WO2015190478A1 - Temporary adhesion laminate, temporary adhesion laminate manufacturing method, and laminate equipped with device wafer - Google Patents

Temporary adhesion laminate, temporary adhesion laminate manufacturing method, and laminate equipped with device wafer Download PDF

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Publication number
WO2015190478A1
WO2015190478A1 PCT/JP2015/066595 JP2015066595W WO2015190478A1 WO 2015190478 A1 WO2015190478 A1 WO 2015190478A1 JP 2015066595 W JP2015066595 W JP 2015066595W WO 2015190478 A1 WO2015190478 A1 WO 2015190478A1
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group
laminate
device wafer
film
elastomer
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PCT/JP2015/066595
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French (fr)
Japanese (ja)
Inventor
悠 岩井
一郎 小山
沢野　充
義貴 加持
中村　敦
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富士フイルム株式会社
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Priority to KR1020167032859A priority Critical patent/KR20160149245A/en
Priority to JP2016527818A priority patent/JP6321163B2/en
Publication of WO2015190478A1 publication Critical patent/WO2015190478A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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

Definitions

  • the present invention relates to a temporary adhesion laminate, a method for producing a temporary adhesion laminate, and a laminate with a device wafer. More specifically, the present invention relates to a temporary bonding laminate, a method for producing a temporary adhesion laminate, and a laminate with a device wafer, which 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 wafer is supported by a support layer system, and a plasma polymer layer obtained by a plasma deposition method is interposed as a separation layer between the wafer and the support layer system.
  • the adhesive bond between the support layer system and the separation layer is made larger than the bond bond between the wafer and the separation layer, so that when the wafer is detached from the support layer system, the wafer is easily detached from the separation layer.
  • a technique configured to be separated is also known (see Patent Document 2).
  • a pressure-sensitive adhesive film made of syndiotactic 1,2-polybutadiene and a photopolymerization initiator and having an adhesive force that changes by irradiation with radiation is known (see Patent Document 6). Further, the support substrate and the 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 the substrate from the support substrate is known (see Patent Document 7).
  • the support substrate and device wafer are temporarily bonded with two layers with different softening points, and after processing the device wafer, the support substrate 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 device wafer and a support are bonded using an adhesive composition containing a styrene unit as a main chain constituent unit and a wax.
  • an adhesive layer is applied and formed on the device surface of a device wafer, and a release layer containing a fluorinated silane compound is applied and formed on the surface of the support. It is disclosed that the device wafer and the support are bonded by bonding the release layer of the device.
  • Patent Document 12 a device wafer and a support are bonded using a temporary fixing film sheet having a low adhesion layer on both sides or one side of a temporary fixing film containing a specific polyimide resin. It is disclosed.
  • the surface of the device wafer on which the device is provided (that is, the device surface of the device wafer) and the support substrate (carrier substrate) are temporarily bonded via a layer made of an adhesive known in Patent Document 1 or the like.
  • the adhesive layer is required to have a certain degree of adhesion to stably support the device wafer. Therefore, in the case where the entire device surface of the device wafer and the support are temporarily bonded via the pressure-sensitive adhesive layer, the temporary bonding between the device wafer and the support is sufficient, and the device wafer is stably and However, the temporary adhesion between the device wafer and the support is too strong, so that the device may be damaged or detached from the device wafer. There is a tendency for the device to be detached.
  • a plasma polymer layer as a separation layer is formed between the wafer and the support layer system by a plasma deposition method.
  • the forming method is (1) the equipment cost for carrying out the plasma deposition method is usually high; (2) the layer formation by the plasma deposition method requires time for vacuuming and monomer deposition in the plasma apparatus; and (3) Even when a separation layer composed of a plasma polymer layer is provided, when supporting a wafer to be processed, the wafer is released from support while the adhesive bond between the wafer and the separation layer is sufficient. In such a case, it is not easy to control the adhesive bond so that the wafer is easily detached from the separation layer;
  • Patent Document 9 when the adhesive of Patent Document 9 is used as a temporary fixing material, there is a problem that the device is easily damaged when the device wafer is peeled because the peelability is insufficient.
  • an adhesive composition is formed by applying an adhesive composition to a device wafer or a support.
  • uneven thickness was likely to occur.
  • the adhesion to the device wafer or the support tends to be inferior.
  • the peelability of the support from the device wafer was insufficient.
  • Patent Document 12 has a problem in that the followability to the shape of the device surface is insufficient, the adhesiveness is not sufficient, and voids are generated.
  • the back surface of the device is ground and thinned, there is a problem that it cannot be thinned to a uniform thickness.
  • the present invention has been made in view of the above background, and its purpose is that the flatness of the bonding surface between the device wafer and the support is good, and the device wafer and the support can be stably temporarily bonded together.
  • An object of the present invention is to provide a laminated body for temporary bonding that can easily release temporary bonding between a device wafer and a support, a manufacturing method of the laminated body for temporary bonding, and a laminated body with a device wafer.
  • the present inventors have provided a release layer containing a release agent containing at least one selected from a fluorine atom and a silicon atom on one or both sides of a specific film described later.
  • a release layer containing a release agent containing at least one selected from a fluorine atom and a silicon atom on one or both sides of a specific film described later.
  • a laminate for temporary bonding used to temporarily bond a device surface of a device wafer and a support so as to be peelable, and includes a polystyrene-based elastomer, a polyester-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, and a polyamide-based material.
  • a laminate for temporary bonding having a release layer containing a release agent containing at least one selected from atoms and silicon atoms.
  • ⁇ 3> The laminate for temporary adhesion according to ⁇ 1>, wherein the film includes a polystyrene-based elastomer.
  • ⁇ 4> The laminate for temporary adhesion according to any one of ⁇ 1> to ⁇ 3>, wherein the polystyrene elastomer is a hydrogenated product.
  • ⁇ 5> The temporary adhesive laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the 5% thermal mass reduction temperature of the polystyrene-based elastomer raised from 25 ° C. at 20 ° C./min is 250 ° C. or more. .
  • ⁇ 6> The temporary adhesive laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the release agent is a silane coupling agent.
  • ⁇ 7> The temporary adhesive laminate according to any one of ⁇ 1> to ⁇ 6>, wherein a release layer is provided on both surfaces of the film.
  • ⁇ 8> The temporary bonding laminate according to any one of ⁇ 1> to ⁇ 6>, wherein the release layer is provided only on one surface of the film.
  • the temporary adhesion laminate according to any one of ⁇ 1> to ⁇ 8> is provided between the device wafer and the support, and one surface of the temporary adhesion laminate is a device surface of the device wafer.
  • the temporary bonding laminate has release layers on both surfaces of the film.
