WO2015190477A1 - 仮止め接着剤、接着フィルム、接着性支持体、積層体およびキット - Google Patents

仮止め接着剤、接着フィルム、接着性支持体、積層体およびキット Download PDF

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Publication number
WO2015190477A1
WO2015190477A1 PCT/JP2015/066594 JP2015066594W WO2015190477A1 WO 2015190477 A1 WO2015190477 A1 WO 2015190477A1 JP 2015066594 W JP2015066594 W JP 2015066594W WO 2015190477 A1 WO2015190477 A1 WO 2015190477A1
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Prior art keywords
group
adhesive layer
adhesive
elastomer
support
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PCT/JP2015/066594
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English (en)
French (fr)
Japanese (ja)
Inventor
悠 岩井
一郎 小山
義貴 加持
沢野　充
中村　敦
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富士フイルム株式会社
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Priority to JP2016527817A priority Critical patent/JP6424221B2/ja
Priority to KR1020167031935A priority patent/KR101959770B1/ko
Publication of WO2015190477A1 publication Critical patent/WO2015190477A1/ja

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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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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
    • 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

Definitions

  • the present invention relates to a temporary fixing adhesive, an adhesive film, an adhesive support, a laminate, and a kit. More specifically, the present invention relates to a temporary fixing adhesive, an adhesive film, an adhesive support, a laminate, and a kit that can be preferably used for manufacturing a semiconductor device or the like.
  • 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 device wafer In order to reduce the size of an IC chip, a device wafer 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 device wafer by multilayering an integrated circuit 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 device wafer is being considered as a thinning of such a member, which not only leads to the miniaturization of the IC chip, but also saves the process of manufacturing the through hole of the device wafer in the production of the silicon through electrode. Because it is possible, it is considered promising.
  • thinning of semiconductor devices such as power devices and image sensors has been attempted from the viewpoint of improving the degree of integration and improving the degree of freedom of the device structure.
  • a device wafer having a thickness of about 700 to 900 ⁇ m is widely known, but in recent years, for the purpose of reducing the size of an IC chip or the like, the thickness of the device wafer can be reduced to 200 ⁇ m or less. Has been tried. However, since a device wafer having a thickness of 200 ⁇ m or less is very thin and a semiconductor device manufacturing member based on the device wafer is very thin, such a member may be further processed, or When the member is simply moved, it is difficult to support the member stably and without damage.
  • the device wafer on which the device is provided on the surface and the support are temporarily bonded to each other with a silicone adhesive, and the back surface of the device wafer is ground to reduce the thickness.
  • a technique is known in which a wafer is punched to provide a silicon through electrode, and then a support is detached from the device wafer (see Patent Document 1).
  • 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).
  • an adhesive film is known that is composed of syndiotactic 1,2-polybutadiene and a photopolymerization initiator and whose adhesive force changes upon irradiation with radiation (see Patent Document 6). Further, the support and the device wafer are temporarily bonded with an adhesive made of polycarbonate, and the device wafer is processed, irradiated with irradiation radiation, and then heated to process the device wafer. A technique for detaching from the support is known (see Patent Document 7).
  • the support and device wafer are temporarily bonded with two layers with different softening points, and after processing the device wafer, the support and device wafer are detached by heating and sliding laterally.
  • the technique to do is known (refer patent document 8).
  • Patent Document 9 discloses a cycloolefin polymer, at least one of a silicone structure, a fluorinated alkyl group structure, a fluorinated alkenyl structure and an alkyl structure having 8 or more carbon atoms, a polyoxyalkylene structure, and phosphoric acid. It is disclosed that a support and a substrate are temporarily fixed via a temporary fixing material including a compound having a structure having a group and a structure having at least one of a structure having a sulfo group. Patent Document 10 discloses that a substrate and a support are bonded using an adhesive composition containing a styrene unit as a main chain constituent unit and a wax.
  • 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 Document 10 for the purpose of easily separating the device wafer and the support, a support provided with a plurality of holes penetrating in the thickness direction is used, or the support and the device wafer are separated from each other. A layer (reaction layer) having the property of being altered by absorbing light is interposed therebetween, but in this method, it is necessary to use a special support.
  • the present invention has been made in view of the above background, and its purpose is to stably and temporarily bond a base material when a mechanical or chemical treatment is performed on the base material such as a device wafer.
  • Another object of the present invention is to provide a temporary fixing adhesive, an adhesive film, an adhesive support, a laminate, and a kit that can form an adhesive layer that can be easily released from temporary adhesion to a substrate.
  • the present inventors have used a temporary fixing adhesive that is liquid at 25 ° C. and contains a compound containing a lipophilic group and a fluorine atom, and an elastomer.
  • the present inventors have found that the device wafer and the support can be temporarily bonded with high adhesive force, and that the temporary bonding of the device wafer can be easily released, and the present invention has been completed.
  • the present invention provides the following. ⁇ 1> A temporary fixing adhesive that is liquid at 25 ° C. and contains a compound containing a lipophilic group and a fluorine atom, and an elastomer.
  • Temporary fixing adhesive according to ⁇ 1> wherein a compound containing a lipophilic group and a fluorine atom has a 10% thermal mass reduction temperature of 250 ° C. or higher, which is increased from 25 ° C. at 20 ° C./min. .
  • ⁇ 3> The temporary fixing adhesive according to ⁇ 1> or ⁇ 2>, wherein the elastomer has a 5% thermal mass reduction temperature of 250 ° C. or higher, which is increased from 25 ° C. at 20 ° C./min.
  • ⁇ 4> The temporary fixing adhesive according to any one of ⁇ 1> to ⁇ 3>, wherein the elastomer is an elastomer containing a repeating unit derived from styrene.
  • ⁇ 5> The temporary fixing adhesive according to any one of ⁇ 1> to ⁇ 4>, wherein the elastomer is a hydrogenated product.
  • ⁇ 6> The temporary fixing adhesive according to any one of ⁇ 1> to ⁇ 5>, wherein the elastomer is a block copolymer.
  • ⁇ 7> The temporary fixing adhesive according to any one of ⁇ 1> to ⁇ 6>, wherein the elastomer is a block copolymer of styrene at one end or both ends.
  • the elastomer exceeds 50% by mass of the elastomer A containing a repeating unit derived from styrene in a proportion of 10% by mass or more and 50% by mass or less in all repeating units, and the repeating unit derived from styrene in all repeating units.
  • the temporary fixing adhesive according to any one of ⁇ 1> to ⁇ 7>, comprising an elastomer B contained at a ratio of 95% by mass or less.
  • ⁇ 10> The temporary fixing adhesive according to any one of ⁇ 1> to ⁇ 9>, further comprising a radical polymerizable compound.
  • ⁇ 11> The temporary fixing adhesive according to ⁇ 10>, wherein the radical polymerizable compound is a compound having two or more radical polymerizable groups.
  • ⁇ 12> The temporary fixing adhesive according to ⁇ 10> or ⁇ 11>, wherein the radical polymerizable compound has at least one of the partial structures represented by the following (P-1) to (P-4); * In the formula is a connecting hand.
  • the radical polymerizable compound is trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, isocyanuric acid triallyl, pentaerythritol tri (meth).
  • the temporary fixing adhesive according to any one of ⁇ 10> to ⁇ 12>, which is a seed.
  • the concentration of the lipophilic group and the compound containing a fluorine atom in the adhesive layer ranges from 5% in the thickness direction of the adhesive layer, and 5% in the thickness direction from the surface of any one of the adhesive layers.
  • the adhesive film according to ⁇ 15> which differs from the region in the range of more than 50%.
  • the concentration of the lipophilic group and the compound containing a fluorine atom in the adhesive layer is such that the region in the range of 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support is from the surface on the opposite side of the support.
  • Between the substrate and the support there is at least one adhesive layer A, and the adhesive layer A is liquid at 25 ° C. and contains a lipophilic group and a fluorine atom-containing compound.
  • An adhesive layer A1 that is liquid at 25 ° C. and includes a lipophilic group and a fluorine atom, and an elastomer is provided between the substrate and the support, and the adhesive layer A1 is based on The laminate according to ⁇ 19>, which is in contact with the material and the support.
  • the adhesive layer A further includes an adhesive layer A2 other than the adhesive layer A1.
  • ⁇ 23> The laminate according to ⁇ 21> or ⁇ 22>, wherein the adhesive layer A1 is in contact with at least one of the support and the substrate.
  • ⁇ 24> The laminate according to ⁇ 22>, which includes a support, an adhesive layer A1, an adhesive layer A2, and a base material in this order.
  • ⁇ 25> The laminate according to any one of ⁇ 22> to ⁇ 24>, wherein the adhesive layer A includes the adhesive layer A2, and the adhesive layer A2 includes an elastomer.
  • ⁇ 26> The laminate according to any one of ⁇ 19> to ⁇ 25>, wherein at least one layer of the adhesive layer A includes an elastomer containing a repeating unit derived from styrene.
  • ⁇ 27> The laminate according to ⁇ 26>, wherein the elastomer is a hydrogenated product.
  • ⁇ 28> The laminate according to ⁇ 26> or ⁇ 27>, wherein the elastomer is a block copolymer.
  • the elastomer exceeds 50% by mass of the elastomer A containing a repeating unit derived from styrene in a proportion of 10% by mass or more and 50% by mass or less in all repeating units, and the repeating unit derived from styrene in all repeating units.
  • ⁇ 30> The laminate according to any one of ⁇ 19> to ⁇ 29>, wherein the substrate is a device wafer.
  • the adhesive layer A is peeled from the interface between the substrate and the adhesive layer A, and the range of 50% or more of the area of the peeled surface of the substrate with the adhesive layer A ,
  • the residue of the compound containing a lipophilic group and a fluorine atom is attached, or the adhesive layer A is peeled off from the interface between the support and the adhesive layer A, and the release surface of the adhesive layer A of the support is removed.
  • ⁇ 33> The laminate according to any one of ⁇ 19> to ⁇ 32>, wherein the area of the film surface of the adhesive layer A is smaller than the area of the substrate surface of the support.
  • the diameter of the substrate surface of the support is C ⁇ m
  • the diameter of the substrate surface of the substrate is D ⁇ m
  • the diameter of the film surface of the adhesive layer A is T ⁇ m
  • (C-200) ⁇ T ⁇ D is satisfied.
  • ⁇ 35> The diameter of the substrate surface of the support is C ⁇ m, the diameter of the substrate surface of the substrate is D ⁇ m, the diameter of the film surface in contact with the support of the adhesive layer A is T C ⁇ m, The lamination according to any one of ⁇ 19> to ⁇ 34>, wherein (C-200) ⁇ T C > T D ⁇ D is satisfied when the diameter of the film surface in contact with the substrate is T D ⁇ m body.
  • a kit which is liquid at 25 ° C. and includes a compound containing a lipophilic group and a fluorine atom, a temporary adhesive A containing an elastomer, and a temporary adhesive B containing a thermoplastic resin. .
  • a temporary fixing adhesive an adhesive film, an adhesive support, a laminate, and a kit capable of forming an adhesive layer that can stably temporarily bond a substrate and can easily release temporary adhesion to the substrate. Became available.
  • substitution and non-substitution includes what does not have a substituent and what has 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 this specification, “light” means actinic rays or radiation.
  • exposure is not limited to exposure with far-ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. It also means drawing with.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acrylic and methacryl
  • (meth) acryloyl” represents “acryloyl” and “methacryloyl”. Represents.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
  • 0.0 mm (inner diameter) ⁇ 15.0 cm) can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
  • the “lipophilic group” means a functional group that does not contain a hydrophilic group. Further, the “hydrophilic group” means a functional group showing affinity with water.
  • 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.
  • the temporary fixing adhesive of the present invention is liquid at 25 ° C. and contains a compound containing a lipophilic group and a fluorine atom (hereinafter referred to as a fluorine-based liquid compound) and an elastomer.
  • a fluorine-based liquid compound a compound containing a lipophilic group and a fluorine atom
  • an elastomer a compound containing a lipophilic group and a fluorine atom
  • the temporary fixing adhesive of the present invention contains the above-mentioned fluorinated liquid compound, the fluorinated liquid compound tends to be unevenly distributed on the surface layer of the adhesive layer, and the concentration of the fluorinated liquid compound in the surface layer of the adhesive layer can be increased. it can. For this reason, the adhesive layer excellent in the peelability with respect to a base material or a support body can be formed. Moreover, since an elastomer is included, an adhesive layer excellent in adhesiveness can be formed by following the fine irregularities of the support and the substrate and by an appropriate anchor effect. For this reason, both adhesiveness and peelability can be achieved.
