる。アルキニル基は、炭素数３～１０のアルキニル基であることが好ましく、エチニル基、プロパルギル基、トリメチルシリルエチニル基等が挙げられる。アリール基は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。更に、ヘテロ環基は、炭素数２～１０のヘテロ環基であることが好ましく、フラニル基、チオフェニル基、ピリジニル基などが挙げられる。 The monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-ethylhexyl group, A methylhexyl group, a cyclopentyl group, etc. are mentioned. An alkenyl group and an alkenyl group having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group. The alkynyl group is preferably an alkynyl group having 3 to 10 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethylsilylethynyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Furthermore, the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.
　式（６）中のＲ1、Ｒ2、Ｒ3、およびＲ4、式（７）中、Ｒ5、Ｒ6、Ｒ7、式（１０）中、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12、Ｒ13はで表される１価の有機基としては、アルキル基又はアリール基が好ましくい。
　アルキル基の例は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。Ｒ901～Ｒ903はとしては、なかでも、水素原子またはメチル基が好ましい。 R 1 , R 2 , R 3 and R 4 in formula (6), R 5 , R 6 , R 7 in formula ( 7 ), R 8 , R 9 , R 10 , R in formula (10) As the monovalent organic group represented by 11 , R 12 and R 13 , an alkyl group or an aryl group is preferable.
Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples thereof include 2-methylhexyl group and cyclopentyl group. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
　式（７）中のＹ1および、式（１０）中のＹ2およびＹ3で表される－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基の具体例を以下に挙げる。なお、下記例において左側が主鎖に結合し、右側がＲｆに結合する。 -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group represented by Y 1 in formula (7) and Y 2 and Y 3 in formula (10) Specific examples of the divalent linking group selected from the group consisting of these and combinations thereof are given below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to Rf.
Ｌ１：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ２：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ３：－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ５：－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ６：－ＣＯ－ＮＨ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ７：－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ８：－２価の芳香族基－Ｏ－ＣＯ－
Ｌ９：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１０：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１１：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１２：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１３：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１５：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１６：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１７：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１８：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１９：－２価の芳香族基－２価の脂肪族基
Ｌ２０：－２価の芳香族基－２価の脂肪族基－Ｏ－２価の脂肪族基－
Ｌ２１：－２価の芳香族基－２価の脂肪族基－Ｏ－２価の脂肪族基－Ｏ－
Ｌ２２：－ＣＯ－Ｏ－２価の脂肪族基－
Ｌ２３：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ L1: -CO-NH-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
L2: —CO—NH-divalent aliphatic group —O—CO—
L3: —CO-2 valent aliphatic group —O—CO—
L4: —CO—O-2 valent aliphatic group —O—CO—
L5: -valent aliphatic group -O-CO-
L6: —CO—NH-divalent aromatic group —O—CO—
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 divalent aromatic group -O-CO-NH-2 divalent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
L19: -2-valent aromatic group -2-valent aliphatic group L20: -2-valent aromatic group -2-valent aliphatic group -O-2-valent aliphatic group-
L21: a bivalent aromatic group, a bivalent aliphatic group, an O-2 valent aliphatic group, and -O-
L22: -CO-O-2 valent aliphatic group-
L23: —CO—O-2 valent aliphatic group —O—
　ここで２価の脂肪族基とは、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基またはポリアルキレンオキシ基を意味する。なかでもアルキレン基、置換アルキレン基、アルケニレン基、および置換アルケニレン基が好ましく、アルキレン基および置換アルキレン基がさらに好ましい。
　２価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。２価の脂肪族基の炭素原子数は、１～２０であることが好ましく、１～１５であることがより好ましく、１～１２であることがさらに好ましく、１～１０であることがさらにまた好ましく、１～８であることがよりさらに好ましく、１～４であることが特に好ましい。
　２価の脂肪族基の置換基の例としては、ハロゲン原子（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、アリールアミノ基およびジアリールアミノ基等が挙げられる。 Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
　２価の芳香族基の例としては、フェニレン基、置換フェニレン基、ナフタレン基および置換ナフタレン基が挙げられ、フェニレン基が好ましい。２価の芳香族基の置換基の例としては、上記２価の脂肪族基の置換基の例に加えて、アルキル基が挙げられる。 Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
　フッ素原子を有する繰り返し単位の含有量は、フッ素原子を有するラジカル重合性オリゴマーの全繰り返し単位に対して、２モル％～９８モル％であることが好ましく、１０モル％～９０モル％であることがより好ましい。 The content of the repeating unit having a fluorine atom is preferably 2 mol% to 98 mol%, preferably 10 mol% to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. Is more preferable.
　ラジカル重合性官能基を有する繰り返し単位としては、下記式（８）で表される繰り返し単位が好ましい。 As the repeating unit having a radical polymerizable functional group, a repeating unit represented by the following formula (8) is preferable.
Figure JPOXMLDOC01-appb-C000016
 （一般式（８）において、Ｒ801～Ｒ803は、それぞれ独立して、水素原子、アルキル基、又はハロゲン原子を表す。Ｙ8は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｔはラジカル重合性官能基を有する構造を表す。）
Figure JPOXMLDOC01-appb-C000016
 (In the general formula (8), R 801 to R 803 each independently represents a hydrogen atom, an alkyl group, or a halogen atom. Y 8 represents a single bond, or —CO—, —O—, — NH— represents a divalent linking group selected from the group consisting of a divalent aliphatic group, a divalent aromatic group, and combinations thereof, and T represents a structure having a radical polymerizable functional group.
　Ｒ801～Ｒ803としてのアルキル基は、炭素数１～６のアルキル基であることが好ましい。
　Ｔは一般式（９）で表されるラジカル重合性官能基を表すことが好ましい。 The alkyl group as R 801 to R 803 is preferably an alkyl group having 1 to 6 carbon atoms.
T preferably represents a radical polymerizable functional group represented by the general formula (9).
Figure JPOXMLDOC01-appb-C000017
 （　一般式（９）中、Ｒ901～Ｒ903は、それぞれ独立して、水素原子、アルキル基又はアリール基を表す。点線は、Ｙ8へ連結する基への結合を表す。）
Figure JPOXMLDOC01-appb-C000017
 (In the general formula (9), R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group. The dotted line represents a bond to a group linked to Y 8. )
　アルキル基の例は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。Ｒ901～Ｒ903はとしては、なかでも、水素原子またはメチル基が好ましい。 Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples thereof include 2-methylhexyl group and cyclopentyl group. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
　Ｙ8は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。組み合わせからなるＹ8の具体例を以下に挙げる。なお、下記例において左側が主鎖に結合し、右側が式（９）に結合する。 Y 8 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. To express. Specific examples of comprising the combination Y 8 below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the formula (9).
Ｌ１：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ２：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ３：－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ５：－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ６：－ＣＯ－ＮＨ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ７：－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ８：－２価の芳香族基－Ｏ－ＣＯ－
Ｌ９：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１０：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１１：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１２：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１３：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１５：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１６：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１７：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１８：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－ L1: -CO-NH-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
L2: —CO—NH-divalent aliphatic group —O—CO—
L3: —CO-2 valent aliphatic group —O—CO—
L4: —CO—O-2 valent aliphatic group —O—CO—
L5: -valent aliphatic group -O-CO-
L6: —CO—NH-divalent aromatic group —O—CO—
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 divalent aromatic group -O-CO-NH-2 divalent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
　ここで２価の脂肪族基とは、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基またはポリアルキレンオキシ基を意味する。なかでもアルキレン基、置換アルキレン基、アルケニレン基、および置換アルケニレン基が好ましく、アルキレン基および置換アルキレン基がさらに好ましい。
　２価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。２価の脂肪族基の炭素原子数は、１～２０であることが好ましく、１～１５であることがより好ましく、１～１２であることがさらに好ましく、１～１０であることがさらにまた好ましく、１～８であることがよりさらに好ましく、１～４であることが特に好ましい。
　２価の脂肪族基の置換基の例としては、ハロゲン原子（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、アリールアミノ基およびジアリールアミノ基等が挙げられる。 Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
　２価の芳香族基の例としては、フェニレン基、置換フェニレン基、ナフタレン基および置換ナフタレン基が挙げられ、フェニレン基が好ましい。２価の芳香族基の置換基の例としては、上記２価の脂肪族基の置換基の例に加えて、アルキル基が挙げられる。 Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
　ラジカル重合性官能基を有する繰り返し単位の含有量は、フッ素原子を有するラジカル重合性オリゴマーの全繰り返し単位に対して、２モル％～９８モル％であることが好ましく、１０モル％～９０モル％であることがより好ましい。 The content of the repeating unit having a radical polymerizable functional group is preferably 2 mol% to 98 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom, and is preferably 10 mol% to 90 mol%. It is more preferable that
　フッ素原子を有するラジカル重合性オリゴマーのゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によるポリスチレン換算の重量平均分子量は、２０００～２００００であることが好ましく、２０００～１５０００がより好ましく、２０００～１００００であることが最も好ましい。 The weight average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a fluorine atom as measured by gel permeation chromatography (GPC) is preferably 2000 to 20000, more preferably 2000 to 15000, and more preferably 2000 to 10,000. Most preferred.
　接着剤層前駆体がフッ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーを有する場合、フッ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーの含有量は、特に制限はなく、好ましくは、接着剤層前駆体の全固形分に対して、０．０１質量％以上２０質量％以下であることが好ましい。０．０１質量％未満であると、剥離性が不十分となる傾向がある。一方、２０質量％を超えると、接着性が低下する傾向がある。
　フッ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーは１種類のみでもよいし、２種類以上であってもよい。重合性モノマーが２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive layer precursor has a radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom, the content of the radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom is not particularly limited, preferably The total solid content of the adhesive layer precursor is preferably 0.01% by mass or more and 20% by mass or less. If it is less than 0.01% by mass, the peelability tends to be insufficient. On the other hand, when it exceeds 20 mass%, there exists a tendency for adhesiveness to fall.
The radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom may be only one type or two or more types. When there are two or more kinds of polymerizable monomers, the total is preferably in the above range.
［ケイ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマー］
　本発明におけるケイ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーは、シリコーンモノマーまたはシリコーンオリゴマーであることが好ましく、例えば、ポリジメチルシロキサン結合の少なくとも片末端が（メタ）アクリロイル基およびスチリル基等のエチレン性不飽和基となっている化合物が挙げられ、（メタ）アクリロイル基を有する化合物が好ましい。 [Radical polymerizable monomer and / or polymerizable oligomer having a silicon atom]
In the present invention, the radically polymerizable monomer and / or polymerizable oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer. For example, at least one terminal of a polydimethylsiloxane bond is a (meth) acryloyl group or a styryl group. And a compound having a (meth) acryloyl group is preferable.
　ケイ素原子を有するラジカル重合性オリゴマーのゲルパーミエーションクロマトグラフィー法によるポリスチレン換算の数平均分子量は、１，０００～１０，０００であることが好ましい。ケイ素原子を有するラジカル重合性オリゴマーのゲルパーミエーションクロマトグラフィー法によるポリスチレン換算の数平均分子量が１，０００未満または１０，０００以上の場合、ケイ素原子による剥離性等の性質が発現しにくくなる。 The number average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a silicon atom as measured by gel permeation chromatography is preferably 1,000 to 10,000. When the number average molecular weight in terms of polystyrene by a gel permeation chromatography method of a radically polymerizable oligomer having a silicon atom is less than 1,000 or 10,000 or more, properties such as releasability due to a silicon atom are hardly expressed.
　本発明におけるケイ素原子を有するラジカル重合性モノマーとしては、一般式（１１）または（１２）で示される化合物を用いることが好ましい。 As the radically polymerizable monomer having a silicon atom in the present invention, it is preferable to use a compound represented by the general formula (11) or (12).
Figure JPOXMLDOC01-appb-C000018
 （一般式（１１）及び（１２）中、Ｒ11～Ｒ19は、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、又はアリール基を表す。Ｚ11、Ｚ12、及びＺ13は、それぞれ独立に、ラジカル重合性基を表す。Ｌ11、Ｌ12、及び、Ｌ13はそれぞれ独立に、単結合又は二価の連結基を表す。ｎ及びｍは、それぞれ独立に０以上の整数を表す。）
Figure JPOXMLDOC01-appb-C000018
 (In the general formulas (11) and (12), R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group. Z 11 , Z 12 , and Z 13 each independently represents a radically polymerizable group, L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group, and n and m each independently represents 0 or more. Represents an integer.)
　一般式（１１）および（１２）中、Ｒ11～Ｒ19は、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、または、アリール基を表す。 In the general formulas (11) and (12), R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group.
　アルキル基は、直鎖状であっても、分枝鎖状であっても良く、炭素数１～５のアルキル基であることが好ましく、具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等が挙げられる。アルコキシ基は、－ＯＲ20を意味するもので、Ｒ20はアルキル基（好ましくは炭素数１～５のアルキル基）を表し、具体的には、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等が挙げられる。アルコキシカルボニル基は、－Ｃ（＝Ｏ）Ｒ21を意味するもので、Ｒ21はアルコキシ基（好ましくは炭素数１～５のアルコキシ基）を表し、具体的には、メトキシカルボニル、エトキシカルボニル、プロポキシカルボニル等が挙げられる。アリール基は、フェニル基、トリル基、ナフチル基などが挙げられ、それらは置換基を有していても良く、フェニルメチル（ベンジル）基、フェニルエチル基、フェニルプロピル基、フェニルブチル基、ナフチルメチル基等が挙げられる。 The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, n-propyl group. Group, isopropyl group and the like. An alkoxy group means —OR 20 , wherein R 20 represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group And a butoxy group. An alkoxycarbonyl group means —C (═O) R 21 , where R 21 represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specifically includes methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group, which may have a substituent, such as phenylmethyl (benzyl) group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl. Groups and the like.
　Ｌ11、Ｌ12、および、Ｌ13はそれぞれ独立に、単結合または二価の連結基を表す。二価の連結基としては、－ＣＯ－、－Ｏ－、－ＮＨ－、二価の脂肪族基、二価の芳香族基およびそれらの組み合わせからなる群より選ばれる二価の連結基を表す。 L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group. The divalent linking group represents a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. .
　ｎおよびｍは、それぞれ独立に０以上の整数を表し、０～１００の整数が好ましく、０～５０の整数がより好ましい。 N and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, and more preferably an integer of 0 to 50.
　Ｚ11、Ｚ12、およびＺ13は、それぞれ独立に、ラジカル重合性基を表し、下記一般式（ｉ）～（ｉｉｉ）のいずれかで表される官能基が特に好ましい。 Z 11 , Z 12 , and Z 13 each independently represent a radical polymerizable group, and a functional group represented by any one of the following general formulas (i) to (iii) is particularly preferable.
Figure JPOXMLDOC01-appb-C000019
 （一般式（ｉ）中、Ｒ101～Ｒ103はそれぞれ独立に、水素原子又は１価の有機基を表す。Ｘ101は、酸素原子、硫黄原子、又は－Ｎ（Ｒ104）－を表し、Ｒ104は、水素原子又は１価の有機基を表す。）
Figure JPOXMLDOC01-appb-C000019
 (In the general formula (i), R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group. X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —, R 104 represents a hydrogen atom or a monovalent organic group.)
　一般式（ｉ）において、Ｒ101～Ｒ103はそれぞれ独立に、水素原子または１価の有機基を表す。Ｒ101は、好ましくは、水素原子または置換基を有してもよいアルキル基などが挙げられ、なかでも、水素原子およびメチル基は、ラジカル反応性が高いことから好ましい。また、Ｒ102およびＲ103は、それぞれ独立に、好ましくは、水素原子、ハロゲン原子、アミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、または、置換基を有してもよいアリールスルホニル基を表し、なかでも、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基がラジカル反応性が高いことから好ましい。 In the general formula (i), R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group. R 101 preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity. R 102 and R 103 are each independently preferably a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, or optionally substituted alkyl. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent Represents an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, among which a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.
　Ｘ101は、酸素原子、硫黄原子、または－Ｎ（Ｒ104）－を表し、Ｒ104は、水素原子または１価の有機基を表す。１価の有機基としては、置換基を有してもよいアルキル基などが挙げられる。Ｒ104が、水素原子、メチル基、エチル基、または、イソプロピル基であることが、ラジカル反応性が高いことから好ましい。 X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —, and R 104 represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group which may have a substituent. R 104 is preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.
　導入し得る置換基としては、アルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、ハロゲン原子、アミノ基、アルキルアミノ基、アリールアミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、アミド基、アルキルスルホニル基、アリールスルホニル基などが挙げられる。 Examples of substituents that can be introduced include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, A nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.
Figure JPOXMLDOC01-appb-C000020
 （一般式（ｉｉ）中、Ｒ201～Ｒ205は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｙ201は、酸素原子、硫黄原子、又は－Ｎ（Ｒ206）－を表す。Ｒ206は、水素原子又は１価の有機基を表す。）
Figure JPOXMLDOC01-appb-C000020
 (In general formula (ii), R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group. Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —. R 206 represents a hydrogen atom or a monovalent organic group.)
　一般式（ｉｉ）において、Ｒ201～Ｒ205は、それぞれ独立に、水素原子または１価の有機基を表す。Ｒ201～Ｒ205は、それぞれ独立に、水素原子、ハロゲン原子、アミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、または、置換基を有してもよいアリールスルホニル基であることが好ましく、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、または、置換基を有してもよいアリール基であることがより好ましい。 In the general formula (ii), R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group. R 201 to R 205 each independently represents a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent. An aryl group that may have, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent It is preferably a good arylamino group, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group, having a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent. It is more preferably an alkyl group which may be substituted or an aryl group which may have a substituent.
　導入し得る置換基としては、一般式（ｉ）で記載した置換基と同様のものが挙げられる。
　Ｙ201は、酸素原子、硫黄原子、または－Ｎ（Ｒ206）－を表す。Ｒ206は、一般式（ｉ）のＲ104と同義であり、好ましい例も同様である。 Examples of the substituent that can be introduced include the same substituents as those described in formula (i).
Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —. R 206 has the same meaning as R 104 in formula (i), and preferred examples thereof are also the same.
Figure JPOXMLDOC01-appb-C000021
 （一般式（ｉｉｉ）中、Ｒ301～Ｒ303は、それぞれ独立に水素原子又は１価の有機基を表す。Ｚ301は、酸素原子、硫黄原子、－Ｎ（Ｒ304）－又は置換基を有してもよいフェニレン基を表す。Ｒ304は、一般式（ｉ）のＲ104と同義である。）
Figure JPOXMLDOC01-appb-C000021
 (In the general formula (iii), R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group. Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or a substituent. Represents a phenylene group which may have R. R 304 has the same meaning as R 104 in formula (i).
　一般式（ｉｉｉ）において、Ｒ301～Ｒ303は、それぞれ独立に水素原子または１価の有機基を表す。Ｒ301は、水素原子、または、置換基を有してもよいアルキル基であることが好ましく、なかでも、水素原子、または、メチル基であることが、ラジカル反応性が高いことからより好ましい。Ｒ302、および、Ｒ303は、それぞれ独立に、水素原子、ハロゲン原子、アミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、または、置換基を有してもよいアリールスルホニル基であることが好ましく、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、または、置換基を有してもよいアリール基であることが、ラジカル反応性が高いことからより好ましい。 In general formula (iii), R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group. R 301 is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group because of high radical reactivity. R 302 and R 303 are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent. An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent. An alkyl group that may have a substituent or an aryl group that may have a substituent is more preferable because of high radical reactivity.
　導入し得る置換基としては、一般式（ｉ）で記載した置換基と同様のものが挙げられる。Ｚ301は、酸素原子、硫黄原子、－Ｎ（Ｒ304）－または置換基を有してもよいフェニレン基を表す。Ｒ304は、一般式（ｉ）のＲ104と同義であり、１価の有機基としては、置換基を有してもよいアルキル基などが挙げられ、なかでも、メチル基、エチル基、および、イソプロピル基がラジカル反応性が高いことから好ましい。 Examples of the substituent that can be introduced include the same substituents as those described in formula (i). Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or an optionally substituted phenylene group. R 304 has the same meaning as R 104 in the general formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and An isopropyl group is preferable because of high radical reactivity.
　接着剤層前駆体がケイ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーを有する場合、ケイ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーの含有量は、接着剤前駆体の全固形分に対して、０．０１質量％以上２０質量％以下であることが好ましい。０．０１質量％未満であると、剥離性が低下する傾向がある。一方、２０質量％を超えると、接着性が低下する傾向がある。
　ケイ素原子を有するラジカル重合性モノマー又はオリゴマーは１種類のみでもよいし、２種類以上であってもよい。ケイ素原子を有するラジカル重合性モノマー又はオリゴマーが２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive layer precursor has a radically polymerizable monomer and / or polymerizable oligomer having a silicon atom, the content of the radically polymerizable monomer and / or polymerizable oligomer having a silicon atom is the total solid content of the adhesive precursor. It is preferable that it is 0.01 mass% or more and 20 mass% or less with respect to a minute. If it is less than 0.01% by mass, the peelability tends to decrease. On the other hand, when it exceeds 20 mass%, there exists a tendency for adhesiveness to fall.