  • the temporary bonding laminate has a release layer only on one surface of the film, and the release layer is in contact with the surface of the device wafer.
  • the temporary bonding laminate has a release layer only on one surface of the film, and the release layer is in contact with the surface of the device wafer.
  • the flatness on the bonding surface between the device wafer and the support is good, the device wafer and the support can be stably temporarily bonded, and the temporary bonding between the device wafer and the support is easily released. It has become possible to provide a laminate for temporary bonding, a method for producing a laminate for temporary adhesion, and a laminate with a device wafer.
  • 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 ID ⁇ 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
  • 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 laminate for temporary adhesion of the present invention is a laminate for temporary adhesion used for temporarily adhering a device surface of a device wafer and a support, which is a polystyrene-based elastomer, a polyester-based elastomer, and a polyolefin-based elastomer.
  • the laminate for temporary bonding of the present invention uses a film, the flatness on the bonding surface with the device wafer and the support is good. That is, when a coating film formed by coating is used as an adhesive layer, the adhesive layer contains a solvent, so the film thickness is difficult to be uniform due to drying shrinkage, etc. By using as the adhesive layer, the content of the solvent in the adhesive layer can be reduced, the non-uniformity of the thickness of the adhesive layer can be suppressed, and as a result, the adhesiveness can be improved. Furthermore, since the adhesive film includes the above-described material, it is possible to achieve even better adhesiveness by following the fine irregularities of the device wafer and the support body and by an appropriate anchor effect.
  • the laminated body for temporary adhesion of this invention is excellent in flatness, adhesiveness, and peelability.
  • the device surface of the device wafer and the support are temporarily bonded so as to be peelable means that the device wafer and the support are temporarily bonded and integrated (a laminated body with a device wafer) ) To release the temporarily bonded state between the device wafer and the support and separate them.
  • the temporary adhesive state is preferably released by mechanical peeling.
  • the “film” means a flat film or plate.
  • “Flat” means, for example, that the difference between the maximum film thickness and the minimum film thickness is preferably 20% or less of the average film thickness in a cross section along one direction of the film, which will be described later, and is 5% or less. More preferably.
  • the solvent content of the film is, for example, preferably 20% by mass or less, more preferably 5% by mass or less, and particularly preferably not contained.
  • the solvent content of the film can be measured by gas chromatography.
  • the film can be produced by a method such as a melt film forming method or a solution film forming method described later.
  • the laminated body for temporary adhesion of this invention is demonstrated concretely.
  • the average thickness of the adhesive film is not particularly limited, but is preferably 0.1 to 500 ⁇ m, more preferably 0.1 to 200 ⁇ m, and further preferably 10 to 200 ⁇ m. A thickness of 50 to 200 ⁇ m is preferable. If the average thickness of the adhesive film is within the above range, the flatness is good. In the case of a coating film, the flatness tends to decrease as the thickness increases (for example, 10 ⁇ m or more), but the film is excellent in flatness even if the thickness is large.
  • the average thickness of the adhesive film was measured by ellipsometry at five locations at regular intervals from one end face to the other end face in a cross section along one direction of the adhesive film. It is defined as the average value.
  • the “cross section along one direction of the adhesive film” is a cross section orthogonal to the long side direction when the adhesive film is rectangular. Moreover, when an adhesive film is square shape, it is set as the cross section orthogonal to any one side. Moreover, when an adhesive film is circular or elliptical, it is set as the cross section which passes a gravity center.
  • the difference between the maximum film thickness and the minimum film thickness is preferably 20% or less of the average film thickness, and more preferably 5% or less. preferable.
  • the adhesive film may be a thermoplastic film or a thermosetting film. Preferably, it is a thermoplastic film. By being a thermoplastic film, excellent adhesiveness can be obtained. Moreover, even if the surface of the device wafer has irregularities, the followability to the irregularities is good.
  • thermoplastic film for example, the glass transition temperature is the -50 ⁇ 300 ° C., a storage elastic modulus at 0.99 ⁇ 300 ° C.
  • the storage elastic modulus is a value measured using a viscoelasticity measuring device under a constant temperature rise condition.
  • a viscoelasticity measuring device for example, Rheogel-E4000 (manufactured by UBM) can be used.
  • the adhesive film is made of polystyrene elastomer, polyester elastomer, polyolefin elastomer, polyurethane elastomer, polyamide elastomer, polyacryl elastomer, silicone elastomer, polyimide elastomer, polyether ether. It contains one or more polymer components selected from ketones, polyphenylene sulfide, polyphenylene ethers and polyether sulfones.
  • the polymer component is preferably one or more elastomers selected from polystyrene elastomers, polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, polyacryl elastomers, silicone elastomers and polyimide elastomers, and polystyrene elastomers. Is particularly preferred.
  • the elastomer is preferably a hydrogenated product. In particular, a hydrogenated product of a polystyrene-based elastomer is preferable.
  • the adhesive film containing the polymer component can follow a fine unevenness of a support or a device wafer, and can form an adhesive layer having excellent adhesiveness by an appropriate anchor effect. Further, when the support is peeled from the device wafer, the support can be peeled from the device wafer without applying stress to the device wafer or the like, and damage or peeling of the device or the like can be prevented. In particular, when an elastomer, and further, a polystyrene-based elastomer is used, the above effect is remarkable. Further, when the elastomer is a hydrogenated product, the thermal stability and the storage stability are improved.
  • 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 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.
  • the glass transition temperature (hereinafter also referred to as Tg) of the polymer component is preferably ⁇ 50 to 300 ° C., more preferably 0 to 200 ° C.
  • Tg glass transition temperature
  • the value of the said Tg means the lower glass transition temperature.
  • the melting point of the polymer component is preferably ⁇ 50 to 300 ° C., more preferably 0 to 200 ° C.
  • the melting point value means the lower melting point.
  • the polymer component has a weight average molecular weight of preferably 2000 to 200,000, more preferably 10,000 to 200,000, and most preferably 50,000 to 100,000.
  • the polymer component has a 5% thermal mass reduction temperature of 25 ° C. raised at 20 ° C./min, preferably 250 ° C. or higher, more preferably 300 ° C. or higher, and 350 ° C. or higher. Is more preferable, and most preferably 400 ° C. or higher.
  • 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.
  • mass decreasing temperature is a value measured on the said temperature rising conditions in nitrogen stream by the thermogravimetry apparatus (TGA).
  • 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 styrene-butadiene-butylene-styrene.
  • 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 easy peelability, the lower limit is preferably 25% by mass or more, and more preferably 51% by mass or more.
  • the polystyrene elastomer is preferably a block copolymer of styrene and another resin, more preferably a block polymer of styrene at one or both ends, and a block polymer of styrene at both ends. Is particularly preferred.