  • the temporary fixing adhesive of the present invention can be particularly preferably used as a temporary fixing adhesive for manufacturing a semiconductor device. Hereinafter, the temporary fixing adhesive of the present invention will be specifically described.
  • the temporary fixing adhesive of the present invention contains a fluorine-based liquid compound.
  • the liquid state means a compound having fluidity at 25 ° C. and having a viscosity of 1 to 100,000 mPa ⁇ s at 25 ° C., for example.
  • the viscosity of the fluorinated liquid compound at 25 ° C. is more preferably, for example, 10 to 20,000 mPa ⁇ s, and further preferably 100 to 15,000 mPa ⁇ s.
  • the viscosity of the fluorinated liquid compound tends to be unevenly distributed in the surface layer of the adhesive layer.
  • the fluorinated liquid compound can be preferably used in any form of oligomer or polymer.
  • the mixture of an oligomer and a polymer may be sufficient. Such a mixture may further contain a monomer.
  • the fluorinated liquid compound may be a monomer.
  • the fluorine-based liquid compound is preferably an oligomer, a polymer, or a mixture thereof from the viewpoint of heat resistance and the like. Examples of the oligomer and polymer include a radical polymer, a cationic polymer, and an anionic polymer, and any of them can be preferably used. A vinyl polymer is particularly preferred.
  • the weight average molecular weight of the fluorinated liquid compound is preferably 500 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 20,000.
  • the fluorinated liquid compound is preferably a compound that does not denature during the treatment of the base material used for temporary adhesion.
  • a compound that can exist in a liquid state even after heating at 250 ° C. or higher or after treating the substrate with various chemical solutions is preferable.
  • the viscosity at 25 ° C. is 1 to 100,000 mPa ⁇ s after heating to 250 ° C. under a temperature rising condition of 10 ° C./min from a state of 25 ° C. It is preferably 10 to 20,000 mPa ⁇ s, more preferably 100 to 15,000 mPa ⁇ s.
  • the fluorinated liquid compound having such characteristics is preferably a non-thermosetting compound having no reactive group.
  • the reactive group here refers to all groups that react by heating at 250 ° C., and examples thereof include a polymerizable group and a hydrolyzable group. Specifically, for example, a meta (acrylic) group, an epoxy group, an isocyanato group, and the like can be given.
  • the 10% thermal mass reduction temperature raised from 25 ° C. at 20 ° C./min is preferably 250 ° C. or more, and more preferably 280 ° C. or more.
  • an upper limit does not have limitation in particular, For example, 1000 degrees C or less is preferable and 800 degrees C or less is more preferable. According to this aspect, it is easy to form an adhesive layer having excellent heat resistance.
  • mass decreasing temperature is a value measured on the said temperature rising conditions in nitrogen stream by the thermogravimetry apparatus (TGA).
  • the fluorinated liquid compound used in the present invention contains a lipophilic group.
  • the lipophilic group include linear or branched alkyl groups, cycloalkyl groups, and aromatic groups.
  • the number of carbon atoms in the alkyl group is preferably 2 to 30, more preferably 4 to 30, further preferably 6 to 30, and particularly preferably 12 to 20.
  • Specific examples of the alkyl group include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl Group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, 2-ethylhexyl group.
  • the alkyl group may have a substituent.
  • Examples of the substituent include a halogen atom, an alkoxy group, and an aromatic group.
  • Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkoxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkoxy group is preferably linear or branched.
  • the aromatic group may be monocyclic or polycyclic.
  • the carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 14, and most preferably 6 to 10.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the cycloalkyl group preferably has 3 to 30 carbon atoms, more preferably 4 to 30 carbon atoms, still more preferably 6 to 30 carbon atoms, and most preferably 12 to 20 carbon atoms.
  • Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Can be mentioned.
  • the cycloalkyl group may have the substituent described above.
  • the aromatic group may be monocyclic or polycyclic.
  • the carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 14, and most preferably 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the elements constituting the ring.
  • aromatic group examples include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring , Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, thiazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinol
  • the fluorinated liquid compound may be a compound containing only one kind of lipophilic group, or may contain two or more kinds.
  • the lipophilic group may contain a fluorine atom. That is, the fluorinated liquid compound in the present invention may be a compound in which only the lipophilic group contains a fluorine atom.
  • a compound further having a group containing a fluorine element also referred to as a fluorine group
  • it is a compound containing a lipophilic group and a fluorine group.
  • the fluorinated liquid compound is a compound having a lipophilic group and a fluorine group
  • the lipophilic group may or may not contain a fluorine atom, but the lipophilic group contains a fluorine atom. Preferably it is not.
  • the fluorinated liquid compound has at least one lipophilic group in one molecule, preferably 2 to 100, particularly preferably 6 to 80.
  • the fluorine group a known fluorine group can be used. Examples thereof include a fluorine-containing alkyl group and a fluorine-containing alkylene group. Of the fluorine groups, those that function as lipophilic groups are included in the lipophilic groups.
  • the carbon number of the fluorine-containing alkyl group is preferably 1 to 30, more preferably 1 to 20, and more preferably 1 to 15.
  • the fluorine-containing alkyl group may be linear, branched or cyclic. Moreover, you may have an ether bond.
  • the fluorine-containing alkyl group may be a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms.
  • the carbon number of the fluorine-containing alkylene group is preferably 2 to 30, more preferably 2 to 20, and more preferably 2 to 15.
  • the fluorine-containing alkylene group may be linear, branched or cyclic. Moreover, you may have an ether bond.
  • the fluorine-containing alkylene group may be a perfluoroalkylene group in which all of the hydrogen atoms are substituted with fluorine atoms.
  • the fluorine-containing liquid compound preferably has a fluorine atom content of 1 to 90% by mass, more preferably 2 to 80% by mass, and still more preferably 5 to 70% by mass.
  • the content of fluorine atoms is defined as “ ⁇ (number of fluorine atoms in one molecule ⁇ mass of fluorine atoms) / mass of all atoms in one molecule ⁇ ⁇ 100”.
  • a commercially available product can be used as the fluorinated liquid compound.
  • the content of the fluorinated liquid compound in the temporary fixing adhesive of the present invention is preferably 0.01 to 10% by mass with respect to the mass of the temporary fixing adhesive excluding the solvent, and preferably 0.02 to 5%.
  • the mass% is more preferable.
  • the lower limit is preferably 0.03% by mass or more.
  • the upper limit is preferably 1% by mass or less, and more preferably less than 0.5% by mass. If content of a fluorine-type liquid compound is the said range, it is excellent in adhesiveness and peelability.
  • One type of fluorine-based liquid compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that total content is the said range.
  • the temporary fix adhesive of the present invention contains an elastomer.
  • an elastomer By using an elastomer, it is possible to form an adhesive layer having excellent adhesiveness by following the fine irregularities of the support and the base material and by an appropriate anchor effect.
  • an elastomer represents the high molecular compound which shows elastic deformation. That is, when an external force is applied, the polymer compound is defined as a polymer compound that has the property of instantly deforming according to the external force and recovering the original shape in a short time when the external force is removed.
  • the weight average molecular weight of the elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and even more preferably 50,000 to 100,000. By being in this range, the solubility of the temporary fixing adhesive in a solvent will be excellent, and coatability will be improved. In addition, when the remaining adhesive layer is removed after peeling the substrate from the support, there is an advantage that no residue remains on the substrate or the support because of excellent solubility in a solvent.
  • the elastomer is not particularly limited, and examples thereof include a block copolymer, a random copolymer, and a graft copolymer, and a block copolymer is preferable. If it is a block copolymer, the flow of the temporary fix
  • elastomer examples include elastomers containing repeating units derived from styrene (polystyrene elastomers), polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, polyacryl elastomers, silicone elastomers, polyimide elastomers, etc. Can be used.
  • polystyrene-based elastomers, polyester-based elastomers, and polyamide-based elastomers are preferable, and polystyrene-based elastomers are most preferable from the viewpoints of heat resistance and peelability.
  • the elastomer is preferably a hydrogenated product.
  • a hydrogenated product of a polystyrene-based elastomer is preferable.
  • the hydrogenated product means a polymer having a structure in which an elastomer is hydrogenated.
  • the elastomer preferably has a 5% thermal mass decrease temperature of 25 ° C. raised at 20 ° C./min, preferably 250 ° C. or more, more preferably 300 ° C. or more, and further preferably 350 ° C. or more.
  • the temperature is 400 ° C. or higher.
  • the upper limit is not particularly limited, but is preferably 1000 ° C. or lower, and more preferably 800 ° C. or lower. According to this aspect, it is easy to form an adhesive layer having excellent heat resistance.
  • the elastomer of the present invention can be deformed to 200% with a small external force at room temperature (20 ° C.) when the original size is 100%, and 130% or less in a short time when the external force is removed. It is preferable to have the property of returning to.
  • Polystyrene Elastomer >>>
  • a polystyrene-type elastomer According to the objective, it can select suitably.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • styrene-butadiene-butylene-styrene SBS
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SBBS styrene-ethylene-butylene styrene block copolymer
  • SEBS styrene-ethylene-butylene styrene block copolymer
  • SEPS styrene-ethylene-propylene-styrene block copolymer
  • SEPS styrene-ethylene-ethylene-propylene-styrene block A copolymer etc.
  • the content of the repeating unit derived from styrene in the polystyrene elastomer is preferably 10 to 90% by mass. From the viewpoint of peelability, the lower limit is preferably 25% by mass or more, and more preferably 51% by mass or more.
  • the polystyrene-based elastomer has an elastomer A containing a repeating unit derived from styrene in a proportion of 10% by mass or more and 50% by mass or less in all repeating units, and 50% by mass of repeating units derived from styrene in all repeating units. It is also preferable to use in combination with elastomer B contained in a proportion of more than 95% and not more than 95% by mass.
  • the flatness of the polished surface of the base material (hereinafter also referred to as flat polishing property) is good, and the warpage of the base material after polishing is improved. Generation can be effectively suppressed.
  • the mechanism by which such an effect is obtained can be assumed to be as follows. That is, since the elastomer A is a relatively soft material, it is easy to form an adhesive layer having elasticity.
  • the adhesive layer can be easily elastically deformed to return to the original shape. As a result, excellent flat polishing properties can be obtained. Further, even if the laminated body after polishing is subjected to heat treatment and then cooled, the adhesive layer can relieve internal stress generated during cooling and effectively suppress the occurrence of warpage. Moreover, since the said elastomer B is a comparatively hard material, the adhesive layer excellent in peelability can be manufactured by including the elastomer B.
  • the elastomer A preferably contains 13 to 45% by mass, more preferably 15 to 40% by mass, of all styrene-derived repeating units. If it is this aspect, the more excellent flat polishing property will be acquired. Furthermore, the occurrence of warping of the substrate after polishing can be effectively suppressed.
  • the hardness of the elastomer A is preferably 20 to 82, more preferably 60 to 79. The hardness is a value measured with a type A durometer according to the method of JIS K6253.
  • the elastomer B preferably contains 55 to 90% by mass, more preferably 60 to 80% by mass, of all styrene-derived repeating units. According to this aspect, peelability can be improved more effectively.
  • the hardness of the elastomer B is preferably 83 to 100, and more preferably 90 to 99.
  • the polystyrene elastomer is preferably a block copolymer of styrene and another resin, more preferably a block copolymer of styrene at one or both ends, and a block copolymer of styrene at both ends. It is particularly preferred.
  • both ends of the polystyrene-based elastomer are made of a styrene block copolymer (a repeating unit derived from styrene)
  • the thermal stability tends to be further improved. This is because a repeating unit derived from styrene having high heat resistance is present at the terminal.
  • the block part of the repeating unit derived from styrene is preferably a reactive polystyrene hard block, which tends to be more excellent in heat resistance and chemical resistance.
  • a reactive polystyrene hard block which tends to be more excellent in heat resistance and chemical resistance.
  • phase-separation by a hard block and a soft block is performed at 200 degreeC or more.