There may be only one kind of radically polymerizable monomer or oligomer having a silicon atom, or two or more kinds. When there are two or more types of radically polymerizable monomers or oligomers having a silicon atom, the total is preferably in the above range.
　フッ素原子またはケイ素原子を有するラジカル重合性モノマーおよび／または重合性オリゴマーとしては、例えば、ＤＩＣ株式会社製のＲＳ－７５、ＲＳ－７２－Ｋ、ＲＳ－７６－Ｅ、ダイキン工業株式会社製のオプツールＤＡＣ－ＨＰ、信越化学工業株式会社製のＸ－２２－１６４、Ｘ－２２－１６４ＡＳ、Ｘ－２２－１６４Ａ、Ｘ－２２－１６４Ｂ、Ｘ－２２－１６４、Ｘ－２２－１６４Ｃ、Ｘ－２２－１６４Ｅ，ダイセル・サイテック株式会社製のＥＢＥＣＲＹＬ３５０、ＥＢＥＣＲＹＬ１３６０、デグサ社製のＴＥＧＯＲａｄ２７００などを挙げることができる。 Examples of the radical polymerizable monomer and / or polymerizable oligomer having a fluorine atom or a silicon atom include RS-75, RS-72-K, RS-76-E manufactured by DIC Corporation, and OPTOOL manufactured by Daikin Industries, Ltd. DAC-HP, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164, X-22-164C, X-22 manufactured by Shin-Etsu Chemical Co., Ltd. -164E, EBECRYL350, EBECRYL1360 manufactured by Daicel-Cytec, Inc., TEGORad2700 manufactured by Degussa, and the like.
＜＜（ｂ－２）光ラジカル開始剤、（ｂ－３）熱ラジカル開始剤＞＞
　本発明の接着剤層前駆体は、ラジカル重合開始剤、すなわち（ｂ－２）活性光線または放射線の照射（光照射）によりラジカルを発生する化合物（光ラジカル開始剤（光ラジカル重合開始剤））、または（ｂ－３）熱によりラジカルを発生する化合物（熱ラジカル開始剤（熱ラジカル重合開始剤））を含有することが好ましい。ラジカル重合開始剤の存在下で、ラジカル重合性モノマー又はオリゴマーに光を照射または加熱することで、ラジカルによる硬化反応が起こり、接着剤層前駆体の重合率を調整することができ、接着性を調節することができる。 << (b-2) Photoradical initiator, (b-3) Thermal radical initiator >>
The adhesive layer precursor of the present invention is a radical polymerization initiator, that is, (b-2) a compound that generates radicals upon irradiation with actinic rays or radiation (photoirradiation) (photoradical initiator (photoradical polymerization initiator)). Or (b-3) a compound that generates radicals by heat (thermal radical initiator (thermal radical polymerization initiator)). In the presence of a radical polymerization initiator, the radical polymerizable monomer or oligomer is irradiated with light or heated to cause a curing reaction due to radicals, and the polymerization rate of the adhesive layer precursor can be adjusted, thereby improving adhesion. Can be adjusted.
［光ラジカル開始剤］
　光ラジカル開始剤としては、例えば、以下に述べる重合開始剤として知られているものを用いることができる。
　前記光ラジカル開始剤としては、前記重合性モノマーとしての重合性基を有する反応性化合物における重合反応（架橋反応）を開始する能力を有する限り、特に制限はなく、公知の重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視の光線に対して感光性を有するものが好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。
　また、前記重合開始剤は、約３００ｎｍ～８００ｎｍ（好ましくは３３０ｎｍ～５００ｎｍ）の範囲内に少なくとも約５０の分子吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。 [Photo radical initiator]
As a photo radical initiator, what is known as a polymerization initiator described below can be used, for example.
The photoradical initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) in a reactive compound having a polymerizable group as the polymerizable monomer. Among known polymerization initiators It can be selected appropriately. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).
　前記光ラジカル開始剤としては、公知の化合物を制限なく使用できるが、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有するもの、オキサジアゾール骨格を有するもの、トリハロメチル基を有するものなど）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノン、アゾ系化合物、アジド化合物、メタロセン化合物、有機ホウ素化合物、鉄アレーン錯体などが挙げられる。 As the photo radical initiator, known compounds can be used without limitation. For example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group) , Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo Compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like.
　前記トリアジン骨格を有するハロゲン化炭化水素化合物としては、例えば、若林ら著、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，４２、２９２４（１９６９）記載の化合物、英国特許１３８８４９２号明細書記載の化合物、特開昭５３－１３３４２８号公報記載の化合物、独国特許３３３７０２４号明細書記載の化合物、Ｆ．Ｃ．ＳｃｈａｅｆｅｒなどによるＪ．Ｏｒｇ．Ｃｈｅｍ．；２９、１５２７（１９６４）記載の化合物、特開昭６２－５８２４１号公報記載の化合物、特開平５－２８１７２８号公報記載の化合物、特開平５－３４９２０号公報記載化合物、米国特許第４２１２９７６号明細書に記載されている化合物、などが挙げられる。 Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-258241, compound described in JP-A-5-281728, compound described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.
　前記米国特許第４２１２９７６号明細書に記載されている化合物としては、例えば、オキサジアゾール骨格を有する化合物（例えば、２－トリクロロメチル－５－フェニル－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（４－クロロフェニル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（１－ナフチル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（２－ナフチル）－１，３，４－オキサジアゾール、２－トリブロモメチル－５－フェニル－１，３，４－オキサジアゾール、２－トリブロモメチル－５－（２－ナフチル）－１，３，４－オキサジアゾール；２－トリクロロメチル－５－スチリル－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（４－クロロスチリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（４－メトキシスチリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（１－ナフチル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（４－ｎ－ブトキシスチリル）－１，３，４－オキサジアゾール、２－トリプロモメチル－５－スチリル－１，３，４－オキサジアゾールなど）などが挙げられる。 Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) ) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1 , 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 -Oxadiazole and the like).
　また、上記以外の光ラジカル開始剤として、アクリジン誘導体（例えば、９－フェニルアクリジン、１，７－ビス（９，９’－アクリジニル）ヘプタンなど）、Ｎ－フェニルグリシンなど、ポリハロゲン化合物（例えば、四臭化炭素、フェニルトリブロモメチルスルホン、フェニルトリクロロメチルケトンなど）、クマリン類（例えば、３－（２－ベンゾフラノイル）－７－ジエチルアミノクマリン、３－（２－ベンゾフロイル）－７－（１－ピロリジニル）クマリン、３－ベンゾイル－７－ジエチルアミノクマリン、３－（２－メトキシベンゾイル）－７－ジエチルアミノクマリン、３－（４－ジメチルアミノベンゾイル）－７－ジエチルアミノクマリン、３，３’－カルボニルビス（５，７－ジ－ｎ－プロポキシクマリン）、３，３’－カルボニルビス（７－ジエチルアミノクマリン）、３－ベンゾイル－７－メトキシクマリン、３－（２－フロイル）－７－ジエチルアミノクマリン、３－（４－ジエチルアミノシンナモイル）－７－ジエチルアミノクマリン、７－メトキシ－３－（３－ピリジルカルボニル）クマリン、３－ベンゾイル－５，７－ジプロポキシクマリン、７－ベンゾトリアゾール－２－イルクマリン、また、特開平５－１９４７５号公報、特開平７－２７１０２８号公報、特開２００２－３６３２０６号公報、特開２００２－３６３２０７号公報、特開２００２－３６３２０８号公報、特開２００２－３６３２０９号公報などに記載のクマリン化合物など）、アシルホスフィンオキサイド類（例えば、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフェニルホスフィンオキサイド、ＬｕｃｉｒｉｎＴＰＯなど）、メタロセン類（例えば、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフロロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウム、η５－シクロペンタジエニル－η６－クメニル－アイアン（１＋）－ヘキサフロロホスフェート（１－）など）、特開昭５３－１３３４２８号公報、特公昭５７－１８１９号公報、同５７－６０９６号公報、および米国特許第３６１５４５５号明細書に記載された化合物などが挙げられる。 Further, as photo radical initiators other than the above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, 9-phenylacridine, etc.) Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (eg, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1 -Pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 ′ Carbonyl bis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy- 3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2, 4,6-Trimethylbenzoyl) -phenyl Sphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) And compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.
　前記ケトン化合物としては、例えば、ベンゾフェノン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、４－メトキシベンゾフェノン、２－クロロベンゾフェノン、４－クロロベンゾフェノン、４－ブロモベンゾフェノン、２－カルボキシベンゾフェノン、２－エトキシカルボニルベンゾフェノン、ベンゾフェノンテトラカルボン酸またはそのテトラメチルエステル、４，４’－ビス（ジアルキルアミノ）ベンゾフェノン類（例えば、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビスジシクロヘキシルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４，４’－ビス（ジヒドロキシエチルアミノ）ベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４－ジメチルアミノベンゾフェノン、４－ジメチルアミノアセトフェノン、ベンジル、アントラキノン、２－ｔｅｒｔ－ブチルアントラキノン、２－メチルアントラキノン、フェナントラキノン、キサントン、チオキサントン、２－クロロ－チオキサントン、２，４－ジエチルチオキサントン、フルオレノン、２－ベンジル－ジメチルアミノ－１－（４－モルホリノフェニル）－１－ブタノン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノ－１－プロパノン、２－ヒドロキシ－２－メチル－〔４－（１－メチルビニル）フェニル〕プロパノールオリゴマー、ベンゾイン、ベンゾインエーテル類（例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインフェニルエーテル、ベンジルジメチルケタール）、アクリドン、クロロアクリドン、Ｎ－メチルアクリドン、Ｎ－ブチルアクリドン、Ｎ－ブチル－クロロアクリドンなどが挙げられる。
　市販品では、カヤキュアーＤＥＴＸ（日本化薬製）も好適に用いられる。 Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenones (eg, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexyl) Amino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzof Non, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoy Propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.
Kayacure DETX (manufactured by Nippon Kayaku) is also suitably used as a commercial product.
　光ラジカル開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、および、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号公報に記載のアシルホスフィンオキシド系開始剤も用いることができる。
　ヒドロキシアセトフェノン系開始剤としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ－１２７（商品名：いずれもＢＡＳＦ社製）を用いることができる。アミノアセトフェノン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、および、ＩＲＧＡＣＵＲＥ－３７９（商品名：いずれもＢＡＳＦ社製）を用いることができる。アミノアセトフェノン系開始剤として、３６５ｎｍまたは４０５ｎｍ等の長波光源に吸収波長がマッチングされた特開２００９－１９１１７９公報に記載の化合物も用いることができる。また、アシルホスフィン系開始剤としては市販品であるＩＲＧＡＣＵＲＥ－８１９やＤＡＲＯＣＵＲ－ＴＰＯ（商品名：いずれもＢＡＳＦ社製）を用いることができる。 As the photoradical initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
　光ラジカル開始剤として、より好ましくはオキシム系化合物が挙げられる。オキシム系開始剤の具体例としては、特開２００１－２３３８４２号記載の化合物、特開２０００－８００６８号記載の化合物、特開２００６－３４２１６６号記載の化合物を用いることができる。 More preferable examples of the photo radical initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
　本発明で光ラジカル開始剤として好適に用いられるオキシム誘導体等のオキシム化合物としては、例えば、３－ベンゾイロキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイロキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、および２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。 Examples of oxime compounds such as oxime derivatives that are preferably used as a photo radical initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.
　オキシムエステル化合物としては、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐ　ｐ．１６５３－１６６０）、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１５６－１６２、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年）ｐｐ．２０２－２３２、特開２０００－６６３８５号公報記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、特開２００６－３４２１６６号公報の各公報に記載の化合物等が挙げられる。
　市販品ではＩＲＧＡＣＵＲＥ－ＯＸＥ０１（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２（ＢＡＳＦ社製）も好適に用いられる。 Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) p. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used.
　また上記記載以外のオキシムエステル化合物として、カルバゾールＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許７６２６９５７号公報に記載の化合物、色素部位にニトロ基が導入された特開２０１０－１５０２５号公報および米国特許公開２００９－２９２０３９号記載の化合物、国際公開特許２００９－１３１１８９号公報に記載のケトオキシム系化合物、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物、４０５ｎｍに吸収極大を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報記載の化合物、などを用いてもよい。 Further, as oxime ester compounds other than those described above, compounds described in JP-T-2009-519904 in which oxime is linked to carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in Japanese Patent Application Laid-Open No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used. .
　好ましくはさらに、特開２００７－２３１０００号公報、および、特開２００７－３２２７４４号公報に記載される環状オキシム化合物に対しても好適に用いることができる。環状オキシム化合物の中でも、特に特開２０１０－３２９８５号公報、特開２０１０－１８５０７２号公報に記載されるカルバゾール色素に縮環した環状オキシム化合物は、高い光吸収性を有し高感度化の観点から好ましい。
　また、オキシム化合物の特定部位に不飽和結合を有する特開２００９－２４２４６９号公報に記載の化合物も、重合不活性ラジカルから活性ラジカルを再生することで高感度化を達成でき好適に使用することができる。 Preferably, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among cyclic oxime compounds, in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
Further, the compounds described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because high sensitivity can be achieved by regenerating the active radical from the polymerization inert radical. it can.
　最も好ましくは、特開２００７－２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示されるチオアリール基を有するオキシム化合物が挙げられる。 Most preferably, an oxime compound having a specific substituent as disclosed in JP 2007-26997A and an oxime compound having a thioaryl group as disclosed in JP 2009-191061 A can be mentioned.
　化合物のモル吸光係数は、公知の方法を用いることができるが、具体的には、例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｒｙ－５　ｓｐｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer manufactured by Varian) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.
　光ラジカル開始剤としては、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリルイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物およびその誘導体、シクロペンタジエン－ベンゼン－鉄錯体およびその塩、ハロメチルオキサジアゾール化合物、３－アリール置換クマリン化合物からなる群より選択される化合物が好ましい。 As photo radical initiators, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, trimethyl compounds, Selected from the group consisting of allylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 3-aryl substituted coumarin compound Are preferred.
　さらに好ましくは、トリハロメチルトリアジン化合物、α－アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾフェノン化合物、アセトフェノン化合物であり、トリハロメチルトリアジン化合物、α－アミノケトン化合物、オキシム化合物、トリアリールイミダゾールダイマー、ベンゾフェノン化合物からなる群より選ばれる少なくとも一種の化合物が最も好ましく、オキシム化合物を用いるのが最も好ましい。 More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, α-aminoketones Most preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, and most preferred are oxime compounds.
　本発明の接着剤層前駆体が光ラジカル開始剤を有する場合、光ラジカル開始剤の含有量は、接着剤層前駆体の全固形分に対し０．１質量％以上５０質量％以下であることが好ましく、０．１質量％以上３０質量％以下がより好ましく、０．１質量％以上２０質量％以下がさらに好ましい。
　光ラジカル開始剤は１種類のみでもよいし、２種類以上であってもよい。光ラジカル開始剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive layer precursor of the present invention has a photo radical initiator, the content of the photo radical initiator is 0.1% by mass or more and 50% by mass or less based on the total solid content of the adhesive layer precursor. Is preferable, 0.1 mass% or more and 30 mass% or less is more preferable, and 0.1 mass% or more and 20 mass% or less is further more preferable.
Only one type of photo radical initiator may be used, or two or more types may be used. When there are two or more types of photo radical initiators, the total is preferably in the above range.
［熱ラジカル開始剤］
　熱ラジカル開始剤としては、公知の熱ラジカル発生剤を用いることができる。
　熱ラジカル開始剤は、熱のエネルギーによってラジカルを発生し、重合性モノマーの重合反応を開始または促進させる化合物である。熱ラジカル発生剤を添加することによって、仮接着剤を用いて形成された接着剤層前駆体に対して熱を照射した後に、被処理部材と接着性支持体との仮接着を行う場合においては、熱により架橋性基を有する反応性化合物における架橋反応が進行することにより、後に詳述するように、接着剤層前駆体の接着性（すなわち、粘着性およびタック性）を前もって低下させることができる。
　一方、被処理部材と接着性支持体との仮接着を行った後に、接着性支持体における接着剤層前駆体に対して熱を照射した後に場合には、熱により架橋性基を有する反応性化合物における架橋反応が進行する。この結果、より強靭な接着剤層になり、被処理部材の機械的または化学的な処理を施している時などに生じやすい接着剤層前駆体の凝集破壊を抑制できる。すなわち、接着剤層前駆体における接着性を向上できる。
　好ましい熱ラジカル開始剤としては、上述した活性光線または放射線の照射によりラジカルを発生する化合物が挙げられるが、熱分解点が１３０℃～２５０℃、好ましくは１５０℃～２２０℃の範囲の化合物を好ましく使用することができる。
　熱ラジカル開始剤としては、芳香族ケトン類、オニウム塩化合物、有機過酸化物、チオ化合物、ヘキサアリールビイミダゾール化合物、ケトオキシムエステル化合物、ボレート化合物、アジニウム化合物、メタロセン化合物、活性エステル化合物、炭素ハロゲン結合を有する化合物、アゾ系化合物等が挙げられる。中でも、有機過酸化物またはアゾ系化合物がより好ましく、有機過酸化物が特に好ましい。
　具体的には、特開２００８－６３５５４号公報の段落００７４～０１１８に記載されている化合物が挙げられる。
　市販品では、パーブチルＺ（日油（株）製）を好適に用いることができる。 [Thermal radical initiator]
As the thermal radical initiator, a known thermal radical generator can be used.
The thermal radical initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable monomer. In the case of performing temporary adhesion between the member to be treated and the adhesive support after irradiating heat to the adhesive layer precursor formed using the temporary adhesive by adding a thermal radical generator As the crosslinking reaction proceeds in the reactive compound having a crosslinkable group by heat, the adhesiveness (that is, tackiness and tackiness) of the adhesive layer precursor may be lowered in advance as will be described in detail later. it can.
On the other hand, if the adhesive layer precursor in the adhesive support is irradiated with heat after temporary adhesion between the member to be processed and the adhesive support, the reactivity having a crosslinkable group by heat The crosslinking reaction in the compound proceeds. As a result, the adhesive layer becomes tougher, and cohesive failure of the adhesive layer precursor, which is likely to occur when mechanically or chemically treating the member to be treated, can be suppressed. That is, the adhesiveness in the adhesive layer precursor can be improved.
Preferable thermal radical initiators include compounds that generate radicals upon irradiation with actinic rays or radiation as described above, and compounds having a thermal decomposition point of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C. are preferred. Can be used.
Thermal radical initiators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens Examples thereof include a compound having a bond and an azo compound. Among these, organic peroxides or azo compounds are more preferable, and organic peroxides are particularly preferable.
Specifically, compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be mentioned.
In a commercial item, perbutyl Z (made by NOF Corporation) can be used conveniently.
　本発明における接着剤層前駆体が、ラジカル重合開始剤として、（ｂ－３）熱ラジカル重合開始剤を含有する場合（より好ましくは、（ｂ－２）光ラジカル重合開始剤と（ｂ－３）熱ラジカル重合開始剤とを含有する場合）、特に、高温時（例えば、１００℃）における接着性をより向上できる。 When the adhesive layer precursor in the present invention contains (b-3) a thermal radical polymerization initiator as a radical polymerization initiator (more preferably, (b-2) a photoradical polymerization initiator and (b-3) ) When containing a thermal radical polymerization initiator), in particular, the adhesiveness at high temperatures (for example, 100 ° C.) can be further improved.
　本発明における接着剤層前駆体は、（ｂ－２）光ラジカル重合開始剤を含有することが好ましい。
　また、本発明における接着剤層前駆体は、ラジカル重合開始剤を１種で含有しても、２種以上含有しても良い。 The adhesive layer precursor in the present invention preferably contains (b-2) a photoradical polymerization initiator.
Moreover, the adhesive layer precursor in the present invention may contain one kind of radical polymerization initiator or two or more kinds.
　接着剤層前駆体が熱ラジカル開始剤を有する場合、熱ラジカル開始剤の含有量は、接着剤層前駆体の全固形分に対し０．１質量％以上５０質量％以下であることが好ましく、より好ましくは０．１質量％以上３０質量％以下、さらに好ましくは０．１質量％以上２０質量％以下である。
　熱ラジカル開始剤は１種類のみでもよいし、２種類以上であってもよい。熱ラジカル開始剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive layer precursor has a thermal radical initiator, the content of the thermal radical initiator is preferably 0.1% by mass or more and 50% by mass or less based on the total solid content of the adhesive layer precursor, More preferably, it is 0.1 mass% or more and 30 mass% or less, More preferably, it is 0.1 mass% or more and 20 mass% or less.
Only one type of thermal radical initiator may be used, or two or more types may be used. When there are two or more thermal radical initiators, the total is preferably in the above range.