  • both ends of the polystyrene-based elastomer are made of a styrene block polymer (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.
  • 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.
  • Examples of the styrene derivative include ⁇ -methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and the like.
  • Examples of the 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.
  • 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.
  • 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 a temporary adhesive laminate having excellent heat resistance.
  • 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.
  • 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 Toray DuPont
  • Perprene manufactured by Toyobo Co., Ltd.
  • Primalloy manufactured by Mitsubishi Chemical
  • Nouvelan manufactured by Teijin Chemicals
  • Espel 1612, 1620 Hitachi Chemical Industries, Ltd.
  • Primalloy CP300 manufactured by Mitsubishi Chemical Corporation
  • Polyolefin Elastomer >>>>>
  • 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 >>>>>
  • 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 As commercially available products, UBE polyamide elastomer, UBESTA XPA (manufactured by Ube Industries), Daiamide (manufactured by Daicel Huls), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MS Japan), Nopamid (manufactured by Mitsubishi Chemical Corporation), Glais (manufactured by DIC Corporation), polyether ester amide PA-200, PA-201, TPAE-12, TPAE-32, polyester amide TPAE-617, TPAE-617C ( (T & K TOKA Co., Ltd.).
  • Polyimide elastomer >>>>>
  • a polyimide-type elastomer According to the objective, it can select suitably.
  • a block polymer consisting of engineering plastics such as aromatic polyimide and rubber segments such as polyether, polyester, and polyolefin with a molecular weight of several hundred to 1,000, which are soft segments. It can be preferably used.
  • Specific examples of the commercially available product include UBESTA XPA9040F1 (manufactured by Ube Industries).
  • 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 polyether ether ketone can be used without particular limitation, and examples thereof include Ketron 1000 PEEK series, Ketron HPV PEEK series, Ketron GF30PEEK series, and Ketron GA30PEEK series (manufactured by Quadrant Polypenco Japan).
  • Polyphenylenesulfide can be used without particular limitation, and examples thereof include Tektron 1000PPS and Tektron HPVPPS (manufactured by Quadrant Polypenco Japan).
  • the polyphenylene ether can be used without any particular limitation.
  • Iupiace series Remalloy series (Mitsubishi Engineering Plastics), XYRON series (XYRON S201A, etc.) (Asahi Kasei Chemicals), NORYL series (SABIC Innovative) Plastics Japan).
  • Polyethersulfone >>>>>>> Examples of the polyethersulfone include those described in JP-A-2006-89595, JP-A-2004-352920, JP-A-2002-338688, JP-A-07-97447, and JP-A-4-20530. Examples include polyethersulfone.
  • the use of polyethersulfone having an arene structure in the polymer increases the crystallinity of the film, and the shear force applied during processing of device wafers even in high temperature environments above a certain temperature. Thus, it is easy to obtain a laminate for temporary bonding that can maintain a shearing adhesive force capable of holding a device wafer.
  • Examples of the polyethersulfone having an arene structure include polyethersulfone having a structural unit represented by the formula (IV).
  • R 1 to R 3 are divalent organic groups having an arene structure, provided that the bond in formula (IV) is directly connected to the arene structure in R 1 to R 3 . (That is, —O— and —SO 2 — in —O—R 1 —O—, —O—R 2 —SO 2 — and —SO 2 —R 3 —O— in Formula (IV) are R 1 Is directly connected to the arene structure in R 3 ).
  • R 1 to R 3 may be the same or different.
  • divalent organic group examples include arylene groups such as a phenylene group, a naphthalenediyl group, an anthracenediyl group, and a pyrenediyl group; and two arylene groups such as —C 6 H 4 —C 6 H 4 — A group having a divalent hydrocarbon group between two arylene groups represented by formulas (IV-1) to (IV-3), and the like.
  • the weight average molecular weight (Mw) of the polyethersulfone is preferably 1,000 to 1,000,000, and more preferably 5,000 to 500,000.
  • Mn the number average molecular weight of the polyethersulfone
  • Mw / Mn the molecular weight distribution represented by Mw / Mn is preferably 1 to 5, and more preferably 1 to 3.5.
  • a commercially available product can also be used as the polyethersulfone. Examples of commercially available polyethersulfone include “Ultrason E series” (such as Ultrason E6020) manufactured by BASF, “Radel A series” manufactured by Solvay Advanced Polymer, and “Sumika Excel series” manufactured by Sumitomo Chemical.
  • Examples of the “Sumika Excel series” include Sumika Excel (registered trademark) PES 3600P, Sumika Excel (registered trademark) PES 4100P, Sumika Excel (registered trademark) PES 4100MP, Sumika Excel (registered trademark) PES 4800P, Sumika Excel (registered trademark) PES 5003P, SUMIKAEXCEL (registered trademark) PES5200P, SUMIKAEXCEL (registered trademark) PES5400P, and the like.
  • the adhesive film preferably contains the polymer component in an amount of 50 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 88 to 100% by mass with respect to the total solid content of the film. According to this aspect, it is easy to obtain a temporary adhesion laminate having excellent adhesion and peelability.
  • the polymer component may contain a plurality of the types listed above. Further, the polymer component preferably contains 50 to 100% by mass of a styrene elastomer, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and only the styrene elastomer. It is particularly preferable that it is configured. According to this aspect, it is easy to obtain a temporary adhesion laminate having excellent adhesion and peelability.
  • the adhesive film may contain an antioxidant from the viewpoint of preventing the polymer component from being lowered in molecular weight or gelled 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.
  • the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, “Irganox (registered trademark) 1010” and “Irganox (registered trademark) 1330 manufactured by BASF Corporation.
  • sulfur-based antioxidant examples include 3,3′-thiodipropionate distearyl, “Sumilizer (registered trademark) TPM”, “Sumilizer (registered trademark) TPS”, and “Sumilizer (registered trademark)” manufactured by Sumitomo Chemical Co., Ltd. TP-D ”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 (registered trademark) 168” manufactured by BASF Corporation, and “Irgafos (registered trademark) 38”.
  • Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
  • Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
  • the antioxidant is preferably Irganox® 1010, Irganox® 1330, 3,3′-thiodipropionate distearyl, Sumilizer® TP-D, Irganox® 1010, Irganox (Registered trademark) 1330 is more preferable, and Irganox (registered trademark) 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.
  • the combination of antioxidants includes Irganox® 1010 and Sumilizer® TP-D, Irganox® 1330 and Sumilizer® TP-D, and Sumilizer® GA-80.
  • Sumilizer (R) TP-D are preferred, Irganox (R) 1010, Sumilizer (R) TP-D, Irganox (R) 1330 and Sumilizer (R) TP-D are more preferred, and Irganox (R) Trademark) 1010 and Sumilizer® TP-D are particularly preferred.