  • the shape of the phase separation is considered to contribute to the suppression of the occurrence of irregularities on the substrate surface of the device wafer.
  • such a resin is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.
  • the unsaturated double bond amount of the polystyrene elastomer is preferably less than 15 mmol, more preferably less than 5 mmol, and more preferably less than 0.5 mmol per 1 g of the polystyrene elastomer from the viewpoint of peelability after the heating step. Most preferably it is.
  • the amount of unsaturated double bonds here does not include the unsaturated double bond in the benzene ring derived from styrene.
  • the amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (NMR) measurement.
  • a repeating unit derived from styrene is a structural unit derived from styrene contained in a polymer when styrene or a styrene derivative is polymerized, and may have a substituent.
  • the styrene derivative include ⁇ -methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and the like.
  • substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group.
  • Examples of commercially available polystyrene elastomers include Tufprene A, Tufprene 125, Tufprene 126S, Solprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene T-439, Tuftec H1272 Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftech H1051, Tuftec H1053, Tuftec P2000, Tuftec H1043 (above, manufactured by Asahi Kasei 8) , Elastomer AR815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer AR8 0C, Elastomer AR-875C, Elastomer AR-885C, Elastomer AR-SC-15
  • Polyester elastomer >>>
  • a polyester-type elastomer According to the objective, it can select suitably.
  • examples thereof include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
  • the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, and the like.
  • Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more.
  • Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 1,4-cyclohexanediol, Examples thereof include alicyclic diols and divalent phenols represented by the following structural formulas.
  • Y DO represents any one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, and —SO 2 —, or benzene.
  • R DO1 and R DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms.
  • p do1 and p do2 each independently represent an integer of 0 to 4, and n do1 represents 0 or 1.
  • polyester elastomer examples include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcin. These may be used alone or in combination of two or more.
  • a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component should be used. You can also.
  • the multi-block copolymer includes various grades depending on the kind, ratio, and molecular weight of the hard segment and the soft segment.
  • Hytrel manufactured by DuPont-Toray Industries, Inc.
  • Perprene manufactured by Toyobo Co., Ltd.
  • Primalloy manufactured by Mitsubishi Chemical
  • Nouvelan manufactured by Teijin Chemicals
  • Espel 1612 and 1620 Hitachi Chemical Industries, Ltd.
  • Polyolefin Elastomer >>>
  • a polyolefin-type elastomer According to the objective, it can select suitably.
  • copolymers of ⁇ -olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene.
  • examples thereof include ethylene-propylene copolymer (EPR) and ethylene-propylene-diene copolymer (EPDM).
  • non-conjugated dienes having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene, and ⁇ -olefin copolymers can be used.
  • a carboxy-modified nitrile rubber obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer can be mentioned.
  • ethylene / ⁇ -olefin copolymer rubber ethylene / ⁇ -olefin / non-conjugated diene copolymer rubber, propylene / ⁇ -olefin copolymer rubber, butene / ⁇ -olefin copolymer rubber, etc.
  • Miralastomer Mitsubishi Chemicals
  • Thermoran Mitsubishi Chemical
  • EXACT Exxon Chemical
  • ENGAGE Low Chemical
  • Espolex Espolex
  • Sarlink Toyobo
  • Newcon Nippon Polypro
  • JSR EXCELLINK
  • Polyurethane Elastomer >>>
  • a polyurethane-type elastomer According to the objective, it can select suitably.
  • an elastomer containing structural units of a hard segment composed of low-molecular glycol and diisocyanate and a soft segment composed of a high-molecular (long-chain) diol and diisocyanate can be used.
  • the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, and poly (1,6-hexene).
  • the number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000.
  • the low molecular weight glycol short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used.
  • the number average molecular weight of the short chain diol is preferably 48 to 500.
  • Examples of commercially available polyurethane-based elastomers include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), milactolan (manufactured by Nippon Milactolan), elastollan (manufactured by BASF), rezemin (manufactured by Dainichi Seika Kogyo), peresen ( Dow Chemical), Iron Rubber (NOK), Mobilon (Nisshinbo Chemical), and the like.
  • Polyamide elastomer >>>
  • a polyamide-type elastomer According to the objective, it can select suitably.
  • an elastomer using a polyamide such as polyamide-6, 11, or 12 as a hard segment and a polyether such as polyoxyethylene, polyoxypropylene, or polytetramethylene glycol and / or polyester as a soft segment may be used.
  • These elastomers are roughly classified into two types: polyether block amide type and polyether ester block amide type.
  • UBE polyamide elastomer examples include UBE polyamide elastomer, UBESTA XPA (manufactured by Ube Industries), Daiamide (manufactured by Daicel Evonik), PEBAX (manufactured by ARKEMA), Grilon ELX (manufactured by Emschemy Japan Co., Ltd.), Nopamid ( Mitsubishi Chemical Co., Ltd.), Glais (Toyobo), Polyetheresteramide PA-200, PA-201, TPAE-12, TPAE-32, Polyesteramide TPAE-617, TPAE-617C (T & K TOKA) Manufactured).
  • UBE polyamide elastomer examples include UBE polyamide elastomer, UBESTA XPA (manufactured by Ube Industries), Daiamide (manufactured by Daicel Evonik), PEBAX (manufactured by ARKEMA), Grilon ELX (manufactured by Emsche
  • Polyacrylic elastomer >>>
  • a polyacrylic-type elastomer According to the objective, it can select suitably.
  • those based on acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, Examples include acrylic acid esters, glycidyl methacrylate, and allyl glycidyl ether.
  • crosslinking point monomers such as acrylonitrile and ethylene, etc. are mentioned.
  • acrylonitrile-butyl acrylate copolymer examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.
  • Silicone elastomer >>>
  • a silicone type elastomer According to the objective, it can select suitably.
  • it is mainly composed of organopolysiloxane, and examples thereof include polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane.
  • Specific examples of the commercially available products include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.
  • Epoxy elastomers include, for example, bisphenol F-type epoxy resins, bisphenol A-type epoxy resins, salicylaldehyde-type epoxy resins, phenol novolac-type epoxy resins or cresol novolac-type epoxy resins with a part or all of the epoxy groups at both terminal carboxylic acids. It can be obtained by modification with modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.
  • the content of the elastomer in the temporary fixing adhesive of the present invention is preferably 50.00 to 99.99% by mass, and 70.00 to 99.99% by mass with respect to the mass of the temporary fixing adhesive excluding the solvent. More preferred is 88.00 to 99.99% by mass. If the content of the elastomer is in the above range, the adhesiveness and peelability are excellent.
  • the elastomer in the temporary fixing adhesive of the present invention may be a combination of a plurality of types.
  • the temporary fixing adhesive of the present invention preferably contains a radically polymerizable compound.
  • a temporary fixing adhesive containing a radical polymerizable compound By using a temporary fixing adhesive containing a radical polymerizable compound, it is easy to suppress fluid deformation of the adhesive layer during heating. For this reason, for example, in the case of heat-treating the laminate after polishing the base material, the flow deformation of the adhesive layer during heating can be suppressed, and the occurrence of warpage can be effectively suppressed.
  • the adhesive layer with hardness can be formed, even if a pressure is locally applied at the time of grinding
  • the radical polymerizable compound is a compound having a radical polymerizable group, and a known radical polymerizable compound that can be polymerized by a radical can be used.
  • a radical polymerizable compound that can be polymerized by a radical can be used.
  • Such compounds are widely known in the industrial field, and can be used without particular limitation in the present invention. These may be any of chemical forms such as monomers, prepolymers, oligomers or mixtures thereof and multimers thereof.
  • a monomer type radical polymerizable compound (hereinafter also referred to as a polymerizable monomer) is a compound different from a 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 of the polymerizable monomer is usually 100 or more.
  • the oligomer type radical polymerizable compound (hereinafter also referred to as polymerizable oligomer) is typically a polymer having a relatively low molecular weight, and is a polymer in which 10 to 100 polymerizable monomers are bonded. It is preferable.
  • 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 number of functional groups of the radical polymerizable compound in the present invention means the number of radical polymerizable groups in one molecule.
  • the radically polymerizable group is a group that can be polymerized by the action of actinic rays, radiation, or radicals.
  • Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond.
  • a styryl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable. That is, the radical polymerizable compound used in the present invention is preferably a (meth) acrylate compound, and more preferably an acrylate compound.
  • the radical polymerizable compound preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups from the viewpoint of warpage suppression, and preferably contains at least one trifunctional or higher functional radical polymerizable compound. More preferably, seeds are included.
  • the upper limit of the radically polymerizable group which the radically polymerizable compound has is not particularly limited, for example, it can be 15 or less, and can be 6 or less.
  • the radically polymerizable compound in this invention contains at least 1 sort (s) of radically polymerizable compounds more than trifunctional from the point that a three-dimensional crosslinked structure can be formed and heat resistance can be improved. Further, it may be a mixture of a bifunctional or lower radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound.
  • radical polymerizable compound examples 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.
  • esters of unsaturated carboxylic acids and polyhydric alcohol compounds are preferred.
  • amides of unsaturated carboxylic acids and polyvalent amine compounds are preferred.
  • 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.
  • 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 compound compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be preferably used in the present invention.
  • radical polymerizable compound a compound having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • the compound described in paragraph No. 0040 of JP-A-2014-189696 can be suitably used in the present invention.
  • 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 compounds 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 radically polymerizable compounds represented by the above general formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.
  • JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a radically polymerizable compound.
  • radical polymerizable compound examples include dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.).
  • Dipentaerythritol penta (meth) acrylate (commercially available: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available: KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) ), And a structure in which these (meth) acryloyl groups are via ethylene glycol or propylene glycol residues. These oligomer types can also be used.
  • the radical polymerizable compound may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • the polyfunctional monomer having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polyfunctional monomer having an acid group is preferred, and particularly preferred in this ester is that 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.
  • the polyfunctional monomer having an acid group may be used alone or in combination of two or more.
  • a preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is within the above range, the production and handling properties are excellent.
  • the polyfunctional monomer which has a caprolactone structure can also be used as a radically polymerizable compound.
  • the polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, diester.
  • ⁇ -caprolactone modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols such as pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone Can be mentioned.
  • 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, and “*” represents a bond.
  • the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.
  • radical polymerizable compound 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) —, wherein y is 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.
  • 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.
  • the total number of (meth) acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10
  • the total of each n is an integer of 0 to 60.
  • 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, 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.
  • — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents a terminal on the oxygen atom side. Is preferred in which X is bonded to X.
  • the compound represented by the general formula (i) or (ii) has a ring-opening skeleton by a ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide, which is a conventionally known process. It can be synthesized from the step of bonding and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. 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 compounds 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 compound 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. Further, as radically polymerizable compounds, addition polymerization 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 is described. Monomers can also be used.
  • radical polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester A-9300, NK ester M-9300, NK Ester A-TMMT, NK ester A-DPH, NK ester A-BPE-4, 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), Blemmer PME400 (manufactured by NOF Corporation), and the like.
  • the radically polymerizable compound preferably has at least one of the partial structures represented by the following (P-1) to (P-4) from the viewpoint of heat resistance. More preferably, it has a partial structure represented. * In the formula is a connecting hand.
  • radical polymerizable compound having the above partial structure examples include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, and isocyanuric acid.
  • the content when the radical polymerizable compound is added is the mass of the temporary fixing adhesive excluding the solvent from the viewpoints of good adhesiveness, flat polishing property, peelability, and warpage.
  • it is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and further preferably 5 to 30% by mass.
  • a radically polymerizable compound may be used alone or in combination of two or more.
  • the mass ratio of the elastomer and the radical polymerizable compound is within the above range, an adhesive layer excellent in adhesiveness, flat polishing property, peelability and warpage suppression can be formed.
  • the temporary tacking adhesive of the present invention may contain an antioxidant from the viewpoint of preventing lowering the molecular weight or gelation of the elastomer due to oxidation during heating.
  • an antioxidant a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, and the like can be used.
  • phenolic antioxidants include para-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, “Irganox 1010”, “Irganox 1330”, “Irganox 3114”, “Irganox 1035” manufactured by BASF Corporation, Examples thereof include “Sumilizer MDP-S” and “Sumilizer GA-80” manufactured by Sumitomo Chemical Co., Ltd.
  • sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, “Sumilizer TPM”, “Sumilizer TPS”, “Sumilizer TP-D” manufactured by Sumitomo Chemical Co., Ltd., and the like.
  • phosphorus antioxidants include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and poly (dipropylene glycol) phenyl.
  • examples thereof include phosphite, diphenylisodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, “Irgafos 168” and “Irgafos 38” manufactured by BASF Corporation.
  • Examples of the quinone antioxidant include para-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
  • Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
  • IRGANOX 1010, Irganox 1330, 3,3′-thiodipropionate distearyl and Sumilizer TP-D are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.
  • a phenol-based antioxidant and a sulfur-based antioxidant or a phosphorus-based antioxidant in combination, and a phenol-based antioxidant and a sulfur-based antioxidant are used in combination.
  • a phenol-based antioxidant and a sulfur-based antioxidant are used in combination.
  • a polystyrene-based elastomer when used as the elastomer, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination.
  • phenolic antioxidant: sulfurous antioxidant 95: 5 to 5:95 is preferable, and 25:75 to 75:25 is more preferable.
  • Irganox 1010 and Sumilizer TP-D Irganox 1330 and Sumilizer TP-D, and Sumilizer GA-80 and Sumilizer TP-D are preferable, Irganox 1010 and Sumilizer TP-D, 13g More preferred are Irganox 1010 and Sumilizer TP-D.
  • the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more, from the viewpoint of preventing sublimation during heating.
  • the content of the antioxidant is preferably 0.001 to 20.0% by mass with respect to the total solid content of the temporary adhesive, and 0.005 to 10. 0 mass% is more preferable.
  • One type of antioxidant may be sufficient and two or more types may be sufficient. When there are two or more kinds of antioxidants, the total is preferably within the above range.
  • the temporary fixing adhesive of the present invention may have a polymer compound other than the above-described fluorinated liquid compound and elastomer as necessary in order to adjust applicability.
  • 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.
  • the polymer compound is a compound that does not contain a polymerizable group.
  • the weight average molecular weight of the polymer compound is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and still more preferably 100,000 to 300,000.
  • the polymer compound include, for example, hydrocarbon resins, novolac resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyimide resins, polyvinyl chloride resins, and polyvinyl acetate resins. , Teflon (registered trademark), polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, polyetherether Examples thereof include ketone resins and polyamideimide resins. Among these, hydrocarbon resins, novolac resins, and polyimide resins are preferable, and hydrocarbon resins are more preferable. You may use a high molecular compound in combination of 2 or more type as needed.
  • the hydrocarbon resin basically means a resin consisting 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.
  • 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.
  • 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.
  • the hydrocarbon resin meeting the above conditions include terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, and 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, indene petroleum resin, etc.
  • the hydrocarbon resin is preferably a terpene resin, rosin, petroleum resin, hydrogenated rosin, or polymerized rosin, more preferably a terpene resin or rosin, and particularly preferably a terpene resin or rosin.
  • the content of the polymer compound is preferably 5% by mass or more with respect to the total solid content of the temporary fixing adhesive, and is 10% by mass or more. More preferably, it is more preferably 20% by mass or more.
  • the upper limit of the content of the polymer compound is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and 40% by mass with respect to the total solid content of the temporary fixing adhesive.
  • adhesive adhesive of this invention can also be set as the structure which does not contain high molecular compounds other than a fluorine-type liquid compound and an elastomer.
  • substantially no polymer compound means, for example, that the content of the polymer compound is preferably 1% by mass or less, more preferably 0.1% by mass or less, based on the total solid part of the temporary adhesive. More preferably, it is not contained.
  • the temporary fixing adhesive of the present invention preferably contains a solvent.
  • a solvent Any known solvent can be used without limitation, and an organic solvent is preferred.
  • organic solvents examples include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (examples) : Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (example: 3 -Methyl oxypropionate, ethyl 3-oxypropionate, etc.
  • 2-oxy Alkyl propionate Stealth (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • solvents are preferably mixed in two or more types from the viewpoint of improving the coated surface.
  • the content of the solvent of the temporary adhesive is preferably such that the total solid concentration of the temporary adhesive is 5 to 80% by mass from the viewpoint of applicability. 70 mass% is more preferable, and 10 to 60 mass% is particularly preferable.
  • 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.
  • the temporary fixing adhesive of the present invention preferably contains a surfactant.
  • a surfactant any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and silicone surfactants.
  • the temporary fixing adhesive preferably contains a silicone surfactant as a surfactant from the viewpoint of applicability.
  • a silicone surfactant as a surfactant from the viewpoint of applicability.
  • it becomes easier to apply a uniform thickness by containing a silicone surfactant so that it can be more preferably used.
  • silicone surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, The surfactants described in Kaihei 7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 can be mentioned. An agent can also be used.
  • examples of commercially available silicone surfactants include KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP-341, KP-104, KP-110.
  • the content of the surfactant in the temporary adhesive is 0.001 to 5% by mass with respect to the total solid content of the temporary adhesive from the viewpoint of applicability.
  • 0.005 to 1% by mass is more preferable, and 0.01 to 0.5% by mass is particularly preferable.
  • 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 temporary fixing adhesive in the present invention is various additives as required, for example, a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, and an ultraviolet absorber as long as the effects of the present invention are not impaired.
  • An agent, an anti-aggregation agent and the like can be blended.
  • the total blending amount is preferably 3% by mass or less based on the total solid content of the temporary adhesive.
  • the temporary fixing adhesive of the present invention preferably does not contain impurities such as metals.
  • the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and particularly preferably (not more than the detection limit of the measuring device).
  • Examples of a method for removing impurities such as metals from the temporary fixing adhesive include filtration using a filter.
  • the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel.
  • filters having different hole diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • a raw material having a low metal content is selected as a raw material constituting the temporary fixing adhesive.
  • Examples of the method include filtering and performing distillation under conditions in which the inside of the apparatus is lined with polytetrafluoroethylene or the like and contamination is suppressed as much as possible.
  • the preferable conditions for filter filtration performed on the raw materials constituting the temporary fixing adhesive are the same as those described above.
  • impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
  • adsorbent known adsorbents can be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • the temporary fix adhesive of the present invention can form an adhesive layer excellent in adhesiveness and peelability. Therefore, for example, when a mechanical or chemical treatment is performed on a device wafer, the device wafer and the support can be stably temporarily bonded, and the temporary bonding to the device wafer can be easily released. It can be suitably used as a temporary fixing adhesive for production.
  • the adhesive film of this invention has the contact bonding layer containing the fluorine-type liquid compound mentioned above and an elastomer.
  • the adhesive layer preferably includes the above-described elastomer A and elastomer B as the elastomer.
  • an adhesive layer contains the radically polymerizable compound mentioned above.
  • This adhesive layer can be formed using the above-described temporary fixing adhesive of the present invention.
  • the fluorinated liquid compound is unevenly distributed in the surface layer of the adhesive layer. For this reason, it is excellent in peelability.
  • the adhesive layer contains an elastomer, excellent adhesiveness can be obtained by following the fine irregularities of the support and the substrate and by an appropriate anchor effect. For this reason, both adhesiveness and peelability can be achieved.
  • the adhesive layer has a concentration of the fluorinated liquid compound exceeding 5% in the thickness direction and in a region in the range of 5% of the thickness of the adhesive layer from either surface of the adhesive layer. It is preferable that the difference in the region in the range of 50%.
  • the concentration of the fluorinated liquid compound in the adhesive layer can be determined by combining, for example, a method of performing X-ray photoelectron spectroscopy (ESCA) measurement while etching, or oblique cutting and time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurement. It can be measured by the method.
  • ESA X-ray photoelectron spectroscopy
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the solvent content of the adhesive film of the present invention is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably not contained.
  • the solvent content of the adhesive film can be measured by a gas chromatography method.
  • the average thickness of the adhesive layer is not particularly limited, but is preferably 0.1 to 500 ⁇ m, more preferably 0.1 to 200 ⁇ m, still more preferably 10 to 200 ⁇ m, and 50 Particularly preferred is ⁇ 200 ⁇ m.
  • the average thickness of the adhesive layer is in the above range, it is easy to obtain an adhesive film having excellent flatness.
  • the average thickness of the adhesive layer is defined as the average value of five points measured by ellipsometry.
  • a release layer may be formed on one side or both sides of the adhesive layer.
  • the average thickness of the release layer is preferably 0.001 to 1 ⁇ m, and more preferably 0.01 to 0.5 ⁇ m. If it is the said range, while an adhesive film has moderate adhesive force and adhesiveness with a base material or a support body is good, an adhesive film can be easily peeled from a base material or a support body.
  • the average thickness of the release layer is defined as the average value of five points measured by ellipsometry.
  • the release layer preferably contains a compound containing at least one selected from fluorine atoms and silicon atoms, and more preferably contains a fluorine-based silane coupling agent.
  • the fluorine content of the release layer is preferably 30 to 80% by mass, more preferably 40 to 76% by mass, and particularly preferably 60 to 75% by mass.
  • the fluorine content is defined by “ ⁇ (number of fluorine atoms in one molecule ⁇ mass of fluorine atoms) / mass of all atoms in one molecule ⁇ ⁇ 100”.
  • the release layer preferably contains 10 to 100% by mass, preferably 50 to 100% by mass, of a compound containing at least one selected from fluorine atoms and silicon atoms, based on the total solid content of the release layer. Is more preferable. It is preferable that a release layer contains the three-dimensional crosslinked material containing a fluorine atom from a heat resistant viewpoint. Among these, a three-dimensional crosslinked product of a fluorine-containing polyfunctional monomer / oligomer or a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is preferable, and a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is particularly preferable.
  • fluorine-containing silane coupling agent a non-halogen silane coupling agent having a low risk to human body and low metal corrosivity is preferable, and fluorine-containing alkoxysilane is particularly preferable.
  • commercially available products include OPTOOL DAC-HP and OPTOOL DSX manufactured by Daikin Industries, Ltd.
  • Examples of the halogen-based silane coupling agent include a fluorinated chlorosilane compound.
  • the release layer can contain a polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms.
  • the non-three-dimensional crosslinked structure means that the compound does not contain a crosslinked structure or the ratio of the crosslinked structure forming the three-dimensional crosslinked structure to the total crosslinked structure in the compound is 5% or less. % Or less is preferable. It is preferable that it is contained substantially.
  • the polymer compound having a non-three-dimensional crosslinked structure having a 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, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester.
  • Homopolymers of one or more fluorine-containing monofunctional monomers or copolymers of these monomers copolymers of one or more fluorine-containing monofunctional monomers with ethylene, fluorine-containing monofunctional monomers And at least one fluorine-containing resin selected from a copolymer of one or more of these and chlorotrifluoroethylene.
  • the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic acid 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 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.
  • acrylate esters such as alkyl acrylate (alkyl group preferably has 1 to 20 carbon atoms), such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid Butyl, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol Monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg 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, ste Lil, include such glycidyl ester, 2-ethylhexyl, lauryl, higher alcohol (meth) acrylate stearyl, especially acrylate.
  • a commercially available polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom may be used.
  • Teflon registered trademark
  • DuPont Teflon
  • Tefzel DuPont
  • Fullon Asahi Glass
  • Halar SolvaySolexis
  • Heiler SolvaySolexis
  • Lumiflon Alignment
  • Afras Alignment
  • Cytop Align
  • Cefral Soft Central Glass Co., Ltd.
  • Cefral Coat Central Glass Co., Ltd.
  • Dionine Dionine
  • fluororesins Vuitton (DuPont Co., Ltd.), Kalrez (DuPont Co., Ltd.)
  • Various fluoro oils including perfluoropolyether oils such as fluoro rubber, Krytox (DuPont), Fomblin (Daitotech), Demnam (Daikin Industries), etc., and
  • the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) of the non-three-dimensional crosslinked polymer compound having a fluorine atom is preferably 100000 to 2000, more preferably 50000 to 2000, and 10,000 to Most preferred is 2000.
  • the content of the polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms in the release layer is preferably 1 to 99% by mass with respect to the total solid content of the release layer, from the viewpoint of good releasability. More preferably, it is preferably -95% by mass, more preferably 5-90% by mass.
  • the ratio (mass ratio) of the three-dimensional crosslinked product containing fluorine atoms and the polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms is preferably 5:95 to 50:50, and 10:90 to 40:60 is more preferable, and 15:85 to 30:70 is still more preferable.