＜＜(ｂ－４)高分子化合物＞＞
　本発明の接着剤層前駆体は、塗布性を調節するために、必要に応じて高分子化合物を有していてもよい。なお、ここでいう塗布性とは、塗布後の膜厚の均一性や塗布後の膜形成性のことをいう。
　本発明においては、高分子化合物は任意のものを使用できる。
　例えば、炭化水素樹脂、ポリスチレン樹脂（例えば、アクリルニトリル／ブタジエン／スチレン共重合体（ＡＢＳ樹脂）、アクリルニトリル／スチレン共重合体（ＡＳ樹脂）、メチルメタクリレート／スチレン共重合体（ＭＳ樹脂）を含む）、ノボラック樹脂、フェノール樹脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂、アルキド樹脂、ポリウレタン樹脂、ポリイミド樹脂、ポリエチレン樹脂、ポリプロピレン、ポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、テフロン（登録商標）、（メタ）アクリル樹脂（例えばポリメタクリル酸メチル）、ポリアミド樹脂、ポリアセタール樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリブチレンテラフタレート樹脂、ポリエチレンテレフタラート樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリアリレート樹脂、ポリエーテルエーテルケトン樹脂、ポリアミドイミド樹脂などの合成樹脂や、天然ゴムなどの天然樹脂が挙げられる。中でも、炭化水素樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ＭＳ樹脂、ポリウレタン樹脂、ノボラック樹脂、ポリイミド樹脂が好ましく、炭化水素樹脂、ＭＳ樹脂、がさらに好ましく、アクリル樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ＭＳ樹脂がよりさらに好ましい。
　本発明において、バインダーは必要に応じて２種以上を組み合わせて使用しても良い。 << (b-4) polymer compound >>
The adhesive layer precursor of the present invention may have a polymer compound as necessary in order to adjust the coating property. Here, the coating property means the uniformity of the film thickness after coating and the film forming property after coating.
In the present invention, any polymer compound can be used.
For example, hydrocarbon resin, polystyrene resin (for example, acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene copolymer (AS resin), methyl methacrylate / styrene copolymer (MS resin) are included. ), Novolac resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyimide resin, polyethylene resin, polypropylene, polyvinyl chloride resin, polyvinyl acetate resin, Teflon (registered trademark) ), (Meth) acrylic resin (for example, polymethyl methacrylate), polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, polyethylene terephthalate resin, poly E double sulfide resins, polysulfone resins, polyethersulfone resins, polyarylate resins, polyether ether ketone resin, and synthetic resins such as polyamide-imide resins, and natural resins such as natural rubber. Among these, hydrocarbon resin, ABS resin, AS resin, MS resin, polyurethane resin, novolac resin, and polyimide resin are preferable, hydrocarbon resin and MS resin are more preferable, and acrylic resin, ABS resin, AS resin, and MS resin are more preferable. Further preferred.
In this invention, you may use a binder in combination of 2 or more type as needed.
　本発明においては、炭化水素樹脂として任意のものを使用できる。
　本発明における炭化水素樹脂は基本的には炭素原子と水素原子のみからなる樹脂を意味するが、基本となる骨格が炭化水素樹脂であれば、側鎖としてその他の原子を含んでいても良い。すなわち、炭素原子と水素原子のみからなる炭化水素樹脂に、アクリル樹脂、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルピロリドン樹脂のように、主鎖に炭化水素基以外の官能基が直接結合する場合も本発明における炭化水素樹脂に包含されるものであり、この場合、主鎖に炭化水素基が直接結合されてなる繰り返し単位の含有量が、樹脂の全繰り返し単位に対して３０モル％以上であることが好ましい。 In the present invention, any hydrocarbon resin can be used.
The hydrocarbon resin in the present invention basically means a resin composed of only carbon atoms and hydrogen atoms, but if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, when a functional group other than a hydrocarbon group is directly bonded to the main chain, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, or a polyvinylpyrrolidone resin, to a hydrocarbon resin consisting of only carbon atoms and hydrogen atoms. It is included in the hydrocarbon resin in the invention, and in this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is 30 mol% or more based on the total repeating unit of the resin. Is preferred.
　上記条件に合致する炭化水素樹脂としては例えば、ポリスチレン樹脂、テルペン樹脂、テルペンフェノール樹脂、変性テルペン樹脂、水添テルペン樹脂、水添テルペンフェノール樹脂、ロジン、ロジンエステル、水添ロジン、水添ロジンエステル、重合ロジン、重合ロジンエステル、変性ロジン、ロジン変性フェノール樹脂、アルキルフェノール樹脂、脂肪族石油樹脂、芳香族石油樹脂、水添石油樹脂、変性石油樹脂、脂環族石油樹脂、クマロン石油樹脂、インデン石油樹脂、ポリスチレン－ポリオレフィン共重合体、オレフィンポリマー（例えば、メチルペンテン共重合体）、および、シクロオレフィンポリマー（例えば、ノルボルネン共重合体、ジシクロペンタジエン共重合体、テトラシクロドデセン共重合体）などが挙げられる。 Examples of hydrocarbon resins that meet the above conditions include polystyrene resin, terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, and hydrogenated rosin ester. , Polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenolic resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, inden petroleum Resin, polystyrene-polyolefin copolymer, olefin polymer (eg, methylpentene copolymer), and cycloolefin polymer (eg, norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer), etc. Is mentioned.
　炭化水素樹脂は、中でも、ポリスチレン樹脂、テルペン樹脂、ロジン、石油樹脂、水素化ロジン、重合ロジン、オレフィンポリマー、または、シクロオレフィンポリマーであることが好ましく、ポリスチレン樹脂、テルペン樹脂、ロジン、オレフィンポリマー、または、シクロオレフィンポリマーであることがより好ましく、ポリスチレン樹脂、テルペン樹脂、ロジン、オレフィンポリマー、ポリスチレン樹脂、または、シクロオレフィンポリマーであることがさらに好ましく、ポリスチレン樹脂、テルペン樹脂、ロジン、シクロオレフィンポリマー、または、オレフィンポリマーであることがよりさらにポリスチレン樹脂またはシクロオレフィンモノマーポリマーであることが特に好ましい。 The hydrocarbon resin is preferably a polystyrene resin, a terpene resin, a rosin, a petroleum resin, a hydrogenated rosin, a polymerized rosin, an olefin polymer, or a cycloolefin polymer, and a polystyrene resin, a terpene resin, a rosin, an olefin polymer, Or it is more preferably a cycloolefin polymer, more preferably a polystyrene resin, terpene resin, rosin, olefin polymer, polystyrene resin, or cycloolefin polymer, polystyrene resin, terpene resin, rosin, cycloolefin polymer, Alternatively, an olefin polymer is more preferably a polystyrene resin or a cycloolefin monomer polymer.
　ポリスチレン樹脂としては、具体的にはポリスチレン、スチレン・アクリロニトリル樹脂、アクリロニトリル・ブタジエン・スチレン樹脂、メタクリル酸メチル・スチレン樹脂が挙げられる。好ましくは、メタクリル酸メチル・スチレン樹脂である。半導体基板の高温処理工程に対する耐熱性が求められることから２５０℃加熱時のアウトガスの発生量が３質量％以下が好ましい。より好ましくは２質量％以下の樹脂が好ましい。メタクリル酸メチル・スチレン樹脂の市販品として、エスチレンＭＳ－２００ＮＴ、エスチレンＭＳ－３００、エスチレンＭＳ－５００、エスチレンＭＳ－６００（新日鉄住金化学（株））や、セビアンＭＡＳ１０、ＭＡＳ３０（ダイセルポリマー（株）が特に好ましく使用できる。 Specific examples of polystyrene resin include polystyrene, styrene / acrylonitrile resin, acrylonitrile / butadiene / styrene resin, and methyl methacrylate / styrene resin. A methyl methacrylate / styrene resin is preferable. Since the heat resistance with respect to the high temperature process of a semiconductor substrate is calculated | required, the generation amount of the outgas at the time of 250 degreeC heating is 3 mass% or less. More preferably, the resin is 2% by mass or less. Commercial products of methyl methacrylate / styrene resin include Estyrene MS-200NT, Estyrene MS-300, Estyrene MS-500, Estyrene MS-600 (Nippon Steel & Sumikin Chemical Co., Ltd.), Sebian MAS10, MAS30 (Daicel Polymer Co., Ltd.) Can be particularly preferably used.
　シクロオレフィンポリマーとしては、ノルボルネン系重合体、単環の環状オレフィンの重合体、環状共役ジエンの重合体、ビニル脂環式炭化水素重合体、およびこれら重合体の水素化物などが挙げられる。シクロオレフィンポリマーの好ましい例としては、下記一般式（ＩＩ）で表される繰り返し単位を少なくとも１種以上含む付加（共）重合体、および、一般式（Ｉ）で表される繰り返し単位の少なくとも１種以上をさらに含んでなる付加（共）重合体が挙げられる。また、シクロオレフィンポリマーの他の好ましい例としては、一般式（ＩＩＩ）で表される環状繰り返し単位を少なくとも１種含む開環（共）重合体が挙げられる。 Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferred examples of the cycloolefin polymer include addition (co) polymers containing at least one repeating unit represented by the following general formula (II), and at least one repeating unit represented by the general formula (I). An addition (co) polymer further comprising a species or more is mentioned. Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式中、ｍは０～４の整数を表す。Ｒ1～Ｒ6は、それぞれ、水素原子または炭素数１～１０の炭化水素基を表し、Ｘ1～Ｘ3、および、Ｙ1～Ｙ3は、それぞれ、水素原子、炭素数１～１０の炭化水素基、ハロゲン原子、ハロゲン原子で置換された炭素数１～１０の炭化水素基、－（ＣＨ2）ｎＣＯＯＲ11、－（ＣＨ2）ｎＯＣＯＲ12、－（ＣＨ2）ｎＮＣＯ、－（ＣＨ2）ｎＮＯ2、－（ＣＨ2）ｎＣＮ、－（ＣＨ2）ｎＣＯＮＲ13Ｒ14、－（ＣＨ2）ｎＮＲ15Ｒ16、－（ＣＨ2）ｎＯＺ、－（ＣＨ2）ｎＷ、または、Ｘ1とＹ1、Ｘ2とＹ2、若しくはＸ3とＹ3から構成された（－ＣＯ）2Ｏ、（－ＣＯ）2ＮＲ17を表す。Ｒ11、Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ16およびＲ17は、それぞれ、水素原子、または、炭化水素基（好ましくは炭素数１～２０の炭化水素基）、Ｚは、炭化水素基、または、ハロゲンで置換された炭化水素基を表し、Ｗは、ＳｉＲ18 pＤ3-p（Ｒ18は炭素数１～１０の炭化水素基を表し、Ｄはハロゲン原子を表し、－ＯＣＯＲ18または－ＯＲ18を表し、ｐは０～３の整数を示す）を表す。ｎは０～１０の整数を表す。 In the formula, m represents an integer of 0 to 4. R 1 to R 6 each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X 1 to X 3 and Y 1 to Y 3 are each a hydrogen atom, or a carbon group having 1 to 10 carbon atoms. A hydrocarbon group, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted by a halogen atom, — (CH 2 ) nCOOR 11 , — (CH 2 ) nOCOR 12 , — (CH 2 ) nNCO, — (CH 2 ) NNO 2 , — (CH 2 ) nCN, — (CH 2 ) nCONR 13 R 14 , — (CH 2 ) nNR 15 R 16 , — (CH 2 ) nOZ, — (CH 2 ) nW, or X 1 It represents (—CO) 2 O, (—CO) 2 NR 17 composed of Y 1 , X 2 and Y 2 , or X 3 and Y 3 . R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), and Z is a carbon atom Represents a hydrogen group or a hydrocarbon group substituted with halogen, W represents SiR 18 p D 3-p (R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, Represents OCOR 18 or —OR 18 , and p represents an integer of 0 to 3. n represents an integer of 0 to 10.
　ノルボルネン系重合体は、特開平１０－７７３２号公報、特表２００２－５０４１８４号公報、ＵＳ２００４／２２９１５７Ａ１号公報あるいはＷＯ２００４／０７０４６３Ａ１号公報等に開示されている。ノルボルネン系重合体は、ノルボルネン系多環状不飽和化合物同士を付加重合することによって得ることができる。また、必要に応じ、ノルボルネン系多環状不飽和化合物と、エチレン、プロピレン、ブテン；ブタジエン、イソプレンのような共役ジエン；エチリデンノルボルネンのような非共役ジエンとを付加重合することもできる。このノルボルネン系重合体は、三井化学（株）よりアペルの商品名で発売されており、ガラス転移温度（Ｔｇ）の異なる例えばＡＰＬ８００８Ｔ（Ｔｇ７０℃）、ＡＰＬ６０１３Ｔ（Ｔｇ１２５℃）あるいはＡＰＬ６０１５Ｔ（Ｔｇ１４５℃）などのグレードがある。ポリプラスチック（株）よりＴＯＰＡＳ８００７、同５０１３、同６０１３、同６０１５などのペレットが発売されている。
　さらに、Ｆｅｒｒａｎｉａ社よりＡｐｐｅａｒ３０００が発売されている。 Norbornene-based polymers are disclosed in JP-A-10-7732, JP-T 2002-504184, US2004 / 229157A1 or WO2004 / 070463A1. The norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, a norbornene-based polycyclic unsaturated compound and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene can also be subjected to addition polymerization. This norbornene polymer is marketed by Mitsui Chemicals, Inc. under the name of Apel, and has different glass transition temperatures (Tg) such as APL8008T (Tg70 ° C), APL6013T (Tg125 ° C), APL6015T (Tg145 ° C), etc. There are grades. Pellets such as TOPAS 8007, 5013, 6013, 6015, etc. are available from Polyplastics.
Further, Appear 3000 is sold by Ferrania.
　ノルボルネン系重合体の水素化物は、特開平１－２４０５１７号公報、特開平７－１９６７３６号公報、特開昭６０－２６０２４号公報、特開昭６２－１９８０１号公報、特開２００３－１１５９７６７号公報あるいは特開２００４－３０９９７９号公報等に開示されているように、多環状不飽和化合物を付加重合あるいはメタセシス開環重合した後、水素添加することにより製造できる。
　前記一般式（ＩＩＩ）中、Ｒ5およびＲ6は、水素原子またはメチル基であることが好ましく、Ｘ3およびＹ3は水素原子であることが好ましく、その他の基は適宜選択される。このノルボルネン系重合体は、ＪＳＲ（株）からアートン（Ａｒｔｏｎ）ＧあるいはアートンＦという商品名で発売されており、また日本ゼオン（株）からゼオノア（Ｚｅｏｎｏｒ）ＺＦ１４、ＺＦ１６、ゼオネックス（Ｚｅｏｎｅｘ）２５０、同２８０、同４８０Ｒという商品名で市販されており、これらを使用することができる。 The hydrides of norbornene polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, and JP-A-2003-1159767. Alternatively, as disclosed in JP-A-2004-309979, etc., it can be produced by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization and then hydrogenation.
In the general formula (III), R 5 and R 6 are preferably hydrogen atoms or methyl groups, X 3 and Y 3 are preferably hydrogen atoms, and other groups are appropriately selected. This norbornene polymer is sold under the trade name Arton G or Arton F by JSR Co., Ltd., and Zeonor ZF14, ZF16, Zeonex 250, Nippon Zeon Co., Ltd., These are commercially available under the trade names 280 and 480R, and these can be used.
　高分子化合物のゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によるポリスチレン換算の重量平均分子量は、１０，０００～１，０００，０００であることが好ましく、５０，０００～５００，０００であることが好ましく、１００，０００～３００，０００であることがより好ましい。 The polystyrene equivalent weight average molecular weight of the polymer compound by gel permeation chromatography (GPC) method is preferably 10,000 to 1,000,000, preferably 50,000 to 500,000, More preferably, it is 100,000 to 300,000.
　接着剤層前駆体が高分子化合物を有する場合、高分子化合物の含有量は、本発明の接着剤層前駆体の全固形分に対して、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、２０質量％以上であることがさらに好ましい。
　また、高分子化合物の含有量は、本発明の接着剤層前駆体の全固形分に対して、７０質量％以下であることが好ましく、６０質量％以下であることがより好ましく、５０質量％以下であることがさらに好ましく、４０質量％以下であることが特に好ましい。
　高分子化合物は１種類のみでもよいし、２種類以上であってもよい。高分子化合物が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive layer precursor has a polymer compound, the content of the polymer compound is preferably 5% by mass or more based on the total solid content of the adhesive layer precursor of the present invention. More preferably, it is more preferably 20% by mass or more.
The content of the polymer compound is preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass with respect to the total solid content of the adhesive layer precursor of the present invention. More preferably, it is more preferably 40% by mass or less.
Only one type of polymer compound may be used, or two or more types may be used. When there are two or more kinds of polymer compounds, the total is preferably within the above range.
　また、重合性モノマーおよび高分子化合物の含有量の比率（質量比）（ラジカル重合性モノマー／高分子化合物）は、１００／０～１０／９０であることが好ましく、１００／０～２０／８０であることがより好ましく、１００／０～３０／７０であることがさらに好ましい。 Further, the content ratio (mass ratio) of the polymerizable monomer and the polymer compound (radical polymerizable monomer / polymer compound) is preferably 100/0 to 10/90, and preferably 100/0 to 20/80. It is more preferable that the ratio is 100/0 to 30/70.
＜非重合性のフッ素原子を有する高分子化合物＞
　本発明の接着剤前駆体層は、非重合性のフッ素原子を有する高分子化合物を含むことが好ましい。非重合性のフッ素原子を有する高分子化合物としては、１種または２種以上の含フッ素単官能モノマーからなる重合体を好ましく使用できる。より具体的には、テトラフルオロエチレン、ヘキサフルオロプロペン、テトラフルオロエチレンオキシド、ヘキサフルオロプロペンオキシド、パーフルオロアルキルビニルエーテル、クロロトリフルオロエチレン、ビニリデンフルオライド、パーフルオロアルキル基含有（メタ）アクリル酸エステルから選ばれる１種又は２種以上の含フッ素単官能モノマーの単独重合体又はこれらモノマーの共重合体、該含フッ素単官能モノマーの１種又は２種以上とエチレンとの共重合体、該含フッ素単官能モノマーの１種又は２種以上とクロロトリフルオロエチレンとの共重合体から選ばれる少なくとも１種の含フッ素樹脂等を挙げることができる。 <High molecular compound having non-polymerizable fluorine atom>
The adhesive precursor layer of the present invention preferably contains a polymer compound having a non-polymerizable fluorine atom. As the polymer compound having a non-polymerizable fluorine atom, a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used. More specifically, it is selected from tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester. Homopolymer of one or more fluorine-containing monofunctional monomers or a copolymer of these monomers, a copolymer of one or more of the fluorine-containing monofunctional monomers and ethylene, the fluorine-containing monomer Examples thereof include at least one fluorine-containing resin selected from a copolymer of one or more functional monomers and chlorotrifluoroethylene.
　非重合性のフッ素原子を有する高分子化合物としては、パーフルオロアルキル基含有（メタ）アクリル酸エステルから合成できるパーフルオロアルキル基含有の（メタ）アクリル樹脂であることが好ましい。 The polymer compound having a non-polymerizable fluorine atom is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic ester.
　パーフルオロアルキル基含有（メタ）アクリル酸エステルとしては、具体的には下記式（１０１）で表される化合物であることが好ましい。
　式（１０１）
Figure JPOXMLDOC01-appb-C000023
 Specifically, the perfluoroalkyl group-containing (meth) acrylic acid ester is preferably a compound represented by the following formula (101).
Formula (101)
Figure JPOXMLDOC01-appb-C000023
　一般式（１０１）中、Ｒ101、Ｒ102、Ｒ103はそれぞれ独立に、水素原子、アルキル基、又はハロゲン原子を表す。Ｙ101は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｒｆはフッ素原子またはフッ素原子を少なくとも一つ有する一価の有機基である。 In General Formula (101), R 101 , R 102 , and R 103 each independently represent a hydrogen atom, an alkyl group, or a halogen atom. Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. To express. Rf is a fluorine atom or a monovalent organic group having at least one fluorine atom.
　一般式（１０１）中、Ｒ101、Ｒ102、Ｒ103で表されるアルキル基の例は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。Ｒ101～Ｒ103はとしては、なかでも、水素原子またはメチル基が好ましい。 In the general formula (101), examples of the alkyl group represented by R 101 , R 102 , R 103 are preferably alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Examples include octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 101 to R 103 are preferably a hydrogen atom or a methyl group.
　Ｙ101は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表し、２価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。２価の脂肪族基の炭素原子数は、１～２０であることが好ましく、１～１５であることがより好ましく、１～１２であることがさらに好ましく、１～１０であることがさらにまた好ましく、１～８であることがよりさらに好ましく、１～４であることが特に好ましい。　２価の芳香族基の例としては、フェニレン基、置換フェニレン基、ナフタレン基および置換ナフタレン基が挙げられ、フェニレン基が好ましい。
Ｙ101としては、２価の直鎖状構造の脂肪族基であることが好ましい。 Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. The divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4. Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
Y 101 is preferably an aliphatic group having a divalent linear structure.