  • 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, and 0.005 to 10.0% by mass with respect to the total solid content of the adhesive film. More preferred.
  • One type of antioxidant may be sufficient and two or more types may be sufficient.
  • the total is preferably within the above range.
  • the adhesive film may have a polymer compound other than the above-described polymer component as necessary.
  • any polymer compound can be used.
  • the polymer compound is a compound having a weight average molecular weight of 2000 or more and is usually a compound not containing a polymerizable group.
  • the weight average molecular weight of the polymer compound is preferably 10,000 to 1,000,000, preferably 50,000 to 500,000, and more preferably 100,000 to 300,000. .
  • the polymer compound include, for example, hydrocarbon resins, novolak resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyvinyl chloride resins, polyvinyl acetate resins, Teflon ( Registered resins), polyamide resins, polyacetal resins, polycarbonate resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polysulfone resins, polyethersulfone resins, polyarylate resins, and natural resins such as natural rubber. .
  • hydrocarbon resins and novolac 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 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, polystyrene -Polyolefin copolymers, olefin polymers (eg methylpentene copolymer), and cycloolefin polymers (eg norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer), etc. .
  • the hydrocarbon resin is preferably a terpene resin, rosin, petroleum resin, hydrogenated rosin, polymerized rosin, olefin polymer, or cycloolefin polymer, and is preferably a terpene resin, rosin, olefin polymer, or cycloolefin polymer. More preferably, it is a terpene resin, rosin, olefin polymer or cycloolefin polymer, more preferably a terpene resin, rosin, cycloolefin polymer or olefin polymer, and a cycloolefin polymer. It is particularly preferred.
  • cycloolefin polymers examples include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers.
  • Preferred examples of the cycloolefin polymer include addition (co) polymers containing at least one repeating unit represented by the following general formula (II), and at least one repeating unit represented by the general formula (I).
  • An addition (co) polymer further comprising a species or more is mentioned.
  • Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).
  • m represents an integer of 0 to 4.
  • R 1 to R 6 each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • X 1 to X 3 and Y 1 to Y 3 are each a hydrogen atom, or a carbon group having 1 to 10 carbon atoms.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), and Z is a carbon atom Represents a hydrogen group or a hydrocarbon group substituted with halogen, W represents SiR 18 p D 3-p (R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, Represents OCOR 18 or —OR 18 , and p represents an integer of 0 to 3. n represents an integer of 0 to 10.
  • Norbornene polymers are disclosed in JP-A-10-7732, JP-T 2002-504184, US2004 / 229157A1, WO2004 / 070463A1, and the like.
  • the norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, a norbornene-based polycyclic unsaturated compound and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene can also be subjected to addition polymerization.
  • This norbornene-based polymer is marketed by Mitsui Chemicals, Inc.
  • Tg glass transition temperatures
  • APL8008T Tg70 ° C
  • APL6013T Tg125 ° C
  • APL6015T Tg145 ° C
  • Pellets such as TOPAS 8007, 5013, 6013, 6015, etc. are available from Polyplastics. Further, Appear 3000 is sold by Ferrania.
  • hydrides of norbornene polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, and JP-A-2003-1159767.
  • it can be produced by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization and then hydrogenation.
  • R 5 and R 6 are preferably hydrogen atoms or methyl groups
  • X 3 and Y 3 are preferably hydrogen atoms, and other groups are appropriately selected.
  • This norbornene polymer is sold under the trade name Arton G or Arton F by JSR Co., Ltd., and Zeonor ZF14, ZF16, Zeonex 250, Nippon Zeon Co., Ltd., These are commercially available under the trade names 280 and 480R, and these can be used.
  • the content of the polymer compound is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the adhesive film, More preferably, it is 20 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.
  • An adhesive film can also be set as the structure which does not contain polymer compounds other than a polymer component substantially. “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 adhesive film. More preferably not.
  • the adhesive film may contain a surfactant.
  • a surfactant various surfactants such as a fluorosurfactant, nonionic surfactant, cationic surfactant, anionic surfactant, and silicone surfactant can be used. Is preferred.
  • the surfactant By containing the surfactant, the liquid properties (particularly fluidity) are improved, and in the case of coating and forming an adhesive film, the uniformity of coating thickness and the liquid-saving property can be further improved.
  • the fluorine-containing surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties. Furthermore, the solubility is also good.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2 manufactured by BASF) 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Spa Scan 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
  • cationic surfactants examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) heavy. Combined polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
  • anionic surfactants examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, and 0.005 to 1.0% by mass with respect to the total solid content of the adhesive film. More preferred. Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
  • the adhesive film may contain various additives such as a curing agent, a curing catalyst, a filler, an adhesion promoter, an ultraviolet absorber, an anti-aggregation agent, etc. Can do.
  • the total blending amount is preferably 3% by mass or less based on the total solid content of the adhesive film.
  • the laminate for temporary bonding comprises a release layer containing a release agent containing at least one selected from fluorine atoms and silicon atoms on one surface (one surface) or both surfaces (both surfaces) of an adhesive film.
  • a release layer containing a release agent containing at least one selected from fluorine atoms and silicon atoms on one surface (one surface) or both surfaces (both surfaces) of an adhesive film.
  • the film thickness of the release layer is not particularly limited because an effect can be obtained even if it is a thin film. For example, 0.001 to 1 ⁇ m is preferable, and 0.01 to 0.5 ⁇ m is more preferable. If it is the said range, while the laminated body for temporary adhesion has moderate adhesive force, while adhering with a device wafer or a support body is favorable, the laminated body for temporary adhesion is easily peeled from a base material or a support body. can do.
  • the average thickness of the release layer is determined by ellipsometry in five sections at equal intervals from one end face to the other end face in a cross section along one direction of the release layer. Defined as the average of the measured values.
  • the “cross section along one direction of the release layer” is synonymous with the above-described “cross section along one direction of the adhesive film”.
  • the fluorine content of the release layer is preferably 5 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 50 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 5 to 100% by weight, preferably 50 to 100% by weight, of a release agent containing at least one selected from fluorine atoms and silicon atoms, based on the total solid content of the release layer. Is more preferable, and 90 to 100% by mass is even more preferable.
  • the release layer may have a plurality of types of release agents.
  • the release agent is preferably a compound containing at least a fluorine atom, and more preferably a compound containing a fluorine atom and a silicon atom.
  • the release agent is preferably a silane coupling agent, and more preferably a silane coupling agent containing at least a fluorine atom.
  • the release agent containing at least one selected from a fluorine atom and a silicon atom may be a thermosetting compound or a non-thermosetting compound. Examples of the thermosetting compound include a silane coupling agent.
  • Such a compound is preferably a compound having a group generally called a perfluoro group containing two or more fluorine atoms in one molecule.