  • the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom may be only one kind or two or more kinds. In the case of two or more types, the total is preferably in the above range.
  • the release layer can be formed using a composition containing a release component (release layer forming composition).
  • the release component is preferably a material containing at least one selected from fluorine atoms and silicon atoms. Examples of the material containing at least one selected from a fluorine atom and a silicon atom include polymerizable monomers having a fluorine atom or a silicon atom. A fluorine-based silane coupling agent is more preferable.
  • the content of the release component is preferably 5 to 100% by mass, more preferably 50 to 100% by mass, and more preferably 90 to 90% by mass with respect to the total solid content of the release layer forming composition from the viewpoint of good releasability. 100 mass% is more preferable.
  • the polymerizable monomer having a fluorine atom or a silicon atom is preferably a radical polymerizable monomer or oligomer in which one or more fluorine atoms or silicon atoms are contained in one molecule, and two or more fluorine atoms are contained in one molecule.
  • Particularly preferred is a polymerizable monomer having a group generally called a perfluoro group.
  • the radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom has a radically polymerizable functional group, and the radically polymerizable functional group is not particularly limited, but is an unsaturated group (such as an ethylenically unsaturated bond group). ) Is preferred.
  • the radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom preferably has two or more radically polymerizable functional groups, whereby the device wafer after undergoing a process at a high temperature in the device manufacturing process.
  • the peelability from can be further improved.
  • the polymerizable monomer having a fluorine atom can be selected from known monomers, preferably a monomer having a polymerizable group, and more preferably a fluorine-based silane coupling agent.
  • Examples of the polymerizable group include a silyl group having a hydroxyl group or a hydrolyzable group (for example, 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.
  • a silyl group having a hydroxyl group or a hydrolyzable group for example
  • the radically polymerizable monomer having a fluorine atom is preferably a compound 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 is preferably 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) —, and a combination of two or more thereof are 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 that 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.
  • radical polymerizable monomer or 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 to 98 mol%, preferably 10 to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. More preferred.
  • 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 radically polymerizable monomer or oligomer having a fluorine atom is not particularly limited and is preferably a release layer.
  • the content is preferably 0.01 to 15% by mass with respect to the total solid content of the forming composition. If it is 0.01 mass% or more, sufficient peelability is obtained. If it is 15 mass% or less, sufficient adhesive force will be obtained.
  • the radically polymerizable monomer or oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer.
  • at least one terminal of a polydimethylsiloxane bond is an ethylenically unsaturated group such as a (meth) acryloyl group and 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.
  • radical polymerizable monomer having a silicon atom a compound represented by the general formula (11) or (12) is preferable.
  • 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 or oligomer having a silicon atom is based on the total solid content of the release layer forming composition. 0.01 to 15% by mass is preferable. If it is 0.01 mass% or more, sufficient peelability is obtained. If it is 15 mass% or less, sufficient adhesive force will be obtained. 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.
  • radical polymerizable monomer having a fluorine atom or a silicon atom examples include RS-75, RS-72-K, RS-76-E, RS-72-K manufactured by DIC Corporation, and OPTOOL manufactured by Daikin Industries, Ltd.
  • DAC-HP fluorine silane coupling agent
  • Examples thereof include -22-164E, EBECRYL350, EBECRYL1360 manufactured by Daicel-Cytec, TEGORad2700 manufactured by Degussa, and UV-3500B (manufactured by BYK).
  • materials having fluorine atoms or silicon atoms include (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane, (fluoro) alkyl phosphate, parylene fluoride, silicon acrylate copolymer, tetra Examples include copolymers of fluoroethylene and 2,2-bis-trifluoromethyl-4,5-difluoro-1,3-dioxole, polymers having pendant perfluoroalkoxy groups, and fluorinated ethylene-propylene copolymers.
  • the release layer forming composition preferably contains a solvent.
  • a known solvent can be used without limitation, and the same solvent as the solvent in the temporary fixing adhesive described above can be used.
  • the release layer-forming composition can further contain various compounds depending on the purpose within a range not impairing the effects of the present invention.
  • a thermal polymerization initiator, a sensitizing dye, and a chain transfer agent can be preferably used.
  • the solid content concentration at 25 ° C. of the release layer forming composition is preferably 3 to 40% by mass, more preferably 5 to 40% by mass.
  • the release layer is formed by applying the above-described release layer forming composition onto a support using a conventionally known spin coat method, spray method, roller coat method, flow coat method, doctor coat method, dipping method, or the like. And then dried.
  • a conventionally known spin coat method, spray method, roller coat method, flow coat method, doctor coat method, dipping method, or the like are preferable, the spin coat method and the spray method are more preferable, and the spin coat method is particularly preferable.
  • the adhesive film of this invention is good also as a "adhesive film with a release film" by sticking a release film on the single side
  • a long adhesive film is roll shape. It is possible to prevent troubles that the surface of the adhesive layer is scratched or sticks during storage when it is rolled up.
  • the release film can be peeled off when used. For example, in the case where the release film is bonded on both sides, by peeling off the release film on one side, laminating the adhesive surface to a substrate or support, and then peeling off the remaining release film, The sheet surface can be kept as clean as possible.
  • the adhesive film of the present invention can be produced by a conventionally known method.
  • it can be produced by a melt film forming method, a solution film forming method or the like.
  • the melt film forming method realizes fluidity by heating and melting the raw material composition, and forming this melt into a sheet using an extrusion molding apparatus or an injection molding apparatus, and cooling it to form a film (sheet) Is the way to get.
  • a roll-like long film can be obtained.
  • high film thickness accuracy can be obtained.
  • Other additives can also be added by mixing, melting and stirring.
  • a release film may be bonded to one side or both sides of the film to form an “adhesive film with a release film”.
  • the solution casting method realizes fluidity by dissolving the raw material composition with a solvent, and coats this solution on a support such as a film, drum or band to form a sheet, and then the film (sheet) ).
  • a support such as a film, drum or band
  • To apply apply the solution by extruding the solution with pressure from the slit-shaped opening, transferring the solution with a gravure or an aronics roller, and scanning while discharging the solution from a spray or dispenser. Examples include coating methods, dip coating by storing the solution in a tank and passing it through a film, drum or band, and coating by scraping the solution with a wire bar. .
  • a single film (sheet) can be obtained by coating the solution on the support, then drying to form a solid sheet, and then mechanically peeling the sheet from the support.
  • a release layer may be applied on the support in advance by applying a release layer, immersion treatment, gas treatment, electromagnetic wave irradiation treatment, plasma irradiation treatment, or the like. Or it is good also as an "adhesive film with a release film", leaving a film as it is, without peeling off from a support body, and the sheet
  • a release film may be bonded to both sides of the adhesive film to form a “sheet with a double-sided release film”.
  • the adhesive support of the present invention has a support and an adhesive layer containing the above-described fluorinated liquid compound and elastomer.
  • the adhesive layer preferably includes the above-described elastomer A and elastomer B as the elastomer.
  • an adhesive layer contains the radically polymerizable compound mentioned above.
  • This adhesive layer can be formed using the above-described temporary fixing adhesive of the present invention.
  • the average thickness of the adhesive layer varies depending on the application, but is preferably, for example, 0.1 to 500 ⁇ m.
  • the adhesive layer is applied to the support surface by applying the temporary adhesive of the present invention using a spin coating method, a spray method, a roller coating method, a flow coating method, a doctor coating method, a dipping method, or the like, and is dried (baked). Can be formed. Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
  • the average thickness of the adhesive layer in this case is not particularly limited, but is preferably 1 to 100 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • the adhesive layer can also be formed by laminating the above-described adhesive film of the present invention on a support.
  • an adhesive layer By forming an adhesive layer using an adhesive film, it is possible to form an adhesive layer even with materials such as elastomers that are poorly soluble in solvents, making it easy to form an adhesive layer with excellent heat resistance and chemical resistance. .
  • a thick adhesive layer having a thickness of 10 ⁇ m or more can be made flat without thickness unevenness.
  • the average thickness of the adhesive layer in this case is not particularly limited, but is preferably 0.1 to 200 ⁇ m, more preferably 10 to 200 ⁇ m, and particularly preferably 50 to 200 ⁇ m.
  • the adhesive layer has a region where the concentration of the fluorinated liquid compound is 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support. It is preferable to be higher than the region in the range of more than 5% and 50% in the thickness direction of the adhesive layer from the surface. According to this aspect, after temporarily bonding the adhesive support to a substrate such as a device wafer, the peelability is improved when peeling from the device wafer. Furthermore, the adhesive layer can be easily removed from the surface of the substrate or device wafer by a method such as mechanical peeling.
  • the concentration of the fluorinated liquid compound exceeds 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support in the region of 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support. It is preferably more than 10% by mass and more preferably more than 30% by mass than the region in the range of 50%.
  • the support (also referred to as a carrier support) is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate.
  • a silicon substrate in view of the point that it is difficult to contaminate a silicon substrate typically used as a substrate of a semiconductor device and the point that an electrostatic chuck widely used in the manufacturing process of a semiconductor device can be used, it is a silicon substrate.
  • the thickness of the support is not particularly limited, but is preferably 300 ⁇ m to 100 mm, and more preferably 300 ⁇ m to 10 mm.
  • the surface of the support may have a release layer.
  • the support may be a support with a release layer having a release layer on the surface of a substrate such as a silicon substrate.
  • the release layer is preferably a low surface energy layer containing fluorine atoms and / or silicon atoms, and preferably has a material containing fluorine atoms and / or silicon atoms.
  • the fluorine content of the release layer is preferably 30 to 80% by mass, more preferably 40 to 76% by mass, and particularly preferably 60 to 75% by mass.
  • the material for the release layer the same material as the release layer that may be formed on the surface layer of the adhesive film described above can be used.
  • the laminate of the present invention has at least one adhesive layer A between the substrate and the support, and the adhesive layer A is liquid at 25 ° C., and has an oleophilic group and a fluorine atom. It has the contact bonding layer A1 containing the compound to contain and an elastomer.
  • the laminate of the present invention has an adhesive layer A1 containing the above-mentioned fluorinated liquid compound and an elastomer between the substrate and the support, and the adhesive layer A1 is in contact with the substrate and the support. It is preferable that it can improve the throughput of the laminate formation. That is, in the laminated body, it is preferable that only the adhesive layer is not included between the base material and the support without the above-described release layer.
  • the adhesive layer A1 preferably includes the above-described elastomer A and elastomer B as elastomers.
  • the adhesive layer A1 preferably includes the above-described radical polymerizable compound.
  • the adhesive layer A1 can be formed using the above-described temporary fixing adhesive of the present invention.
  • the adhesive layer A may be composed of only one layer. Further, as shown in FIG. 2, it may be composed of two or more adhesive layers. By using two or more adhesive layers, it is easy to bond the support and the substrate with good embedding. In addition, when the adhesive layer A is only one layer, it is preferable in that the throughput can be improved.
  • reference numeral 1 is a base material
  • reference numeral 2 is a support
  • reference numerals 3, 3 ⁇ / b> A, and 3 ⁇ / b> B are adhesive layers A.
  • the adhesive layer A has two or more adhesive layers, it is only necessary to have at least the adhesive layer A1 described above.
  • the adhesive layer A1 described above may have two or more layers.
  • the structure which has 1 layer or more of adhesive layers A1 mentioned above, and 1 or more layers of adhesive layers A2 other than adhesive layer A1 mentioned above may be sufficient.
  • the above-mentioned adhesive layer A1 is in contact with at least one of the base material and the support.
  • the adhesive layer A2 preferably contains a thermoplastic resin.
  • the thermoplastic resin is a resin that softens at 150 to 350 ° C.
  • the storage elastic modulus at 25 ° C. is preferably 10 4 to 10 12 Pa, and 10 5 to 10 11 Pa. More preferably, it is 10 6 to 10 10 Pa.
  • the storage elastic modulus at 150 to 300 ° C. is preferably 10 2 to 10 7 Pa, more preferably 10 1 to 10 6 Pa, and most preferably 10 0 to 10 5 Pa.
  • the storage elastic modulus is a value measured with a dynamic viscoelasticity measuring device (DMA).