　Ｒｆで表される、フッ素原子を有する一価の有機基としては、特に限定はないが、炭素数１～３０の含フッ素アルキル基が好ましく、炭素数１～２０がより好ましく、炭素数１～１５の含フッ素アルキル基が特に好ましい。この含フッ素アルキル基は、直鎖｛例えば－ＣＦ2ＣＦ3、－ＣＨ2（ＣＦ2）4Ｈ、－ＣＨ2（ＣＦ2）8ＣＦ3、－ＣＨ2ＣＨ2（ＣＦ2）4Ｈ等｝であっても、分岐構造｛例えば－ＣＨ（ＣＦ3）2、－ＣＨ2ＣＦ（ＣＦ3）2、－ＣＨ（ＣＨ3）ＣＦ2ＣＦ3、－ＣＨ（ＣＨ3）（ＣＦ2）5ＣＦ2Ｈ等｝を有していてもよく、また脂環式構造（好ましくは５員環又は６員環、例えばペルフルオロシクロへキシル基、ペルフルオロシクロペンチル基又はこれらで置換されたアルキル基等）を有していてもよく、エーテル結合（例えば－ＣＨ2ＯＣＨ2ＣＦ2ＣＦ3、－ＣＨ2ＣＨ2ＯＣＨ2Ｃ4Ｆ8Ｈ、－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2Ｃ8Ｆ17、－ＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2Ｈ等）を有していてもよい。また、ペルフルオロアルキル基であってもよい。 The monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to Fifteen fluorine-containing alkyl groups are particularly preferred. This fluorine-containing alkyl group is a straight chain {for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc. }, A branched structure {eg, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like} and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these). An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , —CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
　即ち、パーフルオロアルキル基含有（メタ）アクリル樹脂としては、具体的には下記式（１０２）で表される繰り返し単位を有する。
　式（１０２）
Figure JPOXMLDOC01-appb-C000024
 That is, the perfluoroalkyl group-containing (meth) acrylic resin specifically has a repeating unit represented by the following formula (102).
Formula (102)
Figure JPOXMLDOC01-appb-C000024
　一般式（１０２）中、Ｒ101、Ｒ102、Ｒ103、Ｙ101、Ｒｆはそれぞれ、一般式（１０１）と同義であり、好ましい態様も同義である。 In General Formula (102), R 101 , R 102 , R 103 , Y 101 , and Rf are each synonymous with General Formula (101), and preferred embodiments are also synonymous.
　パーフルオロアルキル基含有（メタ）アクリル樹脂は、剥離性の観点から任意にパーフルオロアルキル基含有（メタ）アクリル酸エステルに加えて、共重合成分を選択することができる。共重合成分を形成し得るラジカル重合性化合物としては、例えば、アクリル酸エステル類、メタクリル酸エステル類、Ｎ，Ｎ－２置換アクリルアミド類、Ｎ，Ｎ－２置換メタクリルアミド類、スチレン類、アクリロニトリル類、メタクリロニトリル類などから選ばれるラジカル重合性化合物が挙げられる。 In the perfluoroalkyl group-containing (meth) acrylic resin, a copolymer component can be selected in addition to the perfluoroalkyl group-containing (meth) acrylic acid ester from the viewpoint of peelability. Examples of the radical polymerizable compound capable of forming a copolymer component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, and acrylonitriles. And radical polymerizable compounds selected from methacrylonitriles and the like.
　より具体的には、例えば、アルキルアクリレート（該アルキル基の炭素原子数は１～２０のものが好ましい）等のアクリル酸エステル類、（例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸アミル、アクリル酸エチルヘキシル、アクリル酸オクチル、アクリル酸－ｔ－オクチル、クロルエチルアクリレート、２，２－ジメチルヒドロキシプロピルアクリレート、５－ヒドロキシペンチルアクリレート、トリメチロールプロパンモノアクリレート、ペンタエリヌリトールモノアクリレート、グリシジルアクリレート、ベンジルアクリレート、メトキシベンジルアクリレート、フルフリルアクリレート、テトラヒドロフルフリルアクリレートなど）、アリールアクリレート（例えば、フェニルアクリレートなど）、アルキルメタクリレート（該アルキル基の炭素原子は１～２０のものが好ましい）等のメタクリル酸エステル類（例えば、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、アミルメタクリレート、ヘキシルメタクリレート、シクロヘキシルメタクリレート、ベンジルメタクリレート、クロルベンジルメタクリレート、オクチルメタクリレート、４－ヒドロキシブチルメタクゾレート、５－ヒドロキシペンチルメタクリレート、２，２－ジメチル－３－ヒドロキシプロピルメタクリレート、トリメチロールプロパンモノメタクリレート、ペンタエリスリトールモノメタクリレート、グリシジルメタクリレート、フルフリルメタクリレート、テトラヒドロフルフリルメタクリレートなど）、アリールメタクリレート（例えば、フェニルメタクリレート、クレジルメタクリレート、ナフチルメタクリレートなど）、スチレン、アルキルスチレン等のスチレン（例えば、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、イソプロピルスチレン、ブチルスチレン、ヘキシルスチレン、シクロヘキシルスチレン、デシルスチレン、ベンジルスチレン、クロルメチルスチレン、トリフルオルメチルスチレン、エトキシメチルスチレン、アセトキシメチルスチレンなど）、アルコキシスチレン（例えば、メトキシスチレン、４－メトキシ－３－メチルスチレン、ジメトキシスチレンなど）、ハロゲンスチレン（例えば、クロルスチレン、ジクロルスチレン、トリクロルスチレン、テトラクロルスチレン、ペンタクロルスチレン、プロムスチレン、ジブロムスチレン、ヨードスチレン、フルオルスチレン、トリフルオルスチレン、２－ブロム－４－トリフルオルメチルスチレン、４－フルオル－３－トリフルオルメチルスチレンなど）、アクリロニトリル、メタクリロニトリルアクリル酸、カルボン酸を含有するラジカル重合性化合物（アクリル酸、メタクリル酸、イタコン酸、クロトン酸、インクロトン酸、マレイン酸、ｐ－カルボキシルスチレン、及びこれらの酸基の金属塩、アンモニウム塩化合物等）が挙げられるが、剥離性の観点から特に、炭素数１～２４の炭化水素基を有する（メタ）アクリル酸エステルが好ましく、例えば（メタ）アクリル酸のメチル、ブチル、２－エチルヘキシル、ラウリル、ステアリル、グリシジルエステル等が挙げられ、２－エチルヘキシル、ラウリル、ステアリル等の高級アルコールの（メタ）アクリレート、特にアクリレートが好ましい。 More specifically, for example, acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms), such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic Butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerynuri Tall monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (for example, phenyl Methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl) such as acrylate) and alkyl methacrylate (wherein the alkyl group preferably has 1 to 20 carbon atoms). Methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, Glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl Methacrylate), aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), styrene such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl) Styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4-methoxy-3-methyl styrene, Dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene, trichlors) Tylene, tetrachlorostyrene, pentachlorostyrene, prom styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc. ), Radically polymerizable compounds containing acrylonitrile, methacrylonitrile acrylic acid, carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxylstyrene, and the acid groups thereof. Metal salts, ammonium salt compounds, etc.). From the viewpoint of peelability, (meth) acrylic acid esters having a hydrocarbon group having 1 to 24 carbon atoms are particularly preferred, for example, methyl (meth) acrylate, butyl , 2-ethylhexyl, lauryl, su Allyl, include such glycidyl ester, 2-ethylhexyl, lauryl, higher alcohol (meth) acrylate stearyl, especially acrylate.
　上述した非重合性のフッ素原子を有する高分子化合物として、市販されているものとしては、テフロン（登録商標）（デュポン社）、テフゼル（デュポン社）、フルオン（旭硝子社）、ヘイラー（SolvaySolexis社）、ハイラー（SolvaySolexis社）、ルミフロン（旭硝子社）、アフラス（旭硝子社）、セフラルソフト（セントラル硝子社）、セフラルコート（セントラル硝子社）、等のフッ素樹脂、ヴァイトン（デュポン社）、カルレッツ（デュポン社）、ＳＩＦＥＬ（信越化学工業社）等の商標名のフッ素ゴム、クライトックス（デュポン社）、フォンブリン（ダイトクテック社）、デムナム(ダイキン工業社)等のパーフルオロポリエーテルオイルをはじめとする各種のフッ素オイルや、ダイフリーＦＢシリーズ（ダイキン工業社）、メガファックシリーズ（ＤＩＣ社）等の商標名のフッ素含有離型剤などが挙げられるが、これらに限定されるものではなく、非重合性のフッ素原子を有する高分子化合物であればいかなるものでも好適に使用できる。   As the above-mentioned polymer compounds having non-polymerizable fluorine atoms, those commercially available include Teflon (registered trademark) (DuPont), Tefzel (DuPont), Fullon (Asahi Glass), Halar (SolvaySolexis) , Fluororesins such as Hyler (SolvaySolexis), Lumiflon (Asahi Glass), Afras (Asahi Glass), Cefral Soft (Central Glass), Cefral Coat (Central Glass), Vuitton (DuPont), Kalrez (DuPont), Fluoro rubbers with trade names such as SIFEL (Shin-Etsu Chemical Co., Ltd.), various fluorines including perfluoropolyether oils such as Krytox (DuPont Co., Ltd.), Fomblin (Daito Tech Co., Ltd.), and Demnum (Daikin Kogyo Co., Ltd.) Oil, Daifree FB series (Daikin Industries), Mega Fuck Examples include fluorine-containing mold release agents such as series (DIC), but are not limited to these, and any polymer compound having a non-polymerizable fluorine atom can be suitably used. it can.
　非重合性のフッ素原子を有する高分子化合物のゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によるポリスチレン換算の重量平均分子量は、２０００～１０００００であることが好ましく、２０００～５００００がより好ましく、２０００～１００００であることが最も好ましい。 The weight average molecular weight in terms of polystyrene by a gel permeation chromatography (GPC) method of the polymer compound having a non-polymerizable fluorine atom is preferably 2000 to 100,000, more preferably 2000 to 50,000, and more preferably 2000 to 10,000. Most preferably it is.
　非重合性のフッ素原子を有する高分子化合物は、接着剤層前駆体にフッ素原子を有するラジカル重合性化合物を有する場合に、特に剥離性の向上効果が大きく、フッ素原子を有するラジカル重合性化合物と非重合性のフッ素原子を有する高分子化合物の組み合わせで使用することが最も好ましい。 The polymer compound having a non-polymerizable fluorine atom is particularly effective when the adhesive layer precursor has a radical polymerizable compound having a fluorine atom. It is most preferable to use a combination of polymer compounds having non-polymerizable fluorine atoms.
　本発明では、接着剤層前駆体における、フッ素原子を有するラジカル重合性化合物と非重合性のフッ素原子を有する高分子化合物の比（質量比）が５：９５～５０：５０であることが好ましく、１０：９０～４０：６０であることがより好ましく、１５：８５～３０：７０であることが好ましくい。 In the present invention, the ratio (mass ratio) of the radically polymerizable compound having fluorine atoms and the polymer compound having non-polymerizable fluorine atoms in the adhesive layer precursor is preferably 5:95 to 50:50. 10:90 to 40:60 is more preferable, and 15:85 to 30:70 is preferable.
　フッ素原子を有する非重合性の高分子化合物の含有量は、良好な剥離性の観点から、上記接着剤層前駆体の全固形分に対して、１～９９質量％が好ましく、３～９５質量％がより好ましく、５～９０質量％がさらに好ましい。 The content of the non-polymerizable polymer compound having a fluorine atom is preferably 1 to 99% by mass, preferably 3 to 95% by mass with respect to the total solid content of the adhesive layer precursor, from the viewpoint of good releasability. % Is more preferable, and 5 to 90% by mass is more preferable.
＜＜連鎖移動剤＞＞
　本発明における接着剤層前駆体は、連鎖移動剤を含有することが好ましい。連鎖移動剤は、例えば高分子辞典第三版（高分子学会編、２００５年）６８３－６８４頁に定義されている。連鎖移動剤としては、例えば、分子内にＳＨ、ＰＨ、ＳｉＨ、ＧｅＨを有する化合物群が用いられる。これらは、低活性のラジカル種に水素供与して、ラジカルを生成するか、もしくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。仮接着剤には、特に、チオール化合物（例えば、２－メルカプトベンズイミダゾール類、２－メルカプトベンズチアゾール類、２－メルカプトベンズオキサゾール類、３－メルカプトトリアゾール類、５－メルカプトテトラゾール類等）を好ましく用いることができる。 << Chain transfer agent >>
The adhesive layer precursor in the present invention preferably contains a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) are preferably used as the temporary adhesive. be able to.
　接着剤層前駆体が連鎖移動剤を有する場合、連鎖移動剤の好ましい含有量は、接着剤層前駆体の全固形分１００質量部に対し、好ましくは０．０１～２０質量部、さらに好ましくは１～１０質量部、特に好ましくは１～５質量部である。
　連鎖移動剤は１種類のみでもよいし、２種類以上であってもよい。連鎖移動剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive layer precursor has a chain transfer agent, the preferred content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass relative to the total solid content of the adhesive layer precursor. 1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass.
Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably within the above range.
＜＜重合禁止剤＞＞
　本発明における接着剤層前駆体には、接着剤層前駆体の製造中または保存中において高分子化合物およびラジカル重合性モノマーの不要な熱重合を防止するために、少量の重合禁止剤を添加するのが好ましい。
　重合禁止剤としては、例えば、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔｅｒｔ－ブチルカテコール、ベンゾキノン、４，４′－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２′－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシルアミンアルミニウム塩が好適に挙げられる。
　接着剤層前駆体が重合禁止剤を有する場合、重合禁止剤の添加量は、接着剤層前駆体の全固形分に対して、約０．０１～約５質量％であるのが好ましい。
　重合禁止剤は１種類のみでもよいし、２種類以上であってもよい。重合禁止剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 << Polymerization inhibitor >>
A small amount of a polymerization inhibitor is added to the adhesive layer precursor in the present invention to prevent unnecessary thermal polymerization of the polymer compound and the radical polymerizable monomer during the production or storage of the adhesive layer precursor. Is preferred.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and N-nitroso-N-phenylhydroxylamine aluminum salt.
When the adhesive layer precursor has a polymerization inhibitor, the addition amount of the polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the adhesive layer precursor.
Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more polymerization inhibitors, the total is preferably in the above range.
＜＜高級脂肪酸誘導体等＞＞
　本発明における接着剤層前駆体には、酸素による重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体等を添加して、塗布後の乾燥の過程で接着剤層前駆体の表面に偏在させてもよい。
　接着剤層前駆体が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の添加量は、接着剤層前駆体の全固形分に対して、約０．１～約１０質量％であるのが好ましい。
　高級脂肪酸誘導体等は１種類のみでもよいし、２種類以上であってもよい。高級脂肪酸誘導体等が２種類以上の場合は、その合計が上記範囲であることが好ましい。 << Higher fatty acid derivatives, etc. >>
In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the adhesive layer precursor in the present invention, and the adhesive layer precursor in the drying process after coating. It may be unevenly distributed on the surface of the body.
When the adhesive layer precursor has a higher fatty acid derivative, the addition amount of the higher fatty acid derivative is preferably about 0.1 to about 10% by mass with respect to the total solid content of the adhesive layer precursor.
Only one type of higher fatty acid derivative or the like may be used. When two or more types of higher fatty acid derivatives are used, the total is preferably within the above range.
＜＜溶剤＞＞
　本発明における接着剤層前駆体を塗布によって層状にする場合、溶剤を配合することが好ましい。
　溶剤は、接着性層を形成できれば、公知のものを制限なく使用できる。 << Solvent >>
When the adhesive layer precursor in the present invention is layered by coating, it is preferable to blend a solvent.
Any known solvent can be used without limitation as long as an adhesive layer can be formed.
　有機溶剤としては、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、オキシ酢酸アルキル（例：オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－オキシプロピオン酸アルキルエステル類（例：３－オキシプロピオン酸メチル、３－オキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－オキシプロピオン酸アルキルエステル類（例：２－オキシプロピオン酸メチル、２－オキシプロピオン酸エチル、２－オキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－オキシ－２－メチルプロピオン酸メチルおよび２－オキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等、並びに、芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等が好適に挙げられる。 Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )) 2 Oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic Carbonization Preferable examples of hydrogens include toluene, xylene, anisole, limonene and the like.
　これらの溶剤は、塗布面状の改良などの観点から、２種以上を混合する形態も好ましい。この場合、特に好ましくは、上記の３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートから選択される２種以上で構成される混合溶液である。 These solvents are preferably mixed in two or more types from the viewpoint of improving the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
　接着剤層前駆体が溶剤を有する場合、接着剤層前駆体形成用組成物中における溶剤の含有量は、塗布性の観点から、接着剤層前駆体形成用組成物の全固形分濃度が５～８０質量％になる量とすることが好ましく、５～７０質量％がさらに好ましく、１０～６０質量％が特に好ましい。
　溶剤は１種類のみでもよいし、２種類以上であってもよい。溶剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive layer precursor has a solvent, the content of the solvent in the adhesive layer precursor forming composition is 5 in terms of the total solid content of the adhesive layer precursor forming composition from the viewpoint of applicability. The amount is preferably ˜80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass.
One type of solvent may be sufficient and two or more types may be sufficient. When there are two or more solvents, the total is preferably in the above range.
＜＜界面活性剤＞＞
　本発明における接着剤層前駆体には、塗布性をより向上させる観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。 << Surfactant >>
Various surfactants may be added to the adhesive layer precursor in the present invention from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
　特に、フッ素系界面活性剤を含有することで、塗布液として調製したときの液特性（特に、流動性）がより向上することから、塗布厚の均一性や省液性をより改善することができる。
　即ち、フッ素系界面活性剤を含有する塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させることにより、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μｍ程度の薄膜を形成した場合であっても、厚みムラの小さい均一厚の膜形成をより好適に行える点で有効である。 In particular, by containing a fluorosurfactant, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved. it can.
That is, in the case of forming a film using a coating solution containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating solution. The coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
　フッ素系界面活性剤中のフッ素含有率は、３質量％～４０質量％が好適であり、より好ましくは５質量％～３０質量％であり、特に好ましくは７質量％～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、溶解性も良好である。 The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、同Ｆ７８１（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
　ノニオン系界面活性剤として具体的には、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレートおよびプロポキシレート（例えば、グリセロールプロポキシレート、グリセリンエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル（ＢＡＳＦ社製のプルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１、ソルスパース２００００（日本ルーブリゾール（株）製）等が挙げられる。 Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, manufactured by BASF) 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Rusupasu 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
　カチオン系界面活性剤として具体的には、フタロシアニン誘導体（商品名：ＥＦＫＡ－７４５、森下産業（株）製）、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等が挙げられる。 Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
　アニオン系界面活性剤として具体的には、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）社製）等が挙げられる。 Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
　シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング（株）製「トーレシリコーンＤＣ３ＰＡ」、「トーレシリコーンＳＨ７ＰＡ」、「トーレシリコーンＤＣ１１ＰＡ」，「トーレシリコーンＳＨ２１ＰＡ」，「トーレシリコーンＳＨ２８ＰＡ」、「トーレシリコーンＳＨ２９ＰＡ」、「トーレシリコーンＳＨ３０ＰＡ」、「トーレシリコーンＳＨ８４００」、モメンティブ・パフォーマンス・マテリアルズ社製「ＴＳＦ－４４４０」、「ＴＳＦ－４３００」、「ＴＳＦ－４４４５」、「ＴＳＦ－４４６０」、「ＴＳＦ－４４５２」、信越シリコーン株式会社製「ＫＰ３４１」、「ＫＦ６００１」、「ＫＦ６００２」、ビックケミー社製「ＢＹＫ３０７」、「ＢＹＫ３２３」、「ＢＹＫ３３０」等が挙げられる。
　接着剤層前駆体が界面活性剤を有する場合、界面活性剤の添加量は、接着剤層前駆体の全固形分に対して、０．００１質量％～２．０質量％が好ましく、より好ましくは０．００５質量％～１．０質量％である。
　界面活性剤は１種類のみでもよいし、２種類以上であってもよい。界面活性剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
When the adhesive layer precursor has a surfactant, the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably based on the total solid content of the adhesive layer precursor. Is 0.005% by mass to 1.0% by mass.
Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
＜＜その他の添加剤＞＞
　本発明における接着剤層前駆体は、本発明の効果を損なわない範囲で、必要に応じて、各種添加物、例えば、硬化剤、硬化触媒、シランカップリング剤、充填剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は接着剤層前駆体の固形分の３質量％以下とすることが好ましい。 << Other additives >>
The adhesive layer precursor in the present invention is various additives, for example, a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, an oxidation as long as the effects of the present invention are not impaired. An inhibitor, an ultraviolet absorber, an aggregation inhibitor and the like can be blended. When blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the adhesive layer precursor.
　接着剤層前駆体または接着剤層を形成するには、接着剤層前駆体形成用組成物（例えば、接着剤層前駆体塗布液）を、従来公知のスピンコート法、スプレー法、ローラーコート法、フローコート法、ドクターコート法、浸漬法などを用いて、次いで、乾燥（ベーク）することにより形成することができる。乾燥は、例えば、６０～１５０℃で、１０秒～２分行うことができる。 In order to form an adhesive layer precursor or an adhesive layer, a composition for forming an adhesive layer precursor (for example, an adhesive layer precursor coating solution) is applied to a conventionally known spin coating method, spray method, roller coating method. Then, it can be formed by drying (baking) using a flow coating method, a doctor coating method, a dipping method or the like. Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
　接着剤層前駆体および接着剤層の厚みは、それぞれ、１～５００μｍが好ましく、１～１００μｍがより好ましく、１～１０μｍがさらに好ましい。 The thicknesses of the adhesive layer precursor and the adhesive layer are each preferably 1 to 500 μm, more preferably 1 to 100 μm, and even more preferably 1 to 10 μm.