  • thermosetting compound a compound having a fluorine atom and a crosslinkable group can be preferably used.
  • the crosslinkable group include a silyl group having a hydroxyl group or a hydrolyzable group (eg, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) acryloyl group, allyl group, Vinyloxy groups, etc.), ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, mercapto groups, ⁇ -ketoester groups, Hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfon
  • crosslinkable group a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), or a group having a reactive unsaturated double bond ((meth) acryloyl group, Compounds having an allyl group, a vinyloxy group, etc.) are preferred.
  • the compound having a silyl group having a hydroxyl group or a hydrolyzable group include a group having at least one fluorine atom and a compound having at least one silyl group.
  • the group having at least one fluorine atom is preferably a compound having a group generally called a perfluoroalkyl group or a perfluoroether group in which two or more fluorine atoms are contained in one molecule.
  • the group having a fluorine atom may have a substituent. The substituent can be arbitrarily selected from the viewpoints of reactivity and thermal stability.
  • halogen atoms such as chlorine, bromine and iodine atoms
  • alkoxy such as methoxy, ethoxy and tert-butoxy
  • An aryloxy group such as a phenoxy group and a p-tolyloxy group
  • an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group
  • an acyloxy group such as an acetoxy group, a propionyloxy group and a benzoyloxy group
  • Acyl groups such as benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group
  • alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group
  • aryls such as phenylsulfanyl group and p-to
  • the silyl group preferably has a silanol group or a hydrolyzable silyl group.
  • the hydrolyzable silyl group is a hydrolyzable silyl group.
  • Examples of the hydrolyzable group include an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. be able to.
  • the silyl group is hydrolyzed to become a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond.
  • Such a hydrolyzable silyl group or silanol group is preferably one represented by the following formula (B-1).
  • R h1 to R h3 is selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. Represents a hydrolyzable group or a hydroxy group.
  • the remaining R h1 to R h3 are each independently a hydrogen atom, a halogen atom, or a monovalent organic substituent (for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group).
  • the hydrolyzable group bonded to the silicon atom is particularly preferably an alkoxy group or a halogen atom, and more preferably an alkoxy group.
  • the alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms from the viewpoint of peelability. More preferably, it is an alkoxy group having 1 to 15 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, particularly preferably an alkoxy group having 1 to 3 carbon atoms, most preferably a methoxy group or an ethoxy group.
  • the halogen atom include an F atom, a Cl atom, a Br atom, and an I atom. From the viewpoint of ease of synthesis and stability, a Cl atom and a Br atom are preferable, and a Cl atom is more preferable.
  • the compound having at least one of a hydrolyzable silyl group and a silanol group is preferably a compound having one or more groups represented by the above formula (B-1), and a compound having two or more is also used. Can do.
  • the hydrolyzable group can be bonded to one silicon atom in the range of 1 to 4, and the total number of hydrolyzable groups in the formula (B-1) is preferably in the range of 2 or 3. . In particular, it is preferable that three hydrolyzable groups are bonded to a silicon atom. When two or more hydrolyzable groups are bonded to a silicon atom, they may be the same as or different from each other. Specific examples of preferred alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, phenoxy, and benzyloxy groups. A plurality of these alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.
  • alkoxysilyl group to which the alkoxy group is bonded examples include, for example, a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group; a dimethoxymethylsilyl group, a diethoxymethylsilyl group And dialkoxymonoalkylsilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group.
  • a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group
  • a dimethoxymethylsilyl group a diethoxymethylsilyl group
  • dialkoxymonoalkylsilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl
  • the compound having a fluorine atom and a silyl group include trichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, Methyldichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, (3-heptafluoroisopropoxy) propyltrichlorosilane, trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, Triethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, dimethylchloro (1H, 1
  • Examples of the compound having a fluorine atom-containing group and a reactive unsaturated double bond include a radical polymerizable monomer having a fluorine atom, and a compound that can be represented by the following general formula (1) is preferable.
  • 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.
  • 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.
  • 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 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.
  • Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.
  • R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group
  • Y 2 and Y 3 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • Rf represents a divalent organic group having a fluorine atom.
  • the monovalent organic group having a fluorine atom in formula (6) and formula (7) is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
  • a fluorine-containing alkyl group having 1 to 15 carbon atoms is particularly preferred.
  • This fluorine-containing alkyl group is a straight chain (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.
  • branched structures for example, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like, and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these).
  • An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , — CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
  • the divalent organic group having a fluorine atom in the formula (10) is not particularly limited, but is preferably a fluorine-containing alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Fifteen fluorine-containing alkylene groups are particularly preferred.
  • This fluorine-containing alkylene group is a straight chain (for example, —CF 2 CF 2 —, —CH 2 (CF 2 ) 4 —, —CH 2 (CF 2 ) 8 CF 2 —, —CH 2 CH 2 (CF 2 ) 4 -, Etc.), branched structures (eg, —CH (CF 3 ) CF 2 —, —CH 2 CF (CF 3 ) CF 2 —, —CH (CH 3 ) CF 2 CF 2 —, —CH (CH 3 ) (CF 2 ) 5 CF 2- and the like) and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl, perfluorocyclopentyl, or substituted therewith A linking group having an alkyl group, etc.) or an ether bond (for example, —CH 2 OCH 2 CF 2 CF 2 —, —CH 2 CH 2 OCH 2 C 4 F 8 —,
  • the monovalent organic group in the formulas (6), (7), and (10) is preferably an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms. At least one or more selected from atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms Examples include organic groups composed of elements. More specific examples include organic groups composed of the following structures singly or in combination. The monovalent organic group may further have a substituent.
  • substituents that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group.
  • the organic group may contain an ether bond, an ester bond, or a ureido bond.
  • the monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
  • the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
  • a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-ethylhexyl group, A methylhexyl group, a cyclopentyl group, etc. are mentioned.
  • alkenyl group and an alkenyl group having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group.
  • the alkynyl group is preferably an alkynyl group having 3 to 10 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethylsilylethynyl group.
  • the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.
  • an alkyl group or an aryl group is preferable.
  • the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms.
  • the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
  • the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
  • an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
  • the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
  • the content of the repeating unit having a fluorine atom is preferably 2 mol% to 98 mol%, preferably 10 mol% to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. Is more preferable.
  • repeating unit having a radical polymerizable functional group a repeating unit represented by the following formula (8) is preferable.
  • R 801 to R 803 each independently represents a hydrogen atom, an alkyl group, or a halogen atom.
  • Y 8 represents a single bond, or —CO—, —O—, — NH— represents a divalent linking group selected from the group consisting of a divalent aliphatic group, a divalent aromatic group, and combinations thereof, and T represents a structure having a radical polymerizable functional group.