  • DMA dynamic viscoelasticity measuring device
  • thermoplastic resin examples include a block copolymer, a random copolymer, and a graft copolymer, and a block copolymer is preferable.
  • the type of the thermoplastic resin is not particularly limited, and is a polystyrene copolymer, a polyester copolymer, a polyolefin copolymer, a polyurethane copolymer, a polyamide copolymer, a polyacrylic copolymer, Silicone copolymers, polyimide copolymers and the like can be used.
  • thermoplastic resin is preferably a block copolymer of styrene and another monomer, and a styrene block copolymer having a styrene block at one or both ends is particularly preferable.
  • the thermoplastic resin is preferably an elastomer.
  • the elastomer is preferably a hydrogenated product.
  • the elastomer contains more than 50% by mass of the styrene-derived repeating unit and the elastomer A containing 10% by mass or more and 50% by mass or less of the repeating unit derived from styrene in the repeating unit derived from styrene. It is also preferable to use in combination with elastomer B contained at a ratio of 95% by mass or less.
  • the flatness of the polished surface of the substrate is good while having excellent peelability, and the occurrence of warpage of the substrate after polishing can be effectively suppressed.
  • the details of the elastomer include the elastomer described in the above-described temporary fixing adhesive of the present invention, and the preferred range is also the same.
  • the adhesive layer A2 can be formed using a temporary fixing adhesive B containing a thermoplastic resin.
  • the content of the thermoplastic resin is preferably 50.00 to 99.99% by mass, more preferably 70.00 to 99.99% by mass, and more preferably 88.00 to the mass of the temporary adhesive B excluding the solvent. Particularly preferred is ⁇ 99.99% by weight. If content of a thermoplastic resin is the said range, it will be excellent in adhesiveness and peelability.
  • the temporary fixing adhesive B can contain the components described in the above-described temporary fixing adhesive of the present invention as components other than the thermoplastic resin.
  • a radically polymerizable compound, an antioxidant, a polymer compound, a solvent, and a surfactant can be mentioned.
  • bonding adhesive of this invention of this invention can be used, and its preferable range is also the same.
  • the surfactant is preferably a silicone surfactant.
  • the temporary fixing adhesive B can contain a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor, and the like. When these additives are blended, the total blending amount is preferably 3% by mass or less based on the total solid content of the temporary adhesive B.
  • the temporary fixing adhesive B can contain the fluorinated liquid compound described in the temporary fixing adhesive of the present invention, or can have a composition that does not substantially contain the fluorinated liquid compound.
  • the adhesive layer A includes the above-described adhesive layer A1 and the above-described adhesive layer A2
  • At least one layer of the adhesive layer A includes an elastomer containing a repeating unit derived from styrene. That is, when the adhesive layer A is composed of only one layer of the above-described adhesive layer A1, it is preferable that the adhesive layer A1 includes an elastomer containing a repeating unit derived from styrene. Further, when the adhesive layer A is formed by laminating two or more of the above-described adhesive layers A1, it is preferable that at least one layer of the adhesive layer A1 includes an elastomer containing a repeating unit derived from styrene.
  • the adhesive layer A includes the above-described adhesive layer A1 and the above-described adhesive layer A2, it is preferable that at least one of the adhesive layer A1 and the adhesive layer A2 includes an elastomer including a repeating unit derived from styrene.
  • the elastomer is preferably a hydrogenated product.
  • the elastomer is preferably a block copolymer.
  • the above-mentioned elastomer has an elastomer A containing a repeating unit derived from styrene in a proportion of 10% by mass or more and 50% by mass or less in all repeating units, and 50% by mass of the repeating unit derived from styrene in all repeating units. It is preferable to include the elastomer B contained in a proportion of 95% by mass or less.
  • the layer configuration of the laminate of the present invention is not particularly limited.
  • the structure which has a support body, adhesive layer A1, adhesive layer A2, and a base material in this order the structure which has a support body, adhesive layer A2, adhesive layer A1, and a base material in this order are mentioned, Support body, adhesive layer A1,
  • the structure which has adhesive layer A2 and a base material in this order is preferable.
  • it is set as the structure which has a support body, adhesive layer A1, adhesive layer A2, adhesive layer A1, and a base material in this order, a support body, adhesive layer A2, adhesive layer A1, adhesive layer A2, and a base material in this order. You can also.
  • a device wafer is preferably used as the substrate.
  • a known device wafer can be used without limitation, and examples thereof include a silicon substrate and 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.
  • a mechanical structure or a circuit may be formed on the surface of the device wafer. Examples of device wafers on which mechanical structures and circuits are formed include MEMS (Micro Electro Mechanical Systems), power devices, image sensors, micro sensors, light emitting diodes (LEDs), optical devices, interposers, embedded devices, and micro devices. Etc.
  • the device wafer preferably has a structure such as a metal bump.
  • the height of the structure is not particularly limited, but is preferably 1 to 150 ⁇ m, for example, and more preferably 5 to 100 ⁇ m.
  • the film thickness of the device wafer before the mechanical or chemical treatment is preferably 500 ⁇ m or more, more preferably 600 ⁇ m or more, and still more preferably 700 ⁇ m or more.
  • the upper limit is preferably 2000 ⁇ m or less, and more preferably 1500 ⁇ m or less.
  • the film thickness of the device wafer after thinning by mechanical or chemical treatment is preferably less than 500 ⁇ m, more preferably 400 ⁇ m or less, and even more preferably 300 ⁇ m or less.
  • the lower limit is preferably 1 ⁇ m or more, and more preferably 5 ⁇ m or more.
  • the support is synonymous with the support described in the adhesive support described above, and the preferred range is also the same.
  • the laminate of the present invention is a laminate having the adhesive layer A1 between the substrate and the support, and the adhesive layer A1 is in contact with the substrate and the support, the support and the adhesive layer
  • the peel strength A with A and the peel strength B between the adhesive layer A and the substrate preferably satisfy the following formulas (1) and (2).
  • the peel strength A and the peel strength B satisfy the relationship of the above formula (1), when the support is peeled from the substrate, the peel strength A and the peel strength B can be peeled from the interface between the support and the adhesive layer A.
  • peeling strength B when peeling strength B satisfy
  • the peel strength B is preferably 3 N / cm or less, and more preferably 2 N / cm or less.
  • the peel strength in the present invention is a value obtained by measuring the strength when pulled up in the 90 ° C. direction. Peel strength A represents the force applied when the substrate is fixed and the end of the support is pulled up in the 90 ° direction at a speed of 50 mm / min.
  • the peel strength B represents the force applied when the substrate is fixed and the film-like adhesive layer is pulled up in the 90 ° direction at a speed of 50 mm / min.
  • the adhesive layer A is peeled from the interface between the substrate and the adhesive layer, and 50% of the area of the peeled surface of the substrate with the adhesive layer A is 50%.
  • the residue of the fluorinated liquid compound is adhered, or the adhesive layer A is peeled from the interface between the support and the adhesive layer, and the area of the peeling surface of the adhesive layer A of the support is In the range of 50% or more, it is preferable that the residue of the fluorinated liquid compound adheres.
  • the residue derived from an elastomer does not adhere in the range of 50% or more of the area of the peeling surface, and more preferably does not adhere in a range of 99% or more.
  • the residue of the fluorine-based liquid compound and the residue derived from the elastomer can be observed visually, with an optical microscope, a scanning electron microscope, X-ray photoelectron spectroscopy, etc. In the present invention, the peeled surface was measured by X-ray photoelectron spectroscopy. Shall.
  • the “residue of the fluorinated liquid compound” is a fluorinated liquid compound component of the adhesive layer
  • the “residue derived from the elastomer” means the elastomer component of the adhesive layer.
  • the laminate of the present invention can be produced by thermocompression bonding the surface of the adhesive support of the present invention described above on which the adhesive layer is formed and the substrate.
  • the pressure bonding conditions are preferably, for example, a temperature of 100 to 200 ° C., a pressure of 0.01 to 1 MPa, and a time of 1 to 15 minutes.
  • the temporary adhesive of the present invention may be applied to the surface of the substrate, heated (baked) to form an adhesive layer, a support is then placed on the surface of the adhesive layer, and thermocompression bonded. it can.
  • it can also manufacture by arrange
  • the adhesive layer A1 is formed on one of the support and the substrate using the temporary fixing adhesive of the present invention, and the temporary bonding of the present invention is applied to the other of the support and the substrate.
  • the adhesive layer A1 or the adhesive layer A2 can be formed using the adhesive or the temporary fixing adhesive B described above, and the surfaces on which the support layer and the adhesive layer of the base material are formed can be manufactured by thermocompression bonding. According to this method, since the adhesive layers are bonded together, the support and the substrate can be embedded with good embedding.
  • the laminated body of this invention uses the temporary fix adhesive of this invention and the above-mentioned temporary fix adhesive B mentioned above for one of a support body and a base material, and each of adhesive layer A1 and the adhesive layer B is 1 It can also be produced by forming an adhesive layer including at least one layer, placing the other of the support and the substrate on the adhesive layer, and thermocompression-bonding the support and the substrate.
  • FIGS. 3A and 3E are schematic cross-sectional views (FIGS. 3A and 3B) for explaining the temporary bonding between the support and the device wafer, respectively, and the device wafer temporarily bonded to the support.
  • an adhesive support 100 in which an adhesive layer 11 is provided on a support 12 is prepared. It is preferable that the adhesive layer 11 is an embodiment that does not substantially contain a solvent.
  • the device wafer 60 (base material) is formed by providing a plurality of device chips 62 on a surface 61 a of a silicon substrate 61.
  • the thickness of the silicon substrate 61 is preferably 200 to 1200 ⁇ m, for example.
  • the device chip 62 is preferably a metal structure, for example, and the height is preferably 10 to 100 ⁇ m.
  • a step of cleaning the support 12 or the back surface of the device wafer 60 with a solvent may be provided.
  • the contamination of the apparatus can be prevented and the thickness can be reduced.
  • the TTV (Total Thickness Variation) of the device wafer can be reduced.
  • the solvent used in the step of cleaning the support 12 or the back surface of the device wafer 60 with a solvent the solvent contained in the above-described temporary fixing adhesive can be used.
  • the adhesive layer 11 preferably completely covers the device chip 62, and preferably satisfies the relationship of “X + 100 ⁇ Y> X” when the height of the device chip is X ⁇ m and the thickness of the adhesive layer is Y ⁇ m.
  • the fact that the adhesive layer 11 completely covers the device chip 62 is effective when it is desired to further reduce the TTV (Total Thickness Variation) of the thin device wafer (that is, when the flatness of the thin device wafer is to be further improved). It is.
  • the plurality of device chips 62 are protected by the adhesive layer 11, so that it is possible to almost eliminate the uneven shape on the contact surface with the support 12. Therefore, even if the thickness is reduced in such a supported state, the possibility that the shape derived from the plurality of device chips 62 is transferred to the back surface 61b1 of the thin device wafer is reduced, and as a result, the thin shape finally obtained The TTV of the device wafer can be further reduced.
  • the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (though not particularly limited, for example, thinning treatment such as grinding or chemical mechanical polishing (CMP)). , Chemical vapor deposition (CVD), physical vapor deposition (PVD) and other high-temperature / vacuum treatments, treatments using chemicals such as organic solvents, acidic treatment solutions and basic treatment solutions, plating treatments, actinic rays 3) to reduce the thickness of the silicon substrate 61 (for example, the average thickness is preferably less than 500 ⁇ m, preferably 1 to 200 ⁇ m). More preferably, a thin device wafer 60a is obtained.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • other high-temperature / vacuum treatments treatments using chemicals such as organic solvents, acidic treatment solutions and basic treatment solutions
  • plating treatments actinic rays 3
  • the protruding adhesive layer is removed using a solvent that dissolves the adhesive layer, whereby the treatment under high temperature and vacuum is directly applied to the adhesive layer. Deformation and alteration of the adhesive layer can be prevented.
  • the solvent used in the step of washing the adhesive layer protruding outside the area of the substrate surface of the device wafer with a solvent the solvent contained in the temporary adhesive can be used.
  • the area of the film surface of the adhesive layer is preferably smaller than the area of the substrate surface of the support.
  • the diameter of the substrate surface of the support is C ⁇ m
  • the diameter of the substrate surface of the device wafer is D ⁇ m
  • the diameter of the film surface of the adhesive layer is T ⁇ m, (C-200) ⁇ T ⁇ D It is more preferable to satisfy.