　接着剤層前駆体の２５℃における貯蔵弾性率は、１Ｍ～１０ＧＰａであることが好ましく、１０Ｍ～１０ＧＰａであることがより好ましく、１００Ｍ～１０ＧＰａであることがさらに好ましい。弾性率は、例えば粘弾性測定装置Ｒｈｅｏｓｏｌ－Ｇ１０００（ＵＢＭ社製）により測定することが可能である。このような弾性率とし、さらに、保護層を後述するような弾性率とすることにより、デバイスを研磨した際に生じる凹凸をより効果的に抑制でき、後述するデバイスウエハの薄型化時の強接着性と、デバイウエハの分離時の易剥離性をより効果的に両立することができる。 The storage elastic modulus at 25 ° C. of the adhesive layer precursor is preferably 1 M to 10 GPa, more preferably 10 M to 10 GPa, and further preferably 100 M to 10 GPa. The elastic modulus can be measured by, for example, a viscoelasticity measuring device Rheosol-G1000 (manufactured by UBM). By adopting such an elastic modulus, and further, the protective layer having an elastic modulus as described later, unevenness generated when the device is polished can be more effectively suppressed, and strong adhesion at the time of thinning the device wafer described later is achieved. And easy peeling at the time of separation of the Debye wafer can be more effectively achieved.
＜（Ａ）支持体＞
　本発明の積層体は、（Ａ）支持体（キャリア基板ともいう）を有する。
　支持体の素材は特に限定されないが、例えば、シリコン基板、ガラス基板、金属基板などが挙げられるが、半導体装置の基板として代表的に用いられるシリコン基板を汚染しにくい点や、半導体装置の製造工程において汎用されている静電チャックを使用できる点などを鑑みると、シリコン基板であることが好ましい。
　支持体の厚みは、例えば、３００μｍ～５ｍｍの範囲内とされるが、特に限定されるものではない。 <(A) Support>
The laminate of the present invention has (A) a support (also referred to as a carrier substrate).
The material of the support is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and the like. In view of the fact that a widely used electrostatic chuck can be used, a silicon substrate is preferable.
The thickness of the support is, for example, in the range of 300 μm to 5 mm, but is not particularly limited.
＜（Ｃ）保護層＞
　本発明の積層体は、（Ｃ）保護層を有する。保護層を設けることにより、研磨した際の凹凸を抑制することができる。
　保護層は、公知のものを制限なく使用することができるが、後述するデバイスチップを確実に保護できるものが好ましい。 <(C) protective layer>
The laminate of the present invention has (C) a protective layer. By providing the protective layer, unevenness when polished can be suppressed.
Although a well-known thing can be used for a protective layer without a restriction | limiting, what can protect the device chip mentioned later reliably is preferable.
　保護層を構成する材料としては、被処理基材を保護する目的であれば、制限なく公知の化合物を使用することができる。具体的には、フェノール樹脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂、アルキド樹脂、ポリウレタン、ポリイミド、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリ酢酸ビニル、テフロン（登録商標）、ＡＢＳ樹脂、ＡＳ樹脂、アクリル樹脂、ポリアミド、ポリアセタール、ポリカーボネート、ポリフェニレンエーテル、ポリブチレンテラフタレート、ポリエチレンテレフタラート、環状ポリオレフィン、ポリフェニレンスルフィド、ポリスルホン、ポリエーテルスルホン、ポリアリレート、ポリエーテルエーテルケトン、ポリアミドイミドなどの合成樹脂や、ロジン、天然ゴムなどの天然樹脂、炭化水素樹脂を好ましく使用することができる。市販品としては、ＺＥＯＮＥＸ４８０Ｒ（日本ゼオン（株）製）などを好ましく用いることができる。
保護層を構成する材料は１種類のみでもよいし、２種類以上であってもよい。 As a material constituting the protective layer, a known compound can be used without limitation as long as it is intended to protect the substrate to be treated. Specifically, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, polyimide, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, Teflon (registered trademark), ABS Resin, AS resin, acrylic resin, polyamide, polyacetal, polycarbonate, polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polysulfone, polyethersulfone, polyarylate, polyetheretherketone, polyamideimide, etc. Synthetic resins, natural resins such as rosin and natural rubber, and hydrocarbon resins can be preferably used. As a commercial item, ZEONEX480R (made by Nippon Zeon Co., Ltd.) etc. can be used preferably.
There may be only one type of material constituting the protective layer, or two or more types.
　保護層の軟化点は、１７０℃以上２５０℃以下であることが好ましく、２００℃以上２５０℃以下であることがより好ましい。軟化点が１７０℃以上２５０℃以下であるポリエーテルスルホン樹脂、ポリカーボネート樹脂、ポリスチレン樹脂、炭化水素樹脂、及びポリエーテルエーテルケトン樹脂であることがさらに好ましく、軟化点が１７０℃以上２５０℃以下であるポリエーテルスルホン樹脂、ポリカーボネート樹脂、ポリスチレン樹脂及びポリエーテルエーテルケトン樹脂であることが最も好ましい。 The softening point of the protective layer is preferably 170 ° C. or higher and 250 ° C. or lower, and more preferably 200 ° C. or higher and 250 ° C. or lower. More preferred are a polyethersulfone resin, polycarbonate resin, polystyrene resin, hydrocarbon resin, and polyetheretherketone resin having a softening point of 170 ° C. or higher and 250 ° C. or lower, and a softening point of 170 ° C. or higher and 250 ° C. or lower. Most preferred are polyethersulfone resins, polycarbonate resins, polystyrene resins and polyetheretherketone resins.
　保護層の軟化点は、接着剤層前駆体および接着剤層の軟化点よりも低いことが好ましい。保護層の軟化点が、接着剤層前駆体の軟化点より低い場合、保護層の洗浄性が向上する傾向にある。保護層の軟化点と接着剤層前駆体の軟化点の差は、好ましくは、１０℃～２００℃であり、より好ましくは３０℃～２００℃である。 The softening point of the protective layer is preferably lower than the softening point of the adhesive layer precursor and the adhesive layer. When the softening point of the protective layer is lower than the softening point of the adhesive layer precursor, the detergency of the protective layer tends to be improved. The difference between the softening point of the protective layer and the softening point of the adhesive layer precursor is preferably 10 ° C to 200 ° C, more preferably 30 ° C to 200 ° C.
　また、保護層は、本発明の効果を損なわない範囲で必要に応じて、上記接着剤層前駆体に含有され得る化合物を含有できる。 In addition, the protective layer can contain a compound that can be contained in the adhesive layer precursor as necessary within a range not impairing the effects of the present invention.
　保護層を形成するには、保護層形成用組成物（保護層塗布液）を、従来公知のスピンコート法、スプレー法、ローラーコート法、フローコート法、ドクターコート法、浸漬法などを用いて、次いで、乾燥（ベーク）することにより形成することができる。乾燥は、例えば、６０～１５０℃で、１０秒～２分行うことができる。保護層塗布液は、上記樹脂および溶剤を含むことが好ましい。 In order to form the protective layer, the protective layer-forming composition (protective layer coating solution) is applied using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. Then, it can be formed by drying (baking). Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes. The protective layer coating solution preferably contains the resin and solvent.
　保護層の厚みは、１～３００μｍが好ましく、１０～２００μｍがより好ましく、２０～１５０μｍがさらに好ましい。デバイスウエハ表面に構造体を有する場合、構造体以上の厚みであることが好ましい。 The thickness of the protective layer is preferably 1 to 300 μm, more preferably 10 to 200 μm, and further preferably 20 to 150 μm. When having a structure on the surface of the device wafer, the thickness is preferably equal to or greater than the structure.
　保護層の２５℃における貯蔵弾性率は、１０Ｍ～１ＧＰａであることが好ましく、１００Ｍ～５ＧＰａであることがより好ましく、１０００Ｍ～３ＧＰａであることがさらに好ましい。
　保護層の貯蔵弾性率は、接着層前駆体の貯蔵弾性率よりも低い方が好ましく、［保護層の貯蔵弾性率］／［接着層前駆体の貯蔵弾性率］の値が、０．９～０．０１であることが好ましく、０．８～０．０５であることがより好ましく、０．５～０．１であることが最も好ましい。 The storage elastic modulus of the protective layer at 25 ° C. is preferably 10 M to 1 GPa, more preferably 100 M to 5 GPa, and even more preferably 1000 M to 3 GPa.
The storage elastic modulus of the protective layer is preferably lower than the storage elastic modulus of the adhesive layer precursor, and the value of [storage elastic modulus of protective layer] / [storage elastic modulus of adhesive layer precursor] is 0.9 to 0.01 is preferable, 0.8 to 0.05 is more preferable, and 0.5 to 0.1 is most preferable.
　本発明の保護層は、フッ素原子を有する非重合性の高分子化合物を含むことが好ましい。なお、フッ素原子を有する非重合性の高分子化合物の好ましい態様は、前述の接着剤層前駆体に含まれるフッ素原子を有する非重合性の高分子化合物に記載されたものと同様であり、好ましい範囲も同様である。 The protective layer of the present invention preferably contains a non-polymerizable polymer compound having a fluorine atom. The preferred embodiment of the non-polymerizable polymer compound having a fluorine atom is the same as that described in the non-polymerizable polymer compound having a fluorine atom contained in the above-mentioned adhesive layer precursor, and is preferred. The range is the same.
　非重合性のフッ素原子を有する高分子化合物の含有量は、良好な剥離性の観点から、上記保護層およびの全固形分に対して、０．０１～９９質量％が好ましく、０．０３～５０質量％がより好ましく、０．０５～１０質量％がさらに好ましい。 The content of the polymer compound having non-polymerizable fluorine atoms is preferably 0.01 to 99% by mass, preferably 0.03 to 99% by mass with respect to the total solid content of the protective layer, from the viewpoint of good releasability. 50% by mass is more preferable, and 0.05 to 10% by mass is further preferable.
　フッ素原子を有する非重合性の高分子化合物は、接着剤層前駆体にフッ素原子を有するラジカル重合性化合物を有する場合に、特に剥離性の向上効果が大きく、フッ素原子を有するラジカル重合性化合物とフッ素原子を有する非重合性の高分子化合物の組み合わせで使用することが最も好ましい。 The non-polymerizable polymer compound having a fluorine atom is particularly effective in improving the peelability when the adhesive layer precursor has a radical polymerizable compound having a fluorine atom. Most preferably, it is used in combination with a non-polymerizable polymer compound having a fluorine atom.
　フッ素原子を有する非重合性の高分子化合物は、保護層もしくは接着剤層前駆体の少なくともいずれか一層に含まれていることが好ましく、両層にふくまれていてもよい。剥離性の観点から、保護層もしくは接着剤層前駆体のいずれか一層に含まれていることが好ましく、本発明の軟化点が２５０℃以上の接着剤層を形成するために、保護層に含まれていることが最も好ましい。 The non-polymerizable polymer compound having a fluorine atom is preferably contained in at least one of the protective layer and the adhesive layer precursor, and may be contained in both layers. From the viewpoint of releasability, it is preferably contained in any one layer of the protective layer or the adhesive layer precursor, and included in the protective layer in order to form an adhesive layer having a softening point of 250 ° C. or higher of the present invention. Most preferably.
　本発明では、接着剤層前駆体におけるフッ素原子を有するラジカル重合性化合物と、保護層における非重合性のフッ素原子を有する高分子化合物の比（質量比）が５：９５～５：９５であることが好ましく、１０：９０～９０：１０であることがより好ましく、１５：８５～３０：７０であることが好ましくい。 In the present invention, the ratio (mass ratio) of the radical polymerizable compound having a fluorine atom in the adhesive layer precursor and the polymer compound having a non-polymerizable fluorine atom in the protective layer is 5:95 to 5:95. It is preferably 10:90 to 90:10, more preferably 15:85 to 30:70.
＜（Ｄ）デバイスウエハ＞
　本発明の積層体は、（Ｄ）デバイスウエハを有する。
　デバイスウエハは、公知のものを制限なく使用することができ、例えばＭＥＭＳ、センサー用デバイスなどが挙げられる。
　デバイスウエハは、表面上に構造体を有していることが好ましく、構造体としては高さ１μｍ以上１５０μｍ以下の構造体であることが好ましく、高さ１μｍ以上１５０μｍ以下の金属構造体（金属バンプともいう）を有していることが好ましい。構造体の高さは５～１００μｍであることが好ましい。 <(D) Device wafer>
The laminate of the present invention has (D) a device wafer.
A known device wafer can be used without limitation, and examples thereof include a MEMS and a sensor device.
The device wafer preferably has a structure on the surface. The structure is preferably a structure having a height of 1 μm to 150 μm, and a metal structure (metal bump) having a height of 1 μm to 150 μm. It is preferable to have (also called). The height of the structure is preferably 5 to 100 μm.
　デバイスウエハは、５００μｍ以上の膜厚を有することが好ましく、６００μｍ以上であることが好ましく、７００μｍ以上がであることがより好ましい。
　詳細は後述するが、デバイスウエハは、保護層と接している面とは逆の面に機械的または化学的な処理を施し、５００μｍ未満の膜厚に薄化することが好ましい。より好ましい膜厚は、４００μｍ以下であり、さらに好ましい膜厚は３００μｍ以下である。 The device wafer preferably has a film thickness of 500 μm or more, preferably 600 μm or more, and more preferably 700 μm or more.
Although details will be described later, the device wafer is preferably thinned to a thickness of less than 500 μm by subjecting the surface opposite to the surface in contact with the protective layer to mechanical or chemical treatment. A more preferable film thickness is 400 μm or less, and a more preferable film thickness is 300 μm or less.
キット：
　本発明は、樹脂と溶剤を含む保護層形成用組成物と、溶剤と重合性モノマーを含む接着剤層前駆体または接着剤層形成用組成物を含むキットに関する。
　接着剤層前駆体形成用組成物を支持体上に塗布し、接着剤層前駆体を形成後、保護層形成用組成物を塗布することで本発明の積層体を作製することが可能となる。また、保護層形成用組成物は、デバイス上に塗布して硬化してもよい。
　接着剤層前駆体または接着剤層形成用組成物および保護層形成用組成物のそれぞれの組成、好ましい範囲などは、上記接着剤層前駆体、および保護層の項で説明したものと同様である。 kit:
The present invention relates to a protective layer forming composition containing a resin and a solvent, and a kit containing an adhesive layer precursor or an adhesive layer forming composition containing a solvent and a polymerizable monomer.
It becomes possible to produce the laminate of the present invention by applying the composition for forming an adhesive layer precursor on a support, forming the adhesive layer precursor, and then applying the composition for forming a protective layer. . The composition for forming a protective layer may be applied on a device and cured.
The respective compositions and preferred ranges of the adhesive layer precursor or the adhesive layer forming composition and the protective layer forming composition are the same as those described in the paragraphs of the adhesive layer precursor and the protective layer. .
積層体の作製方法、半導体装置の製造方法：
　半導体の製造装置の製造方法は、被処理部材の第１の面と基板とを、本発明の保護層および接着剤層前駆体を介して接着させる工程、上記被処理部材の上記第１の面とは反対側の第２の面に対して、機械的または化学的な処理を施し、処理済部材を得る工程、および、上記接着剤層前駆体または接着剤層前駆体の硬化物（接着剤層）と上記処理済部材を分離する工程を有することを特徴とする。
　また、半導体装置の製造方法は、被処理部材の第１の面と基板とを保護層および接着剤層前駆体を介して接着させる工程の後、かつ、上記被処理部材の上記第１の面とは反対側の第２の面に対して、機械的または化学的な処理を施し、処理済部材を得る工程の前に、上記接着剤層前駆体を１５０℃～３００℃の温度で加熱する工程をさらに有することが好ましい。特に、本発明の積層体は、２５０℃以上の使用環境下での使用に適している。 Laminated body manufacturing method, semiconductor device manufacturing method:
The manufacturing method of the semiconductor manufacturing apparatus includes the step of bonding the first surface of the member to be processed and the substrate through the protective layer and the adhesive layer precursor of the present invention, and the first surface of the member to be processed. The second surface opposite to the first surface is subjected to mechanical or chemical treatment to obtain a treated member, and the adhesive layer precursor or a cured product of the adhesive layer precursor (adhesive) Layer) and the treated member.
Further, the method for manufacturing a semiconductor device includes the first surface of the member to be processed after the step of bonding the first surface of the member to be processed and the substrate through the protective layer and the adhesive layer precursor. The adhesive layer precursor is heated at a temperature of 150 ° C. to 300 ° C. prior to the step of subjecting the second surface opposite to the second surface to a mechanical or chemical treatment to obtain a treated member. It is preferable to further include a step. In particular, the laminate of the present invention is suitable for use in a use environment of 250 ° C. or higher.
　また、本発明の積層体は、（Ａ）支持体上に、（Ｂ２）接着剤層、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有することを特徴とする。このような積層体は、（Ｂ）接着剤層前駆体を有する（Ａ）支持体と（Ｃ）保護層を有する（Ｄ）デバイスウエハとを接着させる方法を接着させる方法により作製することができる。
　接着剤層前駆体は、接着剤層前駆体形成用組成物を活性光線もしくは放射線または熱を照射する工程により接着剤層前駆体形成用組成物中の重合性モノマーおよび／または重合性オリゴマーの重合率を１０～７０％に調節することで、接着剤層前駆体に変換される。この場合、加熱温度は５０℃～２２０℃が好ましく、１００～２１０℃がより好ましく、１６０～２００℃がさらに好ましい。
　また、本発明の積層体を形成した後、さらに活性光線もしくは放射線または熱を照射する工程により接着剤層前駆体中の重合性モノマーおよび／または重合性オリゴマーの重合率を５０～１００％に調節して、接着剤層とすることにより、接着性と易剥離性を向上させることができる。この場合、加熱温度は１５０℃～３００℃が好ましく、１７０～２５０℃がより好ましく、１８０～２２０℃がさらに好ましい。 The laminate of the present invention is characterized by having (B) an adhesive layer, (C) a protective layer, and (D) a device wafer in this order on (A) a support. Such a laminate can be produced by a method of bonding (B) a method of bonding (A) a support having an adhesive layer precursor and (C) a device wafer having a protective layer (D). .
The adhesive layer precursor is formed by polymerizing the polymerizable monomer and / or polymerizable oligomer in the adhesive layer precursor forming composition by irradiating the adhesive layer precursor forming composition with actinic rays, radiation or heat. By adjusting the rate to 10 to 70%, it is converted into an adhesive layer precursor. In this case, the heating temperature is preferably 50 ° C. to 220 ° C., more preferably 100 to 210 ° C., and further preferably 160 to 200 ° C.
In addition, after the laminate of the present invention is formed, the polymerization rate of the polymerizable monomer and / or polymerizable oligomer in the adhesive layer precursor is adjusted to 50 to 100% by a further step of irradiating actinic rays, radiation or heat. And by making it an adhesive bond layer, adhesiveness and easy peelability can be improved. In this case, the heating temperature is preferably 150 ° C. to 300 ° C., more preferably 170 to 250 ° C., and further preferably 180 to 220 ° C.
　以下、これらの詳細について説明するが、本発明の積層体の作製方法、半導体装置の製造方法は以下に限定されるものではない。 Hereinafter, although these details are explained, the production method of the layered product of the present invention and the manufacturing method of a semiconductor device are not limited to the following.
　図１Ａ、図１Ｂ、図１Ｃ、図１Ｄ、図１Ｅ、図１Ｆは、それぞれ、接着性支持体とデバイスウエハとの仮接着を説明する概略断面図、接着性支持体に仮接着されたデバイスウエハが薄型化された状態、接着性支持体とデバイスウエハを剥離した状態、および接着性支持体とデバイスウエハの表面の洗浄後の状態を示す概略断面図である。 1A, FIG. 1B, FIG. 1C, FIG. 1D, FIG. 1E, and FIG. 1F are schematic cross-sectional views illustrating temporary bonding between an adhesive support and a device wafer, respectively, and a device wafer temporarily bonded to the adhesive support It is a schematic sectional drawing which shows the state after washing | cleaning of the surface where the adhesive support body and the device wafer were peeled, and the state which peeled the adhesive support body and the device wafer.
　本発明の実施形態において、図１Ａに示すように、先ず、支持体１２の上に接着性層前駆体１１が設けられてなる接着性支持体前駆体１００が準備される。 In the embodiment of the present invention, as shown in FIG. 1A, first, an adhesive support precursor 100 in which an adhesive layer precursor 11 is provided on a support 12 is prepared.
　接着性支持体前駆体１００は、重合性モノマーおよび／または重合性オリゴマーを含む。 The adhesive support precursor 100 includes a polymerizable monomer and / or a polymerizable oligomer.