  • the alkyl group as R 801 to R 803 is preferably an alkyl group having 1 to 6 carbon atoms.
  • T preferably represents a radical polymerizable functional group represented by the general formula (9).
  • R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • the dotted line represents a bond to a group linked to Y 8.
  • alkyl group examples are preferably alkyl groups having 1 to 8 carbon atoms.
  • the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
  • Y 8 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. To express. Specific examples of comprising the combination Y 8 below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the formula (9).
  • the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
  • an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
  • the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
  • the content of the repeating unit having a radical polymerizable functional group is preferably 2 mol% to 98 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom, and is preferably 10 mol% to 90 mol%. It is more preferable that
  • the weight average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a fluorine atom as measured by gel permeation chromatography (GPC) is preferably 2000 to 20000, more preferably 2000 to 15000, and more preferably 2000 to 10,000. Most preferred.
  • the radical 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.
  • 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 radical polymerizable monomer or oligomer having a silicon atom is 0.01 to 15 mass based on the total solid content of the release agent. % Is preferred. 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.
  • 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).
  • Non-thermosetting compound a polymer compound having a non-polymerizable fluorine atom is preferable.
  • a polymer compound having a non-polymerizable fluorine atom a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used. More specifically, it is selected from tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester.
  • the polymer compound having a non-polymerizable fluorine atom is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic ester.
  • the perfluoroalkyl group-containing (meth) acrylic acid ester is preferably a compound represented by the following formula (101).
  • R 101 , R 102 , and R 103 each independently represent a hydrogen atom, an alkyl group, or a halogen atom.
  • Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • Rf is a fluorine atom or a monovalent organic group having at least one fluorine atom.
  • examples of the alkyl group represented by R 101 , R 102 , R 103 are preferably alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Examples include octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
  • Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 101 to R 103 are preferably a hydrogen atom or a methyl group.
  • Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • the divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Y 101 is preferably an aliphatic group having a divalent linear structure.
  • the monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to Fifteen fluorine-containing alkyl groups are particularly preferred.
  • This fluorine-containing alkyl group is a straight chain ⁇ for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.
  • a branched structure ⁇ eg, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like ⁇ and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these).
  • An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , —CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
  • the perfluoroalkyl group-containing (meth) acrylic resin preferably 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, such as methyl, butyl, 2-ethylhexyl, lauryl, stearyl, and glycidyl esters of (meth) acrylic acid.
  • (Meth) acrylates of higher alcohols such as 2-ethylhexyl, lauryl and stearyl, particularly acrylates are preferred.
  • Examples of commercially available polymer compounds having non-polymerizable fluorine atoms include Teflon (registered trademark) (DuPont), Tefzel (DuPont), Fullon (Asahi Glass Co.), Halar (Solvay Solexis), Heiler. (Solvay Solexis), Lumiflon (Asahi Glass Co., Ltd.), Afras (Asahi Glass Co., Ltd.), Cefral Soft (Central Glass Co., Ltd.), etc.
  • Various fluoro oils such as perfluoropolyether oils such as fluoroelastomers with trade names such as Shin-Etsu Chemical Co., Ltd.
  • Dies such as die-free FB962 Examples include fluorine-containing mold release agents such as Lee FB series (Daikin Industries Co., Ltd.) and Megafax series (DIC Co.), but are not limited to these. Any molecular compound can be suitably used.
  • F-251, F-281, F-477, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F -560, F-561, F-563, F-565, F-567, F-568, F-571, R-40, R-41, R-43, R-94 710F, 710FM, 710FS, 730FL, and 730LM can be preferably used.
  • the weight average molecular weight of the polymer compound having a non-polymerizable fluorine atom is preferably 2000 to 100,000, more preferably 2000 to 50000, and most preferably 2000 to 10,000.
  • the release layer can 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, a chain transfer agent, an antioxidant, and a surfactant can be preferably used. These can use what was demonstrated with the adhesive film mentioned above.
  • the manufacturing method of the laminated body for temporary adhesion of this invention includes the process of forming the mold release layer containing the mold release agent containing at least 1 type chosen from a fluorine atom and a silicon atom on the surface of the adhesive film mentioned above.
  • the adhesive film can be produced by a conventionally known method. For example, it can be produced by a melt film forming method, a solution film forming method or the like. A melt film forming method is preferred. With the melt film forming method, it is possible to increase the thickness while maintaining flatness. Furthermore, polymer components and other additives that are difficult to dissolve in the solvent can be used, and the degree of freedom in material selection is high. In particular, it is possible to use a highly heat-resistant additive that tends to hardly dissolve in a solvent, and an adhesive film excellent in heat resistance can be easily obtained.
  • 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 long film with good flatness can be obtained.
  • the length of the long film is not particularly limited, but the lower limit is preferably, for example, 5000 mm or more, and more preferably 1000 mm or more.
  • the upper limit is preferably 500000 mm or less, and more preferably 200000 mm or less.
  • a release film may be bonded to one 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 solvent known solvents can be used without limitation, and organic solvents are 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 also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface.
  • particularly preferred are mesitylene, p-menthane, ⁇ -butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid.
  • the solution coating method includes a method in which the solution is extruded by applying pressure from a slit-shaped opening, a method in which the solution is transferred by gravure or an aronics roller, and a scan is performed while discharging the solution from a spray or dispenser. Coating method, dip coating by storing the solution in a tank and letting it pass through a film, drum or band, and coating by swirling the solution with a wire bar It is done.
  • 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 coating As a process for imparting peelability to the support in advance so as to be easily peeled off, a release layer coating, dipping process, gas process, electromagnetic wave irradiation process, plasma irradiation process, or the like may be performed. 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 surfaces of the adhesive film to form an “adhesive film with a double-sided release film”.
  • Examples of a method for forming a release layer on the surface of the adhesive film include a laminating method, a coating method, and a co-extrusion method.
  • the release film is coated with a composition containing at least the release agent to form a film-like release layer (release layer film), and the surface of the adhesive film having no release film is used.
  • the release layer film is laminated by bringing it into contact with the surface without the release film.
  • a known apparatus such as roller lamination (which may be heated or pressurized) or vacuum lamination (which may be heated) can be used.
  • the coating method is a method in which a release layer forming solution is applied to the surface of the adhesive film without the release film and then dried.
  • a release layer forming composition it is preferable to use a solution containing the release agent and the solvent described above. Any solvent can be preferably used as long as it can dissolve the release agent.
  • Fluorinert FC40 manufactured by 3M Corporation
  • the release layer forming solution may be applied and dried in-line, after applying and drying the adhesive film forming solution, without winding.
  • the physical properties of the solution are designed so that the adhesive film forming solution and the release layer forming solution are not compatible, they may be applied simultaneously and dried simultaneously.