  • the diameter of the substrate surface of the support is C ⁇ m
  • the diameter of the substrate surface of the device wafer is D ⁇ m
  • the diameter of the film surface in contact with the support of the adhesive layer is T C ⁇ m
  • the device wafer of the adhesive layer is
  • T D ⁇ m it is preferable that (C-200) ⁇ T C > T D ⁇ D.
  • the area of the film surface of the adhesive layer refers to the area when viewed from the direction perpendicular to the support, and the film surface is not considered uneven.
  • the substrate surface of the device wafer here corresponds to, for example, the surface 61a of FIG.
  • the diameter of the adhesive layer such as the film surface.
  • the diameter of the substrate surface of the support and the diameter of the substrate surface of the device wafer refer to the diameter of the surface in contact with the adhesive layer.
  • regulated as a "diameter" about a support body etc. it is not essential that a support body etc. are circular (perfect circle) in a mathematical meaning, and what is necessary is just circular. If it is not a perfect circle, the diameter when converted to a perfect circle of the same area is taken as the diameter.
  • a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b1 of the thin device wafer 60a after the thinning process, and a silicon through electrode ( A process of forming (not shown) may be performed.
  • Heat treatment may be performed after the support 12 and the device wafer 60 are temporarily bonded to each other and then peeled off.
  • heat treatment may be performed in a mechanical or chemical treatment.
  • the maximum temperature achieved in the heat treatment is preferably 80 to 400 ° C, more preferably 130 ° C to 400 ° C, and still more preferably 180 ° C to 350 ° C.
  • the highest temperature achieved in the heat treatment is preferably lower than the decomposition temperature of the adhesive layer.
  • the heat treatment is preferably performed for 30 seconds to 30 minutes at the highest temperature, and more preferably for 1 minute to 10 minutes at the highest temperature.
  • the support 12 is detached from the thin device wafer 60a.
  • 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 60a in a direction perpendicular to the thin device wafer 60a without any treatment.
  • the peeling interface is preferably peeled off at the interface between the support 12 and the adhesive layer 11.
  • the peel strength A at the interface between the support 12 and the adhesive layer 11 and the peel strength B between the device wafer surface 61a and the adhesive layer 11 preferably satisfy the following expressions.
  • the adhesive layer 11 is brought into contact with a later-described stripping solution, and then, if necessary, the thin device wafer 60a is slid with respect to the support 12, and then the end of the thin device wafer 60a is applied to the device wafer. It can also be peeled off by pulling up vertically.
  • the stripping solution water and a solvent (organic solvent) can be used.
  • dissolves the contact bonding layer 11 is preferable.
  • organic solvent examples include aliphatic hydrocarbons (hexane, heptane, isoper E, H, G (manufactured by Esso Chemical Co., Ltd.), limonene, para-menthane, nonane, decane, dodecane, decalin, etc.), aromatic Group hydrocarbons (toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethyl Propyl) benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohex
  • 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 halides, sulfuric acid, nitric acid, phosphoric acid, boric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, para-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.
  • inorganic acids such as hydrogen halides, sulfuric acid, nitric acid, phosphoric acid, boric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, para-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid
  • Organic acids such as formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid
  • 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.
  • the thin device wafer can be obtained by removing the adhesive layer 11 from the thin device wafer 60a.
  • the method for removing the adhesive layer 11 includes, for example, a method of peeling and removing (mechanical peeling) the adhesive layer in the form of a film, a method of peeling and removing the adhesive layer after swelling with a peeling liquid, and spraying the peeling liquid onto the adhesive layer. Examples thereof include a method for destructive removal, a method for dissolving and removing the adhesive layer by dissolving it in a stripping solution, and a method for removing the adhesive layer by decomposition and vaporization by irradiation with actinic rays, radiation or heat.
  • a method of peeling and removing the adhesive layer in the form of a film and a method of dissolving and removing the adhesive layer in an aqueous solution or an organic solvent can be preferably used.
  • an organic solvent the organic solvent demonstrated with the stripping solution mentioned above can be used. From the viewpoint of reducing the amount of solvent used, it is preferable to remove the film as it is. Further, from the viewpoint of reducing damage on the surface of the device wafer, dissolution and removal are preferable.
  • the peel strength B between the device wafer surface 61a and the adhesive layer 11 preferably satisfies the following formula (2).
  • the support can be regenerated by removing the adhesive layer.
  • a method for removing the adhesive layer as it is in the form of a film, a method for physically removing it by brush, ultrasonic waves, ice particles, aerosol spraying, a method for dissolving and removing by dissolving in an aqueous solution or an organic solvent, actinic rays
  • the chemical removal method include a method of decomposing and vaporizing by irradiation with radiation and heat, and a conventionally known cleaning method can be used depending on the support.
  • a silicon substrate is used as the support
  • a conventionally known silicon wafer cleaning method can be used.
  • aqueous solutions or organic solvents that can be used for chemical removal include strong acids, strong bases, The oxidizing agent or a mixture thereof is raised.
  • acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid and organic acids, bases such as tetramethylammonium, ammonia and organic bases, oxidation of hydrogen peroxide and the like Or a mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of hydrofluoric acid and ammonium fluoride, etc. Can be mentioned.
  • the support cleaning liquid preferably contains an acid (strong 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.
  • 30% by mass hydrogen peroxide water can be preferably used, and the mixing ratio of the strong acid and 30% by mass hydrogen peroxide water is preferably 0.1: 1 to 100: 1 by mass ratio. : 1 to 10: 1 is more preferable, and 3: 1 to 5: 1 is most preferable.
  • FIG. 4A to 4E are schematic cross-sectional views (FIGS. 4A and 4B) for explaining the temporary bonding between the support and the device wafer, and the device wafer temporarily bonded to the support.
  • this embodiment is different from the first embodiment in that an adhesive layer is formed on the surface 61a of the device wafer.
  • the adhesive layer 11a is formed by applying (preferably applying) a temporary fixing adhesive to the surface 61a of the device wafer 60 and then drying (baking). be able to. Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
  • FIG. 4B the support 12 and the device wafer 60 are pressure-bonded, and the support 12 and the device wafer 60 are temporarily bonded.
  • FIG. 4B the support 12 and the device wafer 60 are pressure-bonded, and the support 12 and the device wafer 60 are temporarily bonded.
  • the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment, and the thickness of the silicon substrate 61 is reduced as shown in FIG. Thinning to obtain a thin device wafer 60a.
  • the support 12 is detached from the thin device wafer 60a.
  • the adhesive layer 11 is removed from the thin device wafer 60a.
  • FIG. 5A to 5E are schematic cross-sectional views (FIGS. 5A and 5B) for explaining the temporary bonding between the support and the device wafer, respectively, and the device wafer temporarily bonded to the support.
  • FIG. 5C Schematic showing a thinned state (FIG. 5C), a state where the support and the device wafer are peeled off (FIG. 5D), and a state after removing the adhesive layer from the device wafer (FIG. 5E). It is sectional drawing.
  • adhesive layers 11b and 11c are formed on the support 12 and the surface 61a of the device wafer, respectively.
  • attaches the support body 12 and the device wafer 60) is different from said 1st embodiment.
  • At least one of the adhesive layer 11b and the adhesive layer 11c can be formed using the temporary fixing adhesive of the present invention. Both the adhesive layer 11b and the adhesive layer 11c can be formed by using the temporary fixing adhesive of the present invention, and only one adhesive layer is used by using the temporary fixing adhesive of the present invention and the other adhesive layer. Can also be formed using the temporary adhesive B described above.
  • the adhesive layer 11b is formed using the above-described temporary fixing adhesive B, and the adhesive layer 11c is formed using the temporary fixing adhesive of the present invention.
  • the adhesive layers 11b and 11c may be composed of only one layer, or may be a laminate formed by laminating two or more adhesive layers. That is, each adhesive layer can be formed by repeatedly applying two or more types of temporary adhesives.
  • FIG. 6 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 11b formed of a conventional temporary fixing adhesive is provided on the support 12 as an adhesive support.
  • 100a otherwise, the adhesive support 100a and the device wafer are temporarily bonded in the same manner as described with reference to FIG. 3, and the silicon substrate is thinned on the device wafer. Similar to the above-described procedure, the thin device wafer 60a is peeled off from the adhesive support 100a.
  • the conventional temporary fixing adhesive it is difficult to easily release the temporary support to the device wafer without temporarily supporting the device wafer with a high adhesive force and damaging the device wafer.
  • a highly adhesive adhesive is used among the conventional temporary fixing adhesives, the temporary bonding between the device wafer and the support is too strong. It becomes a trend. Therefore, in order to release the temporary bonding that is too strong, for example, as shown in FIG. 6, a tape (for example, dicing tape) 70 is attached to the back surface of the thin device wafer 60a, and the thin device wafer 60a is bonded from the adhesive support 100a.
  • the structure chip 63 is detached from the device chip 62 provided with the structure 63 and the device chip 62 is likely to be damaged.
  • temporary support to the device wafer can be easily released, but the temporary adhesion between the device wafer and the support is too weak in the first place, A problem that the device wafer cannot be reliably supported by the support tends to occur.
  • the laminate of the present invention exhibits sufficient adhesiveness and can easily release the temporary adhesion between the device wafer 60 and the support 11. That is, according to the laminated body of the present invention, the device wafer 60 can be temporarily bonded with high adhesive force, and the temporary bonding to the thin device wafer 60a can be easily released without damaging the thin device wafer 60a.
  • the adhesive layer has a single layer structure, but the adhesive layer may have a multilayer structure.
  • a silicon substrate is used as the device wafer.
  • the present invention is not limited to this, and any device that can be subjected to mechanical or chemical processing in the method of manufacturing a semiconductor device is not limited thereto. It may be a processing member.
  • a compound semiconductor substrate can also be mentioned, and 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.
  • the device wafer (silicon substrate) is mechanically or chemically treated as a device wafer thinning process and a through silicon via formation process, but is not limited thereto. Any processing required in the method of manufacturing a semiconductor device is included.
  • the shape, size, number, arrangement location, and the like of the device chip in the device wafer exemplified in the above-described embodiment are arbitrary and are not limited.
  • the kit of the present invention is in a liquid form at 25 ° C., and includes a temporary fixing adhesive A including a lipophilic group and a fluorine atom-containing compound and an elastomer, and a temporary fixing adhesive B including a thermoplastic resin.
  • the temporary fix adhesive A is synonymous with the temporary fix adhesive of the present invention, and the preferred range is also the same.
  • the temporary fixing adhesive B is synonymous with the temporary fixing adhesive B described in the laminate of the present invention, and the preferred range is also the same.
  • the kit of the present invention preferably further has a base material and a support. Examples of the base material and the support include the base material and the support described in the above-described laminate, and these can be used. By further including the base material and the support, a laminate having an adhesive layer including the above-described adhesive layer A1 and the above-described adhesive layer A2 between the base material and the support can be produced.
  • the adhesive layer forming coating solution 1 is spin-coated on the support 1 with a release layer, and then baked at 110 ° C. for 1 minute, and further baked at 190 ° C. for 4 minutes, thereby having an adhesive layer.
  • the support 1 was produced.
  • A-2) Megafac F-554 (fluorine group / lipophilic group-containing oligomer, liquid compound (viscosity at 25 ° C.
  • A-4 Megafac F-557 (fluorine group / hydrophilic group / lipophilic group-containing oligomer, liquid compound (viscosity at 25 ° C.
  • A-6 Footent 710FL (fluorine group / hydrophilic group / lipophilic group-containing oligomer, liquid compound (viscosity at 25 ° C. in the range of 1 to 100,000 mPa ⁇ s), manufactured by Neos)
  • A-7 Megafac F-477 (fluorine group / hydrophilic group / lipophilic group-containing oligomer, liquid compound (viscosity at 25 ° C.
  • Mw 50,000 to less than 100,000
  • Mw 100,000 to less than 200,000, manufactured by JSR Corporation)
  • Rb-1 ZEONEX 480R (Nippon Zeon cycloolefin polymer)
  • Rb-2 Durimide (registered trademark) 284 (polyimide made by FUJIFILM)
  • Rb-3) PCZ300 (Mitsubishi Gas Chemical Polycarbonate)
  • the amount of unsaturated double bonds is a value calculated by NMR measurement.