　接着性層前駆体形成用組成物１１は、図１Ｂに示すように、活性光線もしくは放射線または熱を照射する工程により、重合性モノマーの重合率を１０～７０％に調節することで、接着剤層前駆体１３となる。また、接着剤層前駆体の２５℃における貯蔵弾性率は、１０ＭＰＡ以上１ＧＰａ未満であることが好ましい。この範囲内に調節することで、後述するデバイスウエハの薄型化時の強接着性と、デバイウエハの分離時の易剥離性を両立することができる。 As shown in FIG. 1B, the adhesive layer precursor forming composition 11 is prepared by adjusting the polymerization rate of the polymerizable monomer to 10 to 70% by the step of irradiating actinic rays, radiation or heat. It becomes the layer precursor 13. Moreover, it is preferable that the storage elastic modulus in 25 degreeC of an adhesive bond layer precursor is 10 MPA or more and less than 1 GPa. By adjusting within this range, it is possible to achieve both strong adhesion at the time of thinning the device wafer described later and easy peelability at the time of separation of the Debye wafer.
　モノマーの重合率は、光開始剤、熱開始剤の含有量や、活性光線もしくは放射線または熱のエネルギー量を調節することがコントロールすることができる。 The monomer polymerization rate can be controlled by adjusting the content of the photoinitiator and thermal initiator, and the amount of actinic light, radiation, or heat energy.
　モノマーの重合率は、フーリエ変換型赤外分光法（FT-IR）を用いて、820-800cm-1付近にあるσ=CH(ビニル基CHの面外変角振動バンド)のピーク面積を測定し、活性光線もしくは放射線または熱を照射する前の状態のピーク面積を0％、ピークが完全に消失した状態を100％として、算出することができる。
フーリエ変換型赤外分光計としては、例えばDIGILAB社製 EXCALIBUR　FTS－３０００を使用することができる。 The polymerization rate of the monomer was measured by using Fourier transform infrared spectroscopy (FT-IR) and measuring the peak area of σ = CH (the out-of-plane bending vibration band of vinyl group CH) near 820-800 cm -1 The peak area before irradiation with actinic rays, radiation, or heat can be calculated as 0%, and the state in which the peak completely disappears can be calculated as 100%.
As the Fourier transform infrared spectrometer, for example, EXCALIBUR FTS-3000 manufactured by DIGILAB can be used.
　支持体１２上に、後述する保護層を設ける場合は保護層の表面に、適用（好ましくは塗布）し、次いで、乾燥（ベーク）することにより形成することができる。乾燥は、例えば、６０～１５０℃で、１０秒～２分行うことができる。 When providing the protective layer mentioned later on the support body 12, it can form by applying (preferably apply | coating) to the surface of a protective layer, and then drying (baking). Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
　次に、支持体と接着剤層前駆体を有する接着性支持体１００’と、保護層を有するデバイスウエハ６０（被処理部材）との仮接着、デバイスウエハの薄型化、および、接着性支持体とデバイスウエハの分離について詳細に説明する。 Next, temporary adhesion between an adhesive support 100 ′ having a support and an adhesive layer precursor and a device wafer 60 (member to be processed) having a protective layer, thinning of the device wafer, and adhesive support The device wafer separation will be described in detail.
　図１Ｂに示すように、デバイスウエハ６０（被処理部材）は、シリコン基板６１の表面６１ａに複数の構造体（デバイスチップ）６２が設けられてなる。
　ここで、シリコン基板６１の厚さは、例えば、２００～１２００μｍの範囲内となっている。デバイスチップ６２は例えば金属構造体であることが好ましく高さは１０～１００μｍの範囲内となっている。 As shown in FIG. 1B, the device wafer 60 (member to be processed) has a plurality of structures (device chips) 62 provided on the surface 61 a of the silicon substrate 61.
Here, the thickness of the silicon substrate 61 is in the range of 200 to 1200 μm, for example. The device chip 62 is preferably a metal structure, for example, and the height is in the range of 10 to 100 μm.
　表面６１ａ上に、保護層７１を設ける場合は保護層の表面に、適用（好ましくは塗布）し、次いで、乾燥（ベーク）することにより形成することができる。乾燥は、例えば、６０～１５０℃で、１０秒～２分行うことができる。保護層７１は、デバイスチップ６２を完全に覆っていることが好ましく、デバイスチップの高さがＸμｍ、保護層の厚みをＹμｍの場合、Ｘ＋１００≧Ｙ＞Ｘの式で表すことが好ましい。 When the protective layer 71 is provided on the surface 61a, it can be formed by applying (preferably coating) the surface of the protective layer and then drying (baking). Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes. The protective layer 71 preferably completely covers the device chip 62. When the height of the device chip is X μm and the thickness of the protective layer is Y μm, the protective layer 71 is preferably represented by the formula X + 100 ≧ Y> X.
　このように保護層７１がデバイスチップ６２を完全に被覆していることは、接着性支持体１００’により仮接着されたデバイスウエハ６０を薄型化することにより得られる薄型デバイスウエハのＴＴＶ（Ｔｏｔａｌ　Ｔｈｉｃｋｎｅｓｓ　Ｖａｒｉａｔｉｏｎ）をより低下したい場合（すなわち、薄型デバイスウエハの平坦性をより向上させたい場合）に有効である。
　すなわち、接着性支持体１００により仮接着されたデバイスウエハ６０を薄型化する場合においては、複数のデバイスチップ６２が為すデバイスウエハ６０の凹凸形状が、薄型デバイスウエハ６０’の裏面６１ｂ’に転写される傾向となり、ＴＴＶが大きくなる要素になり得る。
　一方、接着性支持体１００’により仮接着された保護層付デバイスウエハを薄型化する場合においては、先ず、複数のデバイスチップ６２を保護層によって保護しているため、保護層付デバイスウエハの、接着性支持体１００’との接触面において、凹凸形状をほとんど無くすことが可能である。よって、このような保護層付デバイスウエハを接着性支持体１００’によって支持した状態で薄型化しても、複数のデバイスチップ６２に由来する形状が、保護層付薄型デバイスウエハの裏面６１ｂに転写されるおそれは低減され、その結果、最終的に得られる薄型デバイスウエハのＴＴＶをより低下することができる。 The protective layer 71 completely covers the device chip 62 in this way is that a thin device wafer TTV (Total Thickness) obtained by thinning the device wafer 60 temporarily bonded by the adhesive support 100 ′. This is effective when it is desired to further reduce the variation (that is, when it is desired to further improve the flatness of the thin device wafer).
That is, when the device wafer 60 temporarily bonded by the adhesive support 100 is thinned, the uneven shape of the device wafer 60 formed by the plurality of device chips 62 is transferred to the back surface 61b ′ of the thin device wafer 60 ′. Tend to become a factor that increases TTV.
On the other hand, in the case of thinning the device wafer with a protective layer temporarily bonded by the adhesive support 100 ′, first, since the plurality of device chips 62 are protected by the protective layer, In the contact surface with the adhesive support 100 ′, it is possible to almost eliminate the uneven shape. Therefore, even if such a device wafer with a protective layer is thinned while being supported by the adhesive support 100 ′, the shape derived from the plurality of device chips 62 is transferred to the back surface 61b of the thin device wafer with a protective layer. As a result, the TTV of the thin device wafer finally obtained can be further reduced.
　続いて、図１Ｃに示す通り、表面６１ａ上に保護層７１を設けた場合、そして、接着性支持体１００’の接着剤層前駆体１３に対して、保護層７１を押し当てる。これにより、保護層７１と接着剤層前駆体１３とが接着し、接着性支持体１００’とデバイスウエハ６０とが仮接着する。
　また、この後、必要に応じて、接着性支持体１００’とデバイスウエハ６０との接着体を加熱し（熱を照射し）、接着性層前駆体の接着性をより強靭な接着剤層としてもよい。これにより、接着性支持体と被処理部材との界面におけるアンカー効果が促進され、デバイスウエハ６０の後述する機械的または化学的な処理を施している時などに生じやすい接着性層の凝集破壊を抑制できるため、接着性支持体１００’の接着性を高めることになり、さらに接着性層の弾性率が向上することでデバイウエハの分離時の易剥離性をも向上することができる。 Subsequently, as shown in FIG. 1C, when the protective layer 71 is provided on the surface 61a, the protective layer 71 is pressed against the adhesive layer precursor 13 of the adhesive support 100 ′. As a result, the protective layer 71 and the adhesive layer precursor 13 are bonded, and the adhesive support 100 ′ and the device wafer 60 are temporarily bonded.
Thereafter, if necessary, the adhesive body between the adhesive support 100 ′ and the device wafer 60 is heated (irradiated with heat) so that the adhesive layer precursor has a stronger adhesive layer. Also good. As a result, the anchor effect at the interface between the adhesive support and the member to be processed is promoted, and cohesive failure of the adhesive layer that is likely to occur when the device wafer 60 is subjected to mechanical or chemical processing described later is performed. Since it can suppress, it will raise the adhesiveness of adhesive support body 100 ', and also the ease of peeling at the time of isolation | separation of a Debye wafer can also be improved by improving the elasticity modulus of an adhesive layer.
　この場合の加熱温度は、１５０℃～３００℃であることが好ましく、１７０℃～２５０℃であることがより好ましく、１８０℃～２２０℃であることがさらに好ましい。
　この場合の加熱時間は、２０秒～１０分であることが好ましく、３０秒～５分であることがより好ましく、４０秒～３分であることがさらに好ましい。 In this case, the heating temperature is preferably 150 ° C. to 300 ° C., more preferably 170 ° C. to 250 ° C., and further preferably 180 ° C. to 220 ° C.
In this case, the heating time is preferably 20 seconds to 10 minutes, more preferably 30 seconds to 5 minutes, and further preferably 40 seconds to 3 minutes.
　次いで、図１Ｄに示すように、シリコン基板６１の裏面６１ｂに対して、機械的または化学的な処理、具体的には、グライディングや化学機械研磨（ＣＭＰ）等の薄膜化処理を施すことにより、シリコン基板６１の厚さを薄くし（例えば、厚さ１～２００μｍとし）、薄型デバイスウエハ６０’を得る。
　また、機械的または化学的な処理として、薄膜化処理の後に、薄型デバイスウエハ６０’の裏面６１ｂ’からシリコン基板を貫通する貫通孔（図示せず）を形成し、この貫通孔内にシリコン貫通電極（図示せず）を形成する処理を、必要に応じて行ってもよい。 Next, as shown in FIG. 1D, the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment, specifically, thinning treatment such as gliding or chemical mechanical polishing (CMP). The thickness of the silicon substrate 61 is reduced (for example, a thickness of 1 to 200 μm) to obtain a thin device wafer 60 ′.
Further, as a mechanical or chemical treatment, a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b ′ of the thin device wafer 60 ′ after the thinning process, and the silicon is penetrated into the through hole. You may perform the process which forms an electrode (not shown) as needed.
　次いで、図１Ｅに示すように接着性支持体１００’の接着剤層から薄型デバイスウエハ６０’の表面６１ａを脱離する。
　脱離の方法は特に限定されるものではないが、何ら処理することなく薄型デバイスウエハ６０’の端部からデバイスウエハに対して垂直方向に引き上げて剥離することが好ましい。 Next, as shown in FIG. 1E, the surface 61a of the thin device wafer 60 ′ is detached from the adhesive layer of the adhesive support 100 ′.
The method of detachment is not particularly limited, but it is preferable that the separation is performed by pulling up from the end of the thin device wafer 60 ′ in the direction perpendicular to the device wafer without any treatment.
＜剥離液＞
　以下、剥離液について詳細に説明する。 <Release solution>
Hereinafter, the stripping solution will be described in detail.
　剥離液としては、水および、溶剤（有機溶剤）を使用することができる。また、剥離液としては、保護層７１を溶解する有機溶剤が好ましい。有機溶剤としては、例えば、脂肪族炭化水素類（ヘキサン、ヘプタン、アイソパーＥ、Ｈ、Ｇ（エッソ化学（株）製）等）、芳香族炭化水素類（トルエン、キシレン等）、ハロゲン化炭化水素（メチレンジクロライド、エチレンジクロライド、トリクレン、モノクロルベンゼン等）、極性溶剤が挙げられる。極性溶剤としては、アルコール類（メタノール、エタノール、プロパノール、イソプロパノール、１－ブタノール、１－ペンタノール、１－ヘキサノール、１－ヘプタノール、１－オクタノール、２－オクタノール、２－エチル－１－ヘキサノール、１－ノナノール、１－デカノール、ベンジルアルコール、エチレングリコールモノメチルエーテル、２－エトキシエタノール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノヘキシルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、ポリエチレングリコールモノメチルエーテル、ポリプロピレングリコール、テトラエチレングリコール、エチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル、メチルフェニルカルビノール、ｎ－アミルアルコール、メチルアミルアルコール等）、ケトン類（アセトン、メチルエチルケトン、エチルブチルケトン、メチルイソブチルケトン、シクロヘキサノン等）、エステル類（酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸アミル、酢酸ベンジル、乳酸メチル、乳酸ブチル、エチレングリコールモノブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールアセテート、ジエチルフタレート、レブリン酸ブチル等）、その他（トリエチルフォスフェート、トリクレジルフォスフェート、Ｎ－フェニルエタノールアミン、Ｎ－フェニルジエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、４－（２－ヒドロキシエチル）モルホリン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン等）等が挙げられる。 As the stripping solution, water and a solvent (organic solvent) can be used. Moreover, as a peeling liquid, the organic solvent which melt | dissolves the protective layer 71 is preferable. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons. (Methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents. Polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone) , Cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate Etc.), others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine) , N- phenyldiethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N- dimethylacetamide, N- methylpyrrolidone and the like) and the like.
　さらに、剥離性の観点から、剥離液は、アルカリ、酸、および界面活性剤を含んでいても良い。これらの成分を配合する場合、配合量は、それぞれ、剥離液の０．１～５．０質量％であることが好ましい。
　さらに剥離性の観点から、２種以上の有機溶剤および水、２種以上のアルカリ、酸および界面活性剤を混合する形態も好ましい。 Furthermore, from the viewpoint of peelability, the stripping solution may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amount is preferably 0.1 to 5.0% by mass of the stripping solution.
Further, from the viewpoint of peelability, a form in which two or more organic solvents and water, two or more alkalis, an acid, and a surfactant are mixed is also preferable.
　アルカリとしては、例えば、第三リン酸ナトリウム、第三リン酸カリウム、第三リン酸アンモニウム、第二リン酸ナトリウム、第二リン酸カリウム、第二リン酸アンモニウム、炭酸ナトリウム、炭酸カリウム、炭酸アンモニウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素アンモニウム、ホウ酸ナトリウム、ホウ酸カリウム、ホウ酸アンモニウム、水酸化ナトリウム、水酸化アンモニウム、水酸化カリウムおよび水酸化リチウムなどの無機アルカリ剤や、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、ｎ－ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、エチレンイミン、エチレンジアミン、ピリジン、テトラメチルアンモニウムヒドロキシドなどの有機アルカリ剤を使用することができる。これらのアルカリ剤は、単独若しくは２種以上を組み合わせて用いることができる。 Examples of the alkali include tribasic sodium phosphate, tribasic potassium phosphate, tribasic ammonium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, and ammonium carbonate. , Inorganic alkali agents such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, monomethylamine, Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanol Min, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, may be used an organic alkali agent such as tetramethylammonium hydroxide. These alkali agents can be used alone or in combination of two or more.
　酸としては、ハロゲン化水素、硫酸、硝酸、リン酸、ホウ酸などの無機酸や、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸、トリフルオロメタンスルホン酸、酢酸、クエン酸、ギ酸、グルコン酸、乳酸、シュウ酸、酒石酸などの有機酸を使用することができる。 Acids include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid, boric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid Organic acids such as formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid can be used.
　界面活性剤としては、アニオン系、カチオン系、ノニオン系、両性イオン系の界面活性剤を使用することができる。この場合、界面活性剤の含有量は、アルカリ水溶液の全量に対して１～２０質量％であることが好ましく、１～１０質量％であることがより好ましい。
　界面活性剤の含有量を上記した範囲内とすることにより、接着性支持体１００’と薄型デバイスウエハ６０’との剥離性をより向上できる傾向となる。 As the surfactant, an anionic, cationic, nonionic or zwitterionic surfactant can be used. In this case, the content of the surfactant is preferably 1 to 20% by mass and more preferably 1 to 10% by mass with respect to the total amount of the alkaline aqueous solution.
By setting the content of the surfactant within the above-described range, the peelability between the adhesive support 100 ′ and the thin device wafer 60 ′ tends to be further improved.
　アニオン系界面活性剤としては、特に限定されないが、脂肪酸塩類、アビエチン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホコハク酸塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルジフェニルエーテル（ジ）スルホン酸塩類、アルキルフェノキシポリオキシエチレンアルキルスルホン酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、Ｎ－アルキル－Ｎ－オレイルタウリンナトリウム類、Ｎ－アルキルスルホコハク酸モノアミド二ナトリウム塩類、石油スルホン酸塩類、硫酸化ヒマシ油、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸エステル塩類、スチレン－無水マレイン酸共重合物の部分けん化物類、オレフィン－無水マレイン酸共重合物の部分けん化物類、ナフタレンスルホン酸塩ホルマリン縮合物類等が挙げられる。この中で、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルジフェニルエーテル（ジ）スルホン酸塩類が特に好ましく用いられる。 Examples of the anionic surfactant include, but are not limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid salts, Alkylnaphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid Monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate esters, polio Siethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxy Examples thereof include ethylene alkylphenyl ether phosphoric acid ester salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, and naphthalene sulfonate formalin condensates. Of these, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates are particularly preferably used.
　カチオン系界面活性剤としては、特に限定されないが、従来公知のものを用いることができる。例えば、アルキルアミン塩類、第四級アンモニウム塩類、アルキルイミダゾリニウム塩、ポリオキシエチレンアルキルアミン塩類、ポリエチレンポリアミン誘導体が挙げられる。 The cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkyl imidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
　ノニオン系界面活性剤としては、特に限定されないが、ポリエチレングリコール型の高級アルコールエチレンオキサイド付加物、アルキルフェノールエチレンオキサイド付加物、アルキルナフトールエチレンオキサイド付加物、フェノールエチレンオキサイド付加物、ナフトールエチレンオキサイド付加物、脂肪酸エチレンオキサイド付加物、多価アルコール脂肪酸エステルエチレンオキサイド付加物、高級アルキルアミンエチレンオキサイド付加物、脂肪酸アミドエチレンオキサイド付加物、油脂のエチレンオキサイド付加物、ポリプロピレングリコールエチレンオキサイド付加物、ジメチルシロキサン－エチレンオキサイドブロックコポリマー、ジメチルシロキサン－（プロピレンオキサイド－エチレンオキサイド）ブロックコポリマー、多価アルコール型のグリセロールの脂肪酸エステル、ペンタエリスリトールの脂肪酸エステル、ソルビトールおよびソルビタンの脂肪酸エステル、ショ糖の脂肪酸エステル、多価アルコールのアルキルエーテル、アルカノールアミン類の脂肪酸アミド等が挙げられる。この中で、芳香環とエチレンオキサイド鎖を有するものが好ましく、アルキル置換または無置換のフェノールエチレンオキサイド付加物またはアルキル置換または無置換のナフトールエチレンオキサイド付加物がより好ましい。 The nonionic surfactant is not particularly limited, but is a polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid. Ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block Copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer , Fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines. Among these, those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol ethylene oxide adduct is more preferable.
　両性イオン系界面活性剤としては、特に限定されないが、アルキルジメチルアミンオキシドなどのアミンオキシド系、アルキルベタインなどのベタイン系、アルキルアミノ脂肪酸ナトリウムなどのアミノ酸系が挙げられる。特に、置換基を有してもよいアルキルジメチルアミンオキシド、置換基を有してもよいアルキルカルボキシベタイン、置換基を有してもよいアルキルスルホベタインが好ましく用いられる。具体的には、特開２００８－２０３３５９号公報の段落番号〔０２５６〕の式（２）で示される化合物、特開２００８－２７６１６６号公報の段落番号〔００２８〕の式（Ｉ）、式（ＩＩ）、式（ＶＩ）で示される化合物、特開２００９－４７９２７号公報の段落番号〔００２２〕～〔００２９〕で示される化合物を用いることができる。 Zwitterionic surfactants include, but are not limited to, amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaines, and amino acids such as sodium alkylamino fatty acids. In particular, alkyldimethylamine oxide which may have a substituent, alkylcarboxybetaine which may have a substituent, and alkylsulfobetaine which may have a substituent are preferably used. Specifically, the compound represented by the formula (2) in paragraph [0256] of JP-A-2008-203359, the formula (I) and the formula (II) in paragraph [0028] of JP-A-2008-276166 are disclosed. ), A compound represented by the formula (VI), and compounds represented by paragraph numbers [0022] to [0029] of JP-A-2009-47927 can be used.
　さらに必要に応じ、消泡剤および硬水軟化剤のような添加剤を含有することもできる。 Furthermore, additives such as an antifoaming agent and a water softening agent can be contained as required.