  • the release layer forming solution may be applied without drying, and both may be dried simultaneously.
  • the adhesive film forming solution and release layer forming solution are compatible with each other but are designed to have physical properties that cause phase separation when the concentration increases after drying, the mixed solution is applied and dried. Further, it may be separated into an adhesive film and a release layer.
  • a release layer can be provided on both surfaces of an adhesive film by coating the release layer forming solution on both surfaces of the adhesive film.
  • the material for forming the adhesive film and the material for forming the release layer are respectively melted by heat and integrated while extruding at the same time. How to get.
  • a release layer can be provided on both sides of the adhesive film by extruding the release layer forming material on both sides of the adhesive film forming material.
  • the solvent content is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably not contained.
  • the temporary adhesive laminate of the present invention may be a temporary adhesive laminate with a release film by pasting a release film on one or both sides of the temporary adhesive laminate.
  • the release film can be peeled off when used. For example, in the case where a release film is bonded to both sides, by peeling off the release film on one side, laminating the adhesive surface on a device wafer or support, and then peeling off the remaining release film, The sheet surface can be kept as clean as possible.
  • An adhesive support body has the laminated body for temporary adhesion mentioned above on the surface of a support body.
  • the temporary bonding laminate can be formed by laminating the above-described temporary bonding laminate of the present invention on a support.
  • the temporary bonding laminate is set on a vacuum laminator, the temporary bonding laminate is positioned on the support with this apparatus, the temporary adhesion laminate and the support are brought into contact with each other under vacuum, a roller, etc.
  • a method of fixing (laminating) the temporary bonding laminate to the support by pressing Moreover, you may cut the laminated body for temporary attachment fixed to the support body in desired shapes, such as circular shape, for example.
  • the temporary adhesive laminate may be one in which a release layer is formed only on one side of the adhesive film, or may be one in which a release layer is formed on both sides. Good.
  • the release layer may be disposed on the support side, or the release layer may be disposed on the surface opposite to the support side. .
  • the support (also referred to as 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 particular, 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. preferable.
  • 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.
  • a release layer may be provided on the surface of the support. That is, the support may be a support with a release layer.
  • 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 materials as those described for the release layer of the temporary bonding laminate described above can be used.
  • the laminate with a device wafer of the present invention has the above-mentioned temporary adhesion laminate of the present invention between the device wafer and the support, and the temporary adhesion laminate is in contact with the device wafer and the support. It is. That is, one surface of the temporary bonding laminate is in contact with the device surface of the device wafer, and the other surface is in contact with the surface of the support.
  • the laminated body for temporary adhesion has a release layer on both surfaces of the adhesive film
  • the release layer on one surface is in contact with the device wafer, and the release layer on the other surface is the support and It touches.
  • the laminated body for temporary adhesion has a release layer only on the single side
  • a known device wafer can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate.
  • the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.
  • 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, LEDs, optical devices, interposers, embedded devices, and micro devices. .
  • the device wafer preferably has a structure such as a metal bank.
  • 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 (carrier support) has the same meaning as the support described in the adhesive support described above, and the preferred range is also the same.
  • the laminated body with a device wafer of the present invention can be produced by thermocompression bonding the surface of the adhesive support described above on which the temporary bonding laminated body is formed and the device wafer.
  • 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.
  • it can also be manufactured by disposing the above-mentioned temporary bonding laminate of the present invention between a support and a device wafer and thermocompression bonding.
  • FIGS. 1A and 1E are schematic cross-sectional views (FIGS. 1A and 1B) illustrating temporary bonding between a support and a device wafer, respectively, and a device wafer temporarily bonded to the support.
  • FIG. 1C Schematic showing a thinned state (FIG. 1C), a state where the support and the device wafer are peeled off (FIG. 1D), and a state after removing the adhesive layer from the device wafer (FIG. 1E). It is sectional drawing.
  • an adhesive support 100 is prepared in which a temporary adhesive laminate 11 is provided on a support 12.
  • the adhesive support 100 can be manufactured by the method described above.
  • the adhesive support 100 is preferably in an embodiment that does not substantially contain a solvent.
  • the device wafer 60 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.
  • the adhesive support 100 and the device wafer 60 are pressure-bonded, and the support 12 and the device wafer 60 are temporarily bonded.
  • the temporary bonding laminate 11 preferably completely covers the device chip 62.
  • the height of the device chip is X ⁇ m and the thickness of the temporary bonding laminate is Y ⁇ m, the relationship of “X + 100 ⁇ Y> X” is satisfied. It is preferable to satisfy.
  • the case where the laminated body 11 for temporary adhesion completely covers the device chip 62 is intended to further reduce the TTV (Total Thickness Variation) of the thin device wafer (that is, to improve the flatness of the thin device wafer). ) Is effective.
  • the plurality of device chips 62 are protected by the temporary bonding laminate 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 1) 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.
  • mechanical or chemical treatment though not particularly limited, for example, thinning treatment such as grinding or chemical mechanical polishing (CMP)
  • 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 1
  • 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.
  • the highest temperature achieved in the heat treatment is preferably 130 ° C. to 400 ° C., more preferably 180 ° C. to 350 ° C.
  • the highest temperature achieved in the heat treatment is preferably a temperature lower than the softening point of the adhesive film.
  • 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 temporary bonding laminate 11.
  • the peel strength at the interface between the support 12 and the temporary bonding laminate 11 is A
  • the peel strength B between the device wafer surface 61a and the temporary bonding laminate 11 it is preferable to satisfy the following formula.
  • the thin device wafer 60a after making the laminated body 11 for temporary adhesion contact the peeling liquid mentioned later, and sliding the thin device wafer 60a with respect to the support body 12 as needed after that, it is a device from the edge part of the thin device wafer 60a. It can also be peeled off by pulling up in the direction perpendicular to the wafer.
  • the stripping solution water and a solvent (organic solvent) can be used.
  • the organic solvent which melt
  • the organic solvent include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons. (Methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents.
  • Polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol,
  • the stripping solution may contain an alkali, an acid, and a surfactant.
  • the blending amount is preferably 0.1 to 5.0% by mass of the stripping solution.
  • a form in which two or more organic solvents and water, two or more alkalis, an acid, and a surfactant are mixed is also preferable.
  • alkali examples include tribasic sodium phosphate, tribasic potassium phosphate, tribasic ammonium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, and ammonium carbonate.
  • Inorganic alkali agents such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, monomethylamine, Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanol Min, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, may be used an organic alkali agent such as tetramethylammonium hydroxide. These alkali agents can be used alone or in combination of two or more.
  • Acids include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid, boric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid
  • Organic acids such as formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid can be used.
  • the surfactant an anionic, cationic, nonionic or zwitterionic surfactant can be used.