  • the mass decrease temperature is a value measured by a thermogravimetric apparatus (TGA) under a condition where the temperature is increased from 25 ° C. at 20 ° C./min in a nitrogen stream.
  • TGA thermogravimetric apparatus
  • test piece The surface of the adhesive support 1 on which the adhesive layer is formed and the device surface of a Si wafer (device wafer) having a diameter of 100 mm are subjected to pressure bonding at 190 ° C. under a pressure of 0.11 MPa for 3 minutes under vacuum. A test piece was prepared.
  • Adhesiveness> Using a tensile tester (Imada Digital Force Gauge, Model: ZP-50N), the tensile strength of the test piece was measured in a direction along the surface of the adhesive layer under the condition of 250 mm / min. Evaluation was made according to the following criteria.
  • test piece was set together with a dicing frame in the center of the dicing tape mounter, and the dicing tape was positioned from above.
  • the test piece and the dicing tape were fixed with a roller (and vacuum), the dicing tape was cut on a dicing frame, and the test piece was mounted on the dicing tape.
  • the test piece was pulled in the vertical direction (90 ° direction) of the adhesive layer under the condition of 50 mm / min, and the peelability was evaluated according to the following criteria.
  • the prepared test piece was heated at 250 ° C.
  • the adhesive layer-attached Si wafer (device wafer) is set on a spin coater with the adhesive layer facing up, and the same solvent as the solvent for the adhesive layer forming coating solution shown in Table 1 below is used as a cleaning solvent. And sprayed for 5 minutes. Furthermore, only Comparative Examples 8, 9, and 10 that did not use mesitylene for spraying for 5 minutes were rinsed by spraying isopropyl alcohol (IPA) while rotating the Si wafer. Further, spin drying was performed. Then, the external appearance was observed, the presence or absence of the adhesive layer remaining on the device surface of the Si wafer (device wafer) was visually checked, and evaluated according to the following criteria. A: No adhesive layer remains. B: Remaining adhesive layer was observed.
  • A With a peel strength of 4 N / cm or less, the adhesive layer can be removed without breaking, and no peel residue of the adhesive layer is observed.
  • B With a peel strength exceeding 4 N / cm, the adhesive layer can be removed without breaking, and no peel residue of the adhesive layer is observed.
  • C Not applicable to any of the above A and B (broken during film peeling)
  • the examples had good adhesiveness and peelability. Furthermore, the removability of the adhesive layer was good. On the other hand, the comparative example was inferior in peelability.
  • the examples had good adhesiveness and peelability. Furthermore, the removability of the adhesive layer was good. On the other hand, the comparative example was inferior in peelability.
  • an adhesive film is located on the release layer of the support body 3 with a release layer, the support body 3 with a release layer and an adhesive film are made to contact under vacuum, and an adhesive film is carried out with a roller. And the release layer-attached support 3 were fixed to produce an adhesive support 3 having an adhesive layer (sheet-like adhesive layer).
  • the adhesive film forming compositions of Examples 41 to 54, 57 to 60, and Comparative Examples 21 to 28 were coated on a release polyethylene terephthalate (PET) film having a thickness of 75 ⁇ m with a wire bar at a speed of 1 m / min. By drying at 140 ° C. for 10 minutes, an adhesive film having a film thickness of 100 ⁇ m was produced.
  • the adhesive film forming compositions of Examples 55 and 56 were melted and stirred at 300 ° C. for 5 minutes, and extruded from a slit having a width of 100 ⁇ m to produce an adhesive film (extruded sheet).
  • composition of the composition for forming an adhesive film A component described in Table 3 is the mass part shown in Table 3.-B component: The B component described in Table 3 is the mass part shown in Table 3.-Irganox 1010 (manufactured by BASF Corp.): 0 .9 mass parts (Examples 55 and 56 only are 3.0 mass parts) ⁇ Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 parts by mass (only Examples 55 and 56 are 3.0 parts by mass) Solvent: parts by mass of the solvents listed in Table 3 shown in Table 3
  • the examples had good adhesiveness and peelability. Furthermore, the removability of the adhesive layer was good. On the other hand, the comparative example was inferior in peelability.
  • the adhesive layer-forming coating solution 4 is applied on a Si wafer having a diameter of 100 mm and a thickness of 525 ⁇ m, and then baked at 110 ° C. for 1 minute, and further baked at 190 ° C. for 4 minutes. A support 4 was prepared.
  • composition of coating solution for forming adhesive layer> -A component The A component described in Table 4 is the mass part shown in Table 4.-B component: The B component described in Table 4 is the mass part shown in Table 4.-Irganox 1010 (manufactured by BASF Corporation): 0 .9 parts by mass-Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 parts by mass-Mesitylene: 30 parts by mass
  • ⁇ Preparation of test piece> The surface of the adhesive support 4 on which the adhesive layer is formed and the device surface of a 100 mm Si wafer (device wafer) having a diameter of 100 mm and a thickness of 525 ⁇ m are applied at 190 ° C. under a pressure of 0.11 MPa for 3 minutes. Crimping was performed to prepare a test piece.
  • the polished surface of the device wafer was visually confirmed, and the presence or absence of a dent having a diameter of 1 mm or more was confirmed.
  • ⁇ Wafer warpage> The device wafer of the prepared test piece was polished to a thickness of 35 ⁇ m, and then the heating rate and cooling rate were set to 10 ° C./min using FLX-2320 manufactured by KLA-Tencor, and the temperature was increased from room temperature to 200 ° C. After heating to ° C., it was cooled to room temperature, and the Bow value was measured.
  • C Bow value is 80 ⁇ m or more
  • the examples had good adhesiveness and peelability. Furthermore, the removal property of the adhesive layer and the flat polishing property were good, and the warpage of the wafer was suppressed. Moreover, the Example which used together the elastomer A mentioned above and the elastomer B as an elastomer had especially favorable flat abrasiveness.
  • the adhesive layer-forming coating solution 5 is spin-coated on a Si wafer having a diameter of 100 mm and a thickness of 525 ⁇ m, then baked at 110 ° C. for 1 minute, and further baked at 190 ° C. for 4 minutes, thereby providing an adhesive having an adhesive layer.
  • a support 5 was prepared.
  • composition of coating solution for forming adhesive layer> -A component The A component of Table 5 is the mass part shown in Table 5-B component: The B component of Table 5 is the mass part shown in Table 5-C component: The C component of Table 5 is , Parts by mass shown in Table 5, Irganox 1010 (manufactured by BASF Corporation): 0.9 parts by mass Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 parts by mass, mesitylene: 30 parts by mass
  • NK Ester A-BPE-4 (Shin Nakamura Chemical Co., Ltd., bifunctional metallate, following structure)
  • C-3 NK Ester A-9300 (Shin Nakamura Chemical Co., Ltd., trifunctional acrylate, following structure)
  • C-4 Triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd., trifunctional allyl compound)
  • C-5 NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., tetrafunctional acrylate)
  • C-6 NK ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., 6-functional acrylate)
  • C-7 NK Ester A-BPE-4 (Shin Nakamura Chemical Co., Ltd., bifunctional acrylate)
  • ⁇ Preparation of test piece> The surface of the adhesive support 5 on which the adhesive layer is formed and the device surface of a 100 mm Si wafer (device wafer) having a diameter of 100 mm and a thickness of 525 ⁇ m are subjected to a vacuum of 190 ° C. and a pressure of 0.11 MPa for 3 minutes. Crimping was performed to prepare a test piece.
  • the examples had good adhesiveness and peelability. Furthermore, the removal property of the adhesive layer and the flat polishing property were good, and the warpage of the wafer was suppressed.
  • mesitylene is supplied to the outer periphery of the silicon wafer and the back surface of the silicon wafer for 40 seconds to form an adhesive layer attached to the outer periphery of the silicon wafer and the back surface of the silicon wafer.
  • the coating solution was washed.
  • An adhesive layer was formed on the surface of the silicon wafer by heating at 110 ° C. for 3 minutes using a hot plate and further heating at 190 ° C. for 3 minutes.
  • another 12-inch silicon wafer (carrier base material) is applied to the surface on which the adhesive layer is formed using a wafer bonding apparatus (manufactured by Tokyo Electron, Synapse V) under a vacuum of 190 ° C., 0.
  • the laminate was obtained by pressure bonding for 3 minutes at a pressure of 11 MPa. At this time, the thickness of the adhesive layer was 40 ⁇ m.
  • the previously used silicon wafer side of the laminate was polished to a thickness of 35 ⁇ m using a back grinder DFG8540 (manufactured by Disco) to obtain a thin laminate.
  • the diameter of the thinned silicon wafer of the laminate was 299 mm.
  • a wafer bonding device Tokyo Electron, Synapse V
  • the diameter was smaller than 250 ⁇ m.
  • the diameter of the film surface on the side in contact with the carrier substrate of the adhesive layer was larger than the diameter of the film surface on the side in contact with the device wafer.
  • the adhesive layer-forming coating solution 6 is spin-coated on a Si wafer having a diameter of 100 mm and a thickness of 525 ⁇ m, then baked at 110 ° C. for 1 minute, and further baked at 190 ° C. for 4 minutes, thereby providing an adhesive having an adhesive layer.
  • a support 6 was prepared.
  • the adhesive layer forming coating solution 7 was spin coated on a Si wafer (device wafer) with a bump made of Cu having a diameter of 100 mm, a thickness of 525 ⁇ m, and a height of 10 ⁇ m, and then baked at 110 ° C. for 1 minute.
  • the adhesive base material which has an adhesive layer was produced by baking at 190 degreeC for 4 minutes.
  • test piece The surface of the adhesive support 6 on which the adhesive layer is formed and the surface of the adhesive base material on which the adhesive layer is formed are pressure-bonded under vacuum at 190 ° C. and a pressure of 0.11 MPa for 3 minutes, A test piece was prepared.
  • ⁇ Adhesiveness> The adhesiveness was evaluated by the same method and standard as the adhesiveness evaluation in Test Example 1. ⁇ Embeddability> Using C-SAM (ultrasonic microscope) for the test piece, the adhesive layer after bonding (including the interface between the adhesive layers, the bonding surface between the bonding layer and the substrate, and the bonding surface between the bonding layer and the substrate) The presence or absence of a void was confirmed. A: No void was generated. B: 1 to 5 small voids having a diameter of 10 ⁇ m or less can be confirmed, but there is no actual harm. C: More than 5 small voids having a diameter of 10 ⁇ m or less can be confirmed, but there is no actual harm.
  • Example 87 to 94 and 96 to 98 with two adhesive layers had better embedding properties than Example 95 with one adhesive layer.
  • a coating solution 8 for forming an adhesive layer is applied onto a Si wafer having a diameter of 100 mm and a thickness of 525 ⁇ m, and then baked at 110 ° C. for 1 minute, and further baked at 190 ° C. for 4 minutes to form a first adhesive layer. did.
  • the adhesive layer forming coating solution 9 is spin-coated on the surface of the first adhesive layer, then baked at 110 ° C. for 1 minute, and further baked at 190 ° C. for 4 minutes to form the second adhesive layer.
  • An adhesive support 9 was formed.
  • the A component of Table 7 is the mass part shown in Table 7-B component:
  • the B component of Table 7 is the mass part shown in Table 7-D component:
  • the D component of Table 7 is , Parts by mass shown in Table 7, Irganox 1010 (manufactured by BASF Corporation): 0.9 parts by mass Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 parts by mass, mesitylene: 30 parts by mass
  • test piece The surface of the adhesive support 9 on which the adhesive layer is formed and the device surface of a Si wafer (device wafer) with a bump made of Cu having a diameter of 100 mm, a thickness of 525 ⁇ m, and a height of 10 ⁇ m are subjected to 190 ° C. under vacuum.
  • the test piece was manufactured by pressure bonding for 3 minutes at a pressure of 0.11 MPa.
  • the examples had good adhesion and peelability. Furthermore, the removal property of the adhesive layer and the flat polishing property were good. Further, the embedding property was good.
  • base material 2 supports 3, 3A, 3B, 11, 11a to 11d: adhesive layer 12: support 60: device wafer 60a: thin device wafer 61: silicon substrate 61a: front surface 61b :, 61b1: back surface 62: Device chip 63: Structure 100: Adhesive support

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