　次いで図１Ｆに示す通り、デバイスウエハ表面６１ａ上の保護層７１を除去することにより、薄型デバイスウエハを得ることができる。保護層７１を除去する方法としては、フィルム状のまま除去する方法と、水溶液または有機溶剤に溶解させて溶解除去する方法、活性光線、放射線、または熱の照射により分解、気化させる方法が挙げられるが、有機溶剤に溶解させて溶解除去する方法が好ましく使用できる。水溶液または有機溶剤としては、保護層を溶解除去できる溶液なら任意に使用することができ、具体的には、保護層を溶解除去可能な上述した剥離液を好ましく使用でき、より好ましい態様も剥離液と同じである。 Next, as shown in FIG. 1F, a thin device wafer can be obtained by removing the protective layer 71 on the device wafer surface 61a. Examples of the method for removing the protective layer 71 include a method for removing the protective layer 71 in a film state, a method for dissolving and removing it by dissolving in an aqueous solution or an organic solvent, and a method for decomposing and vaporizing by irradiation with actinic rays, radiation, or heat. However, a method of dissolving and removing by dissolving in an organic solvent can be preferably used. As the aqueous solution or the organic solvent, any solution that can dissolve and remove the protective layer can be used. Specifically, the above-described stripping solution that can dissolve and remove the protective layer can be preferably used. Is the same.
　接着性支持体１００’から薄型デバイスウエハ６０’を脱離した後、必要に応じて、薄型デバイスウエハ６０’に対して、種々の公知の処理を施し、薄型デバイスウエハ６０’を有する半導体装置を製造する。 After the thin device wafer 60 ′ is detached from the adhesive support 100 ′, various known processes are performed on the thin device wafer 60 ′ as necessary to obtain a semiconductor device having the thin device wafer 60 ′. To manufacture.
　また、図１Ｆに示す通り、支持体上の接着剤層を除去することにより、支持体を再生することができる。接着剤層を除去する方法としては、フィルム状のままと、ブラシ、超音波、氷粒子、エアロゾルの吹付けにより物理的に除去する方法、水溶液または有機溶剤に溶解させて溶解除去する方法、活性光線、放射線、熱の照射により分解、気化させる方法などの化学的に除去する方法が挙げられるが、支持体に応じて、従来既知の洗浄方法を利用することができる。
　例えば、シリコン基板を使用した場合、従来既知のシリコンウエハの洗浄方法を使用することができ、例えば化学的に除去する場合に使用できる水溶液または有機溶剤としては、強酸、強塩基、強酸化剤、またはそれらの混合物が上げられ、具体的には、硫酸、塩酸、フッ酸、硝酸、有機酸などの酸類、テトラメチルアンモニウム、アンモニア、有機塩基などの塩基類、過酸化水素などの酸化剤、またはアンモニアと過酸化水素の混合物、塩酸と過酸化水素水の混合物、硫酸と過酸化水素水の混合物、フッ酸と過酸化水素水の混合物、フッ酸とフッ化アンモニウムとの混合物などが挙げられる。 Further, as shown in FIG. 1F, the support can be regenerated by removing the adhesive layer on the support. As a method for removing the adhesive layer, as it is in the form of a film, it is physically removed by spraying with a brush, ultrasonic waves, ice particles, aerosol, a method of dissolving and removing by dissolving in an aqueous solution or an organic solvent, activity A chemical removal method such as a method of decomposing and vaporizing by irradiation with light, radiation, or heat can be mentioned, and conventionally known cleaning methods can be used depending on the support.
For example, when a silicon substrate is used, a conventionally known silicon wafer cleaning method can be used. For example, as an aqueous solution or an organic solvent that can be used for chemical removal, strong acid, strong base, strong oxidizing agent, Or a mixture thereof, specifically, acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, organic acids, bases such as tetramethylammonium, ammonia, organic bases, oxidizing agents such as hydrogen peroxide, or Examples thereof include a mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide solution, a mixture of sulfuric acid and hydrogen peroxide solution, a mixture of hydrofluoric acid and hydrogen peroxide solution, and a mixture of hydrofluoric acid and ammonium fluoride.
　再生した支持体を使った場合の接着性の観点から、以下の基板洗浄液が好ましい。
　基板洗浄液は、ｐＫａが０未満の酸と過酸化水素を含んでいることが好ましい。ｐＫａが０未満の酸としては、ヨウ化水素、過塩素酸、臭化水素、塩化水素、硝酸、硫酸などの無機酸、またはアルキルスルホン酸、アリールスルホン酸などの有機酸から選択される。基板上の接着剤層の洗浄性の観点から無機酸であることが好ましく、硫酸が最も好ましい。 From the viewpoint of adhesiveness when the regenerated support is used, the following substrate cleaning liquid is preferable.
The substrate cleaning liquid preferably contains an acid having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid and sulfuric acid, or organic acids such as alkylsulfonic acid and arylsulfonic acid. From the viewpoint of detergency of the adhesive layer on the substrate, an inorganic acid is preferable, and sulfuric acid is most preferable.
　過酸化水素としては、３０ｗ／ｖ％過酸化水素水が好ましく使用でき、上記強酸と３０ｗ／ｖ％過酸化水素水との混合比は０．１：１～１００：１が好ましく、１：１～１０：１がより好ましく、３：１～５：１が最も好ましい。 As the hydrogen peroxide, 30 w / v% hydrogen peroxide water can be preferably used, and the mixing ratio of the strong acid and 30 w / v% hydrogen peroxide water is preferably 0.1: 1 to 100: 1, and 1: 1. ˜10: 1 is more preferred, and 3: 1 to 5: 1 is most preferred.
　次いで、従来の実施形態について説明する。
　図２は、従来の接着性支持体とデバイスウエハとの仮接着状態の解除を説明する概略断面図である。
　従来の実施形態においては、図２に示すように、接着性支持体として、支持体１２の上に、従来の仮接着剤により形成された接着性層１１’が設けられてなる接着性支持体１００’を使用し、それ以外は、図１Ａおよび図１Ｂを参照して説明した手順と同様に、接着性支持体１００’とデバイスウエハとを仮接着し、デバイスウエハにおけるシリコン基板の薄膜化処理を行い、次いで、上記した手順と同様に、接着性支持体１００’から薄型デバイスウエハ６０’を剥離する。 Next, a conventional embodiment will be described.
FIG. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the conventional adhesive support and the device wafer.
In the conventional embodiment, as shown in FIG. 2, an adhesive support in which an adhesive layer 11 ′ formed of a conventional temporary adhesive is provided on the support 12 as an adhesive support. Otherwise, the adhesive support 100 ′ and the device wafer are temporarily bonded in the same manner as described with reference to FIGS. 1A and 1B, and the silicon substrate is thinned on the device wafer. Then, similarly to the above-described procedure, the thin device wafer 60 ′ is peeled from the adhesive support 100 ′.
　しかしながら、従来の仮接着剤によれば、高い接着力により被処理部材を仮支持し、処理済部材に損傷を与えることなく、処理済部材に対する仮支持を容易に解除することが困難である。例えば、デバイスウエハと支持体との仮接着を充分にしようとするべく、従来の仮接着剤の内、接着性の高いものを採用すると、デバイスウエハと支持体との仮接着が強すぎる傾向となる。よって、この強すぎる仮接着を解除するべく、例えば、図２に示すように、薄型デバイスウエハ６０’の裏面６１ｂ’にテープ（例えば、ダイシングテープ）を貼り付け、接着性支持体１００’から薄型デバイスウエハ６０’を剥離する場合においては、構造体（バンプ）６３が設けられたデバイスチップ６２から、構造体６３が脱離するなどして、デバイスチップ６２を破損する不具合が生じやすい。
　一方、従来の仮接着剤の内、接着性が低いものを採用すると、処理済部材に対する仮支持を容易に解除することはできるが、そもそもデバイスウエハとキャリア基板との仮接着が弱すぎ、デバイスウエハをキャリア基板で確実に支持できないという不具合が生じやすい。 However, according to the conventional temporary adhesive, it is difficult to easily release the temporary support for the processed member without temporarily damaging the processed member with high adhesive force and damaging the processed member. For example, in order to ensure sufficient temporary bonding between the device wafer and the support, if a conventional temporary adhesive having high adhesiveness is adopted, the temporary bonding between the device wafer and the support tends to be too strong. Become. Therefore, in order to release this excessively strong temporary adhesion, for example, as shown in FIG. 2, a tape (for example, dicing tape) is attached to the back surface 61b ′ of the thin device wafer 60 ′, and the adhesive support 100 ′ is thin. When the device wafer 60 ′ is peeled off, the device chip 62 is easily detached from the device chip 62 provided with the structure (bump) 63, and the device chip 62 is easily damaged.
On the other hand, when a conventional temporary adhesive having low adhesiveness is adopted, temporary support to the processed member can be easily released, but the temporary adhesion between the device wafer and the carrier substrate is too weak in the first place. A problem that the wafer cannot be reliably supported by the carrier substrate is likely to occur.
　しかしながら、本発明の接着剤層前駆体により形成された接着剤層は、充分な接着性を発現するとともに、デバイスウエハ６０と接着性支持体１００’との仮接着を容易に解除できる。すなわち、本発明の積層体によれば、高い接着力によりデバイスウエハ６０を仮支持できるとともに、薄型デバイスウエハ６０’に損傷を与えることなく、薄型デバイスウエハ６０’に対する仮支持を容易に解除できる。 However, the adhesive layer formed by the adhesive layer precursor of the present invention exhibits sufficient adhesiveness and can easily release the temporary adhesion between the device wafer 60 and the adhesive support 100 ′. That is, according to the laminate of the present invention, the device wafer 60 can be temporarily supported with high adhesive force, and the temporary support for the thin device wafer 60 ′ can be easily released without damaging the thin device wafer 60 ′.
　本発明の積層体の形成方法、および半導体装置の製造方法は、前述した実施の形態に限定されるものではなく、適宜な変形、改良等が可能である。 The method for forming a laminated body and the method for manufacturing a semiconductor device of the present invention are not limited to the above-described embodiments, and appropriate modifications and improvements can be made.
　前述した実施形態において、本発明における接着剤層前駆体より形成される接着性層は、デバイスウエハの仮接着の前に、支持体の上に設けられることにより接着性支持体を構成したが、先ず、デバイスウエハ等の被処理部材の上に設けられ、次いで、接着剤層が設けられた被処理部材と、支持体とが仮接着されても良い。 In the embodiment described above, the adhesive layer formed from the adhesive layer precursor in the present invention constitutes an adhesive support by being provided on the support before temporary bonding of the device wafer. First, a member to be processed, such as a device wafer, may be temporarily bonded to a member to be processed, which is then provided with an adhesive layer.
　また、前述した実施形態において、接着剤層前駆体および接着性層は単層構造であるが、接着剤層前駆体および接着性層は多層構造であってもよい。多層構造の接着性層を形成する方法としては、活性光線、放射線または熱を照射する前に、前述した従来公知の方法で仮接着剤を段階的に適用する方法や、活性光線、放射線または熱を照射した後に、前述した従来公知の方法で仮接着剤を適用する方法などが挙げられる。 In the above-described embodiment, the adhesive layer precursor and the adhesive layer have a single layer structure, but the adhesive layer precursor and the adhesive layer may have a multilayer structure. As a method for forming an adhesive layer having a multilayer structure, before irradiating actinic light, radiation or heat, a method of applying a temporary adhesive in a stepwise manner by the above-mentioned conventionally known method, or actinic light, radiation or heat is used. And a method of applying a temporary adhesive by a conventionally known method described above.
　また、前述した実施形態においては、接着性支持体により支持される被処理部材として、シリコン基板を挙げたが、これに限定されるものではなく、半導体装置の製造方法において、機械的または化学的な処理に供され得るいずれの被処理部材であっても良い。
　例えば、被処理部材としては、化合物半導体基板を挙げることもでき、化合物半導体基板の具体例としては、ＳｉＣ基板、ＳｉＧｅ基板、ＺｎＳ基板、ＺｎＳｅ基板、ＧａＡｓ基板、ＩｎＰ基板、および、ＧａＮ基板などが挙げられる。 In the above-described embodiment, the silicon substrate is exemplified as the member to be processed supported by the adhesive support. However, the present invention is not limited to this, and in the semiconductor device manufacturing method, mechanical or chemical Any member to be processed that can be subjected to various processing may be used.
For example, the member to be processed can include a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate. Can be mentioned.
　さらに、前述した実施形態においては、接着性支持体により支持されたシリコン基板に対する機械的または化学的な処理として、シリコン基板の薄膜化処理、および、シリコン貫通電極の形成処理を挙げたが、これらに限定されるものではなく、半導体装置の製造方法において必要ないずれの処理も挙げられる。 Further, in the above-described embodiment, the silicon substrate thinning process and the silicon through electrode forming process are exemplified as the mechanical or chemical process for the silicon substrate supported by the adhesive support. However, the present invention is not limited to these, and any processing necessary in the method for manufacturing a semiconductor device can be used.
　デバイスウエハにおけるデバイスチップの形状、寸法、数、配置箇所等は、本発明を達成できるものであれば任意であり、限定されない。 The shape, dimensions, number, arrangement location, and the like of the device chip on the device wafer are arbitrary as long as the present invention can be achieved and are not limited.
　以下、本発明を実施例によりさらに具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。尚、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, “part” and “%” are based on mass.
＜接着剤層前駆体形成用組成物層を有する支持体の形成＞
　２００ｍｍＳｉウエハに下記に記載の接着層前駆体形成用組成物をスピンコーターにより塗布したのち、１２０℃で３０秒ベークし、厚さ０．２μｍの接着性前駆体形成用組成物層が設けられたウエハを形成した。接着性前駆体形成用組成物層が設けられたウエハを、フーリエ変換型赤外分光計（ＥＸＣＡＬＩＢＵＲ　ＦＴＳ－３０００）を用いて、８２０－８００ｃｍ-1付近にあるσ=CH（ビニル基ＣＨの面外変角振動バンド）のピーク面積を測定した。 <Formation of a support having a composition layer for forming an adhesive layer precursor>
The composition for forming an adhesive layer precursor described below was applied to a 200 mm Si wafer by a spin coater, and then baked at 120 ° C. for 30 seconds to provide an adhesive precursor forming composition layer having a thickness of 0.2 μm. A wafer was formed. Using a Fourier transform infrared spectrometer (EXCALIBUR FTS-3000), a wafer provided with the composition layer for forming an adhesive precursor is a surface of σ = CH (vinyl group CH surface) near 820-800 cm −1. The peak area of the external variable vibration band was measured.
＜接着剤層前駆体形成用組成物＞
・重合性モノマーまたはオリゴマー（ｂ－１）　　　下記表に記載の質量部
・重合性モノマーまたはオリゴマー（ｂ－１’）　　下記表に記載の質量部
・光ラジカル重合開始剤（ｂ－２）　　　　　　　　下記表に記載の質量部
・熱ラジカル重合開始剤（ｂ－３）　　　　　　　　下記表に記載の質量部
・高分子化合物（ｂ－４）　　　　　　　　　　　　下記表に記載の質量部
・重合禁止剤（ｐ－メトキシフェノール、東京化成社製）０．００８質量部
・界面活性剤（ＰＦ６３２０、ＯＭＮＯＶＡ社製）　　　０．０３２質量部
・溶剤（プロピレングリコールモノプロピルエーテルアセテート）
　　　　　　　　　　　　　　　　　　　　　　　　　　９４．９６質量部 <Adhesive layer precursor forming composition>
Polymerizable monomer or oligomer (b-1) parts by mass listed in the table below Polymerizable monomer or oligomer (b-1 ′) parts by mass listed in the table below Photoradical polymerization initiator (b-2) Table below Parts by mass / thermal radical polymerization initiator (b-3) described in Table 4 parts by mass / polymer compound (b-4) described in the following table parts by mass / polymerization inhibitor (p-methoxyphenol, Tokyo) (Made by Kasei Co., Ltd.) 0.008 parts by mass / surfactant (PF6320, manufactured by OMNOVA) 0.032 parts by mass / solvent (propylene glycol monopropyl ether acetate)
94.96 parts by mass
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
　表１中に記載の化合物は、以下の通りである。
[（ｂ－１）重合性モノマーまたはオリゴマー]
（ｂ－１－１）　ブレンマーＰＭＥ４００（日油（株）社製））
（ｂ－１－２）　ＮＫエステル　Ａ－ＢＰＥ－４（新中村化学工業（株）社製）
（ｂ－１－３）　ＮＫエステル　Ａ－ＢＰＥ－１０（新中村化学工業（株）社製）
（ｂ－１－４）　ジビニルベンゼン（和光純薬工業（株）社製）
（ｂ－１－５）　ライトアクリレート　ＴＭＰ－Ａ（共栄社化学（株）社製）
（ｂ－１－６）　ＮＫエステル　Ａ－ＴＭＰ－３ＥＯ（新中村化学工業（株）社製）
（ｂ－１－７）　ＮＫエステル　ＡＤ－ＴＭＰ（新中村化学工業（株）社製）
（ｂ－１－８）　ＮＫエステル　Ａ－ＤＰＨ（新中村化学工業（株）社製）
（ｂ－１－９）　イソシアヌル酸トリアリル（東京化成工業（株）社製）
（ｂ－１－１０）　ＲＳ－７６－Ｅ（フッ素系オリゴマー、ＤＩＣ（株）社製）
（ｂ－１－１１）　ＲＳ－７２－Ｋ（フッ素系オリゴマー、ＤＩＣ（株）社製）
（ｂ－１－１２）　オプツールＤＡＣ－ＨＰ（フッ素系オリゴマー、ダイキン工業（株）社製）
（ｂ－１－１３）　Ｘ－２２－１６４（シリコン系オリゴマー、２官能モノマー、信越化学工業（株）社製）
（ｂ－１－１４）　下記構造のフッ素系モノマー The compounds described in Table 1 are as follows.
[(B-1) Polymerizable monomer or oligomer]
(B-1-1) Blemmer PME400 (manufactured by NOF Corporation))
(B-1-2) NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-1-3) NK ester A-BPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-1-4) Divinylbenzene (Wako Pure Chemical Industries, Ltd.)
(B-1-5) Light acrylate TMP-A (manufactured by Kyoeisha Chemical Co., Ltd.)
(B-1-6) NK ester A-TMP-3EO (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-1-7) NK ester AD-TMP (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-1-8) NK ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-1-9) Triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-1-10) RS-76-E (fluorine oligomer, manufactured by DIC Corporation)
(B-1-11) RS-72-K (fluorine oligomer, manufactured by DIC Corporation)
(B-1-12) Optool DAC-HP (fluorine oligomer, manufactured by Daikin Industries, Ltd.)
(B-1-13) X-22-164 (silicon oligomer, bifunctional monomer, manufactured by Shin-Etsu Chemical Co., Ltd.)
(B-1-14) Fluorine monomer having the following structure
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
[（ｂ－２）光ラジカル重合開始剤]
（ｂ－２－１）　ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２（ＢＡＳＦ社製）
（ｂ－２－２）　カヤキュアーＤＥＴＸ（日本化薬社製） [(B-2) Photoradical polymerization initiator]
(B-2-1) IRGACURE OXE 02 (manufactured by BASF)
(B-2-2) Kayacure DETX (Nippon Kayaku Co., Ltd.)
[(ｂ－３)熱ラジカル重合開始剤]
（ｂ－３－１）　パーブチルＺ（ｔｅｒｔ－ブチルパーオキシベンゾエート、分解温度（１０時間半減期温度＝１０４℃）、日油（株）社製）
（ｂ－３－２）　パーヘキサ２２（２，２－ジ－（ｔ－ブチルパーオキシ）ブタン、分解温度（１０時間半減期温度＝１０３℃）、日油（株）社製） [(b-3) Thermal radical polymerization initiator]
(B-3-1) Perbutyl Z (tert-butyl peroxybenzoate, decomposition temperature (10 hour half-life temperature = 104 ° C.), manufactured by NOF Corporation)
(B-3-2) Perhexa 22 (2,2-di- (t-butylperoxy) butane, decomposition temperature (10 hours half-life temperature = 103 ° C.), manufactured by NOF Corporation)
[（ｂ－４）高分子化合物]
（ｂ－４－１）　エスチレンＭＳ６００（メチルメタクリレート・スチレン共重合樹脂、新日鉄住金化学（株）社製）
（ｂ－４－２）　ポリメタクリル酸メチル（Ａｌｄｒｉｃｈ製、Ｍｗ：１２．０万） [(B-4) polymer compound]
(B-4-1) Estyrene MS600 (methyl methacrylate / styrene copolymer resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
(B-4-2) Polymethyl methacrylate (manufactured by Aldrich, Mw: 12 million)
[フッ素原子を有する化合物(ｂ－５)]
  (ｂ－５－１)  ダイフリーＦＢ－９６２　（ダイキン工業（株）製） [Compound having fluorine atom (b-5)]
(b-5-1) Die Free FB-962 (manufactured by Daikin Industries, Ltd.)
＜被処理部材の作製＞
　被処理部材としては、高さ１０μｍのＣｕ製バンプ付きの２００ｍｍＳｉウエハに、下記表に記載の保護層形成用組成物をスピンコーターにより塗布したのち、下記表に記載の条件で１回または２回に分けてベークを行い、厚さ２０μｍの保護層が設けられたウエハを形成した。 <Preparation of member to be treated>
As a member to be processed, a protective layer forming composition described in the following table was applied to a 200 mm Si wafer with a Cu bump having a height of 10 μm using a spin coater, and then once or twice under the conditions described in the following table. Baking was performed separately to form a wafer provided with a protective layer having a thickness of 20 μm.
＜保護層形成用組成物の組成＞
・樹脂成分　　　　　　　　　　　　　　　　　　　下記表に記載の質量部
・溶剤　　　　　　　　　　　　　　　　　　　　　下記表に記載の質量部 <Composition of composition for forming protective layer>
Resin component parts by mass listed in the following table / solvent parts by mass listed in the following table
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　表２中に記載の化合物は、以下の通りである。
[樹脂成分]
（Ｃ－１－１）　ｕｌｔｒａｓｏｎＥ６０２０Ｐ（ポリエーテルスルホン樹脂、ＢＡＳＦ社製）
（Ｃ－１－２）　ＰＣＺ－３００（ポリカーボネート樹脂、三菱ガス化学（株）製）
（Ｃ－１－３）　エスチレンＭＳ２００ＮＴ（ポリスチレン樹脂、新日鐵化学（株）製）
（Ｃ－１－４）　ＴＯＰＡＳ　５０１３（炭化水素樹脂、ポリプラスチック（株）製） The compounds described in Table 2 are as follows.
[Resin component]
(C-1-1) ultrason E6020P (polyether sulfone resin, manufactured by BASF)
(C-1-2) PCZ-300 (polycarbonate resin, manufactured by Mitsubishi Gas Chemical Co., Inc.)
(C-1-3) Estyrene MS200NT (polystyrene resin, manufactured by Nippon Steel Chemical Co., Ltd.)
(C-1-4) TOPAS 5013 (hydrocarbon resin, manufactured by Polyplastics Co., Ltd.)
［溶剤］
（Ｃ－２－１）　Ｎ－メチル－２－ピロリドン（ＮＭＰ）（和光純薬社製）
（Ｃ－２－２）　アニソール（和光純薬社製）
（Ｃ－２－３）　プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）（和光純薬社製）
（Ｃ－２－４）　リモネン（関東化学社製）
[フッ素原子を有する化合物(Ｃ－３)]
  (Ｃ－３－１)  ダイフリーＦＢ－９６２　（ダイキン工業（株）製） [solvent]
(C-2-1) N-methyl-2-pyrrolidone (NMP) (manufactured by Wako Pure Chemical Industries, Ltd.)
(C-2-2) Anisole (Wako Pure Chemical Industries, Ltd.)
(C-2-3) Propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Wako Pure Chemical Industries, Ltd.)
(C-2-4) Limonene (Kanto Chemical Co., Ltd.)
[Compound having fluorine atom (C-3)]
(C-3-1) Die Free FB-962 (manufactured by Daikin Industries, Ltd.)
＜積層体の作製＞
　次に表に記載の通り、接着剤層前駆体形成用組成物層を有するウエハおよび保護層を有する被処理部材を用いて、真空下１２０℃、１０００Ｎの圧力で３分間圧着を行い、ウエハ、接着剤層前駆体、保護層、被処理部材を有する積層体を得た。得られた積層体を、層の垂直方向に引っ張り、接着剤前駆体を有するウエハと保護層を有する被処理部材に分割した。接着剤前駆体を有するウエハをフーリエ変換型赤外分光計（ＥＸＣＡＬＩＢＵＲ　ＦＴＳ－３０００）を用いて、８２０－８００ｃｍ-1付近にあるσ=CH（ビニル基ＣＨの面外変角振動バンド）のピーク面積を測定した。
　貼り合わせ前後のピーク面積値の減少率から、加熱もしくは光照射前後の接着剤前駆体中の重合性モノマーまたはオリゴマーの重合率を算出した。
　再度、表に記載の通り、接着剤層前駆体形成用組成物層を有するウエハおよび保護層を有する被処理部材を用いて、真空下１２０℃、１０００Ｎの圧力で３分間圧着を行い、ウエハ、接着剤層前駆体、保護層、被処理部材を有する積層体を得た。
　さらに、常圧下で２００℃、３分間の加熱を行い、接着剤層前駆体を接着剤層にして、接着性試験片を得た。 <Production of laminate>
Next, as described in the table, using a wafer having a composition layer for forming an adhesive layer precursor and a member to be processed having a protective layer, pressure bonding is performed at 120 ° C. under a pressure of 1000 N for 3 minutes under vacuum, A laminate having an adhesive layer precursor, a protective layer, and a member to be processed was obtained. The obtained laminated body was pulled in the vertical direction of the layer and divided into a wafer having an adhesive precursor and a member to be processed having a protective layer. Using a Fourier transform infrared spectrometer (EXCALIBUR FTS-3000), the peak of σ = CH (an out-of-plane vibration band of vinyl group CH) near 820-800 cm −1 is applied to the wafer having the adhesive precursor. The area was measured.
The polymerization rate of the polymerizable monomer or oligomer in the adhesive precursor before and after heating or light irradiation was calculated from the decreasing rate of the peak area value before and after bonding.
Again, as described in the table, using the wafer having the adhesive layer precursor forming composition layer and the member to be processed having the protective layer, pressure bonding was performed at 120 ° C. under a pressure of 1000 N for 3 minutes under vacuum, A laminate having an adhesive layer precursor, a protective layer, and a member to be processed was obtained.
Furthermore, heating was performed at 200 ° C. for 3 minutes under normal pressure, and the adhesive layer precursor was used as an adhesive layer to obtain an adhesive test piece.
＜接着性試験片の接着力測定＞
　下記表に記載の条件で作製された試験片のせん断接着力を、引っ張り試験機（（株）イマダ製デジタルフォースゲージ、型式：ＺＰ－５０Ｎ）を用いて、２５０ｍｍ／ｍｉｎの条件で接着性層の面に沿った方向に引っ張り測定し、以下の基準で評価した。
Ａ：ウエハが割れるほど強く接着していた
Ｂ：１０Ｎを超え５０Ｎ以下の力で剥がれた
Ｃ：１０Ｎ以下の力で剥がれた <Measurement of adhesive strength of adhesive test piece>
The adhesive strength of the test specimens prepared under the conditions shown in the following table was determined at 250 mm / min using a tensile tester (Imada Digital Force Gauge, Model: ZP-50N). Tensile measurement was performed in the direction along the surface, and evaluation was performed according to the following criteria.
A: The wafer was strongly bonded so that the wafer was cracked. B: Peeled off with a force exceeding 10N and 50N or less C: Peeled off with a force of 10N or less
＜剥離性＞
　下記表に記載の条件で作製された試験片を、２５０ｍｍ／ｍｉｎの条件で接着剤層の垂直方向に引っ張り、剥離性を確認した。また、作製された試験片を２５０℃で３０分加熱した後に、同様に、２５０ｍｍ／ｍｉｎの条件で接着剤層の垂直方向に引っ張り、熱プロセス後の剥離性を確認し、以下の基準で評価した。なお、Ｓｉウエハの破損の有無は目視で確認した。
ＡＡ：最大の剥離力が１０Ｎ未満で剥離できた
Ａ：最大の剥離力が１０Ｎ以上２０Ｎ未満で剥離できた
Ｂ：最大の剥離力が２０Ｎ以上３０Ｎ未満で剥離できた
Ｃ：最大の剥離力が３０Ｎ以上５０Ｎ未満で剥離できた
Ｄ：最大の剥離力が５０Ｎ以上もしくはウエハが破損してしまった <Peelability>
The test piece prepared under the conditions described in the following table was pulled in the vertical direction of the adhesive layer under the condition of 250 mm / min, and the peelability was confirmed. In addition, after the prepared test piece was heated at 250 ° C. for 30 minutes, similarly, it was pulled in the vertical direction of the adhesive layer under the condition of 250 mm / min, and the peelability after the thermal process was confirmed, and evaluated according to the following criteria: did. In addition, the presence or absence of the damage of Si wafer was confirmed visually.
AA: It was able to peel off when the maximum peeling force was less than 10N A: It was able to peel off when the maximum peeling force was 10N or more and less than 20N B: It was able to peel when the maximum peeling force was 20N or more and less than 30N C: The maximum peeling force was D was able to peel off at 30N or more and less than 50N: The maximum peeling force was 50N or more or the wafer was damaged
＜ＴＴＶ：Ｔｏｔａｌ Ｔｈｉｃｋｎｅｓｓ Ｖａｒｉａｔｉｏｎ＞
　接合ウエハを（株）ディスコ社製グラインダ（ＤＦＧ８５６０）を用いて、被処理部材の接合面に対して裏面側を、被処理部材の膜厚を１００μｍまで薄化した。その後、ＩＳＩＳ社製半導体基板表面検査装置（ＳｅｍＤｅｘ３００）を用いて被処理部材の層厚を測定し、厚みの最小値と最大値の差を求め、以下の基準で評価した。
Ａ：最小値と最大値の差が５μｍ以下
Ｂ：最小値と最大値の差が５μｍを超える <TTV: Total Thickness Variation>
Using a grinder (DFG8560) manufactured by DISCO Corporation, the bonded wafer was thinned on the back side with respect to the bonded surface of the processed member, and the film thickness of the processed member was reduced to 100 μm. Then, the layer thickness of the to-be-processed member was measured using the semiconductor substrate surface test | inspection apparatus (SemDex300) by ISIS, the difference of the minimum value and the maximum value of thickness was calculated | required, and the following references | standards evaluated.
A: Difference between minimum and maximum values is 5 μm or less B: Difference between minimum and maximum values exceeds 5 μm
＜洗浄除去性＞
　剥離性試験終了後のダイシングテープを介してダイシングフレームに装着された２００ｍｍウエハ（耐熱性試験条件に晒されたもの）を、接着剤層を上にしてスピンコーターにセットし、洗浄溶剤として下記表に記載の溶剤を使用して、５分間噴霧したのち、ウエハを回転させながらイソプロピルアルコール（ＩＰＡ）を噴霧にてリンスを行った。その後、外観を観察して残存する接着剤樹脂の有無を目視でチェックし、以下の基準で評価した。
Ａ：樹脂の残存が認められない
Ｂ：樹脂の残存が認められた <Cleanability>
A 200 mm wafer (exposed to heat resistance test conditions) mounted on a dicing frame via a dicing tape after completion of the peelability test is set on a spin coater with the adhesive layer facing upward, and the following table is used as a cleaning solvent. After spraying for 5 minutes using the solvent described in 1., isopropyl alcohol (IPA) was rinsed by spraying while rotating the wafer. Thereafter, the appearance was observed and the presence or absence of the remaining adhesive resin was visually checked and evaluated according to the following criteria.
A: Residual resin was not observed B: Resin remained
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　以上のように、（Ａ）支持体上に、（Ｂ）接着剤層前駆体、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有し、上記（Ｂ）接着剤層前駆体が、（ｂ－１）重合性モノマーまたはオリゴマーを含み、その重合率が１０～７０％の実施例は、接着性および剥離性に関して良好な結果が得られるのみならず、ＴＴＶおよび洗浄性にも優れることがわかった。
　一方、重合性モノマーの重合率が１０％未満である比較例１は、剥離性が実施例よりも劣ることが分かった。重合性モノマーの重合率が７０％を超える比較例２は、接着力が実施例よりも劣ることが分かった。また、接着剤層前駆体および保護層のいずれかを有さない比較例３～４は、接着力およびＴＴＶが実施例よりも劣ることが分かった。
　また、接着剤層前駆体に３官能以上のラジカル重合性モノマーを有する、および／またはフッ素原子を有するラジカル重合性モノマーを有すると剥離性がより向上することがわかった（実施例８、１０～１２、１４～３０、３３）。
　さらに、接着剤層前駆体にフッ素原子を有するラジカル重合性化合物を含み、さらに接着剤層前駆体または保護層にフッ素原子を有する非重合性化合物を含むと、剥離性がより向上することがわかった。（実施例３５、３６、３９～４８）） As described above, (B) an adhesive layer precursor, (C) a protective layer, and (D) a device wafer are provided in this order on (A) a support, and (B) the adhesive layer precursor is (B-1) Examples containing a polymerizable monomer or oligomer and having a polymerization rate of 10 to 70% not only give good results with respect to adhesiveness and peelability, but also have excellent TTV and detergency. I understood.
On the other hand, it turned out that the comparative example 1 whose polymerization rate of a polymerizable monomer is less than 10% is inferior to an Example in peelability. It turned out that the comparative example 2 in which the polymerization rate of a polymerizable monomer exceeds 70% is inferior to an Example in adhesive force. Further, it was found that Comparative Examples 3 to 4 which did not have any one of the adhesive layer precursor and the protective layer were inferior in adhesive strength and TTV to the examples.
Further, it was found that the peelability was further improved when the adhesive layer precursor had a radical polymerizable monomer having three or more functional groups and / or a radical polymerizable monomer having a fluorine atom (Examples 8, 10 to 12, 14-30, 33).
Furthermore, it can be seen that when the radically polymerizable compound having a fluorine atom is contained in the adhesive layer precursor and the nonpolymerizable compound having a fluorine atom is further contained in the adhesive layer precursor or the protective layer, the releasability is further improved. It was. (Examples 35, 36, 39 to 48))
１１　接着剤層前駆体形成用組成物
１２　支持体（キャリア基板）
１３　接着性層前駆体
６０　デバイスウエハ
６０’　薄型デバイスウエハ
６１’　シリコン基板
６１ａ　シリコン基板の表面
６１ｂ　シリコン基板の裏面
６１ｂ’　薄型デバイスウエハの裏面
６２　デバイスチップ
６３　バンプ
７１　保護層
１００，１００’　接着性支持体 11 Adhesive Layer Precursor Composition 12 Support (Carrier Substrate)
13 Adhesive layer precursor 60 Device wafer 60 'Thin device wafer 61' Silicon substrate 61a Silicon substrate surface 61b Silicon substrate back surface 61b 'Thin device wafer back surface 62 Device chip 63 Bump 71 Protective layer 100, 100' Adhesive support body

Claims (23)

  1. （Ａ）支持体上に、（Ｂ）接着剤層前駆体、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有し、前記（Ｂ）接着剤層前駆体が、（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含み、かつ、重合性モノマーおよび／または重合性オリゴマーの重合率が１０～７０％である、積層体。 (A) On a support, (B) an adhesive layer precursor, (C) a protective layer, and (D) a device wafer are provided in this order, and (B) the adhesive layer precursor is (b-1) A laminate comprising a polymerizable monomer and / or polymerizable oligomer, and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70%.
  2. （ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、３官能以上のラジカル重合性モノマーを少なくとも１種含む、請求項１に記載の積層体。 (B-1) The laminate according to claim 1, wherein the polymerizable monomer and / or polymerizable oligomer includes at least one radically polymerizable monomer having three or more functions.
  3. （ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、フッ素原子および／またはケイ素原子を有するラジカル重合性化合物を少なくとも１種含む、請求項１または２に記載の積層体。 (B-1) The laminate according to claim 1 or 2, wherein the polymerizable monomer and / or polymerizable oligomer contains at least one radical polymerizable compound having a fluorine atom and / or a silicon atom.
  4. （ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、２官能以下のラジカル重合性モノマーおよび３官能以上のラジカル重合性モノマーを含む、請求項１～３のいずれか１項に記載の積層体。 (B-1) The laminate according to any one of claims 1 to 3, wherein the polymerizable monomer and / or polymerizable oligomer includes a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer. body.
  5. 接着剤層前駆体が、さらに（ｂ－２）光ラジカル開始剤を含有する、請求項１～４のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 4, wherein the adhesive layer precursor further contains (b-2) a photoradical initiator.
  6. 接着剤層前駆体が、さらに（ｂ－３）熱ラジカル開始剤を含有する、請求項１～４のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 4, wherein the adhesive layer precursor further contains (b-3) a thermal radical initiator.
  7. 接着剤層前駆体が、さらに（ｂ－４）高分子化合物を含有する、請求項１～６のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 6, wherein the adhesive layer precursor further contains (b-4) a polymer compound.
  8. （Ａ）支持体上に、（Ｂ２）接着剤層、（Ｃ）保護層、（Ｄ）デバイスウエハをこの順に有し、前記（Ｂ２)接着剤層が接着剤層前駆体の硬化物であり、前記接着剤層前駆体が（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含み、かつ、重合性モノマーおよび／または重合性オリゴマーの重合率が１０～７０％である、積層体。 (A) It has (B2) adhesive layer, (C) protective layer, (D) device wafer in this order on the support, and (B2) adhesive layer is a cured product of the adhesive layer precursor. The laminate in which the adhesive layer precursor includes (b-1) a polymerizable monomer and / or polymerizable oligomer, and the polymerization rate of the polymerizable monomer and / or polymerizable oligomer is 10 to 70%.
  9. （Ｃ）保護層の軟化点が１７０℃以上２５０℃以下である、請求項１～８のいずれか１項に記載の積層体。 (C) The laminate according to any one of claims 1 to 8, wherein the softening point of the protective layer is 170 ° C or higher and 250 ° C or lower.
  10. （Ｃ）保護層が、熱可塑性樹脂である、請求項１～９のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 9, wherein the protective layer (C) is a thermoplastic resin.
  11. （Ｃ）保護層が、ポリエーテルスルホン樹脂、ポリイミド樹脂、ポリエステル樹脂、ポリベンズイミダゾール樹脂、ポリアミドイミド樹脂、ポリカーボネート樹脂、ポリスチレン樹脂およびポリエーテルエーテルケトン樹脂から選ばれる少なくとも１種の熱可塑性樹脂を含む、請求項１～１０のいずれか１項に記載の積層体。 (C) The protective layer contains at least one thermoplastic resin selected from polyethersulfone resin, polyimide resin, polyester resin, polybenzimidazole resin, polyamideimide resin, polycarbonate resin, polystyrene resin, and polyetheretherketone resin. The laminate according to any one of claims 1 to 10.
  12. （Ｄ）デバイスウエハが、表面上に高さ１μｍ以上１５０μｍ以下の構造体を有する、請求項１～１１のいずれか１項に記載の積層体。 (D) The laminate according to any one of claims 1 to 11, wherein the device wafer has a structure having a height of 1 μm or more and 150 μm or less on the surface.
  13. 請求項１～１２のいずれか１項に記載の積層体の保護層を製造するための保護層形成用組成物であって、樹脂と溶剤を含む保護層形成用組成物。 A protective layer forming composition for producing the protective layer of the laminate according to any one of claims 1 to 12, comprising a resin and a solvent.
  14. 樹脂の軟化点が１７０℃以上２５０℃以下である、請求項１３に記載の保護層形成用組成物。 The composition for protective layer formation of Claim 13 whose softening point of resin is 170 degreeC or more and 250 degrees C or less.
  15. 請求項１～７および９～１２のいずれか１項に記載の積層体の接着剤層前駆体または請求項８に記載の接着剤層を製造するための組成物であって、溶剤と（ｂ－１）重合性モノマーおよび／または重合性オリゴマーを含む、組成物。 An adhesive layer precursor for a laminate according to any one of claims 1 to 7 and 9 to 12, or a composition for producing an adhesive layer according to claim 8, comprising a solvent and (b -1) A composition comprising a polymerizable monomer and / or a polymerizable oligomer.
  16. （ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、３官能以上のラジカル重合性モノマーを少なくとも１種含む、請求項１５に記載の組成物。 (B-1) The composition according to claim 15, wherein the polymerizable monomer and / or polymerizable oligomer contains at least one radically polymerizable monomer having three or more functions.
  17. （ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、フッ素原子および／またはケイ素原子を有するラジカル重合性化合物を少なくとも１種含む、請求項１５または１６に記載の組成物。 The composition according to claim 15 or 16, wherein (b-1) the polymerizable monomer and / or polymerizable oligomer contains at least one radical polymerizable compound having a fluorine atom and / or a silicon atom.
  18. （ｂ－１）重合性モノマーおよび／または重合性オリゴマーが、２官能以下のラジカル重合性モノマーおよび３官能以上のラジカル重合性モノマーを含む、請求項１５～１７のいずれか１項に記載の組成物。 The composition according to any one of claims 15 to 17, wherein the (b-1) polymerizable monomer and / or polymerizable oligomer includes a bifunctional or lower radical polymerizable monomer and a trifunctional or higher functional radical polymerizable monomer. object.
  19. さらに（ｂ－２）光ラジカル開始剤を含有する、請求項１５～１８のいずれか１項に記載の組成物。 The composition according to any one of claims 15 to 18, further comprising (b-2) a photoradical initiator.
  20. さらに（ｂ－２）熱ラジカル開始剤を含む、請求項１５～１８のいずれか１項に記載の組成物。 The composition according to any one of claims 15 to 18, further comprising (b-2) a thermal radical initiator.
  21. さらに（ｂ－４）高分子化合物を含む、請求項１５～２０のいずれか１項に記載の組成物。 The composition according to any one of claims 15 to 20, further comprising (b-4) a polymer compound.
  22. 樹脂と溶剤を含む保護層形成用組成物と、溶剤と重合性モノマーおよび／または重合性オリゴマーを含む接着剤層前駆体または接着剤層形成用組成物を含むキット。 A kit comprising a protective layer forming composition comprising a resin and a solvent, and an adhesive layer precursor or an adhesive layer forming composition comprising a solvent and a polymerizable monomer and / or a polymerizable oligomer.
  23. キットが、請求項１～１２のいずれか１項に記載の積層体を製造するためのキットである、請求項２２に記載のキット。 The kit according to claim 22, wherein the kit is a kit for producing the laminate according to any one of claims 1 to 12.
PCT/JP2014/072369 2013-08-30 2014-08-27 Laminate and application therefor WO2015030031A1 (en)

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