  • the content of the surfactant is preferably 1 to 20% by mass and more preferably 1 to 10% by mass with respect to the total amount of the alkaline aqueous solution.
  • anionic surfactant examples include, but are not limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid salts, Alkylnaphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid Monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef oil, sulfate esters of fatty acid alkyl
  • the cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkyl imidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
  • the nonionic surfactant is not particularly limited, but is a polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid.
  • Ethylene oxide adduct polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block Copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer , Fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines.
  • those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol ethylene oxide adduct is more preferable.
  • Zwitterionic surfactants include, but are not limited to, amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaines, and amino acids such as sodium alkylamino fatty acids.
  • alkyldimethylamine oxide which may have a substituent alkylcarboxybetaine which may have a substituent
  • alkylsulfobetaine which may have a substituent
  • the compound represented by the formula (2) in paragraph [0256] of JP-A-2008-203359, the formula (I) and the formula (II) in paragraph [0028] of JP-A-2008-276166 are disclosed.
  • a compound represented by the formula (VI), and compounds represented by paragraph numbers [0022] to [0029] of JP-A-2009-47927 can be used.
  • additives such as an antifoaming agent and a water softening agent can be contained as required.
  • the thin device wafer can be obtained by removing the temporary bonding laminate 11 from the thin device wafer 60a.
  • the removal method of the temporary bonding laminate 11 includes, for example, a method of peeling and removing the temporary bonding laminate in a film state (mechanical peeling), a method of peeling and removing the temporary bonding laminate after swelling with a peeling solution, A method of spraying a release liquid onto a temporary adhesive laminate to remove it by destruction, a method of dissolving and removing a temporary adhesive laminate in a release liquid, and decomposing the temporary adhesive laminate by irradiation with actinic rays, radiation or heat And a method of removing by vaporization.
  • a method of peeling and removing the temporarily adhering laminate in the form of a film and a method of dissolving and removing the temporarily adhering laminate in an aqueous solution or an organic solvent can be preferably used. From the viewpoint of reducing the amount of solvent used, it is preferable to remove the film as it is.
  • the peel strength B between the device wafer surface 61a and the temporary bonding laminate 11 is expressed by the following formula (2 ) Is preferably satisfied.
  • the support 12 when the support 12 is peeled from the thin device wafer 60a, it is preferable that the support 12 is lifted from the end of the thin device wafer 60a in the direction perpendicular to the device wafer without any treatment.
  • a method for removing the temporary adhering laminate 11 on 61a it is preferable to remove the laminated body 11 in the form of a film.
  • the peel strength at the interface between the support 12 and the temporary bonding laminate 11 is A, and the peel strength B between the device wafer surface 61a and the adhesive layer 11, the support is satisfied by satisfying both the above-described formulas (1) and (2).
  • the body 12 and the temporary bonding laminate 11 can be removed from the device wafer in the above-described manner.
  • a support body when the laminated body for temporary adhesion has adhered to the support body, a support body can be reproduced
  • a method for removing the temporary adhesive laminate a method of physically removing the laminated body as a film, by spraying a brush, ultrasonic waves, ice particles or aerosol, a method of dissolving and removing by dissolving in an aqueous solution or an organic solvent
  • a chemical removal method such as a method of decomposing and vaporizing by irradiation with actinic rays, radiation, and heat can be used, and conventionally known cleaning methods can be used depending on 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
  • bases such as tetramethylammonium, ammonia and organic bases, oxidation of hydrogen peroxide and the like
  • 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. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the conventional adhesive support and the device wafer.
  • the adhesive support 100a and the device wafer are temporarily bonded in the same manner as described with reference to FIG. 1, and the silicon wafer is thinned on the device wafer. Similar to the procedure, the thin device wafer 60a is peeled from the adhesive support 100a.
  • the conventional temporary adhesive it is difficult to easily release the temporary support for the processed member without temporarily damaging the processed member with high adhesive force and damaging the processed member.
  • a conventional temporary adhesive having high adhesiveness if a conventional temporary adhesive having high adhesiveness is adopted, the temporary bonding between the device wafer and the support tends to be too strong. Become. Therefore, in order to release the temporary bonding that is too strong, for example, as shown in FIG. 3, a tape (for example, a 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.
  • a conventional temporary adhesive having low adhesiveness is adopted, temporary support to the processed member can be easily released, but the temporary adhesion between the device wafer and the carrier substrate is too weak in the first place. A problem that the wafer cannot be reliably supported by the carrier substrate is likely to occur.
  • the temporary bonding laminate of the present invention exhibits sufficient adhesiveness and can easily release the temporary bonding between the device wafer 60 and the support 11. That is, according to the temporary bonding laminate 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. .
  • 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 film forming composition described below is coated on a polyethylene terephthalate film (release film) having a thickness of 75 ⁇ m with a wire bar at a speed of 1 m / min, and dried at 140 ° C. for 10 minutes, whereby a film thickness of 100 ⁇ m is obtained.
  • An adhesive film was prepared. Also, the film-forming compositions in the temporary bonding laminates 1-4, 1-5, 1-15, 1-16, 1-17, and 1-18 shown in Table 1 below were melted at 300 ° C. for 5 minutes.
  • an extruded sheet (adhesive film) having a film thickness of 100 ⁇ m was prepared.
  • the film-forming composition in the temporary adhering laminate 1-R2 shown in Table 1 below extrudes a commercially available polyimide film (Kapton, manufactured by Toray DuPont) as an extruded sheet (adhesive film) having a film thickness of 100 ⁇ m. used.
  • the following coating solution for forming a release layer is coated on the adhesive film with a bar, oven-dried at 120 ° C. for 1 minute, and a temporary release layer having a release layer having a thickness of 60 nm is formed on both surfaces of the adhesive film.
  • An adhesive laminate was prepared.
  • A-6 SIS-5200P (non-hydrogenated polystyrene elastomer, 250 ° C.
  • ⁇ Creation of adhesive support 1> The adhesive film prepared by the above method was set in a vacuum laminator. Then, with this apparatus, the adhesive film is positioned on a 100 mm Si wafer (support), the Si wafer is brought into contact with the opposite surface of the release layer of the adhesive film under vacuum, and the adhesive film is The Si wafer was fixed and the adhesive support 1 was created.
  • the composition containing 0.9 part by mass and 70 parts by mass of mesitylene is spin-coated on a 100 mm Si wafer, then baked at 110 ° C. for 1 minute, and further baked at 190 ° C. for 4 minutes. A 100 ⁇ m adhesive layer was formed.
  • a composition containing 0.5 parts by mass of the release agent (b-5) and 99.5 parts by mass of the fluorine solvent 1 is spin-coated on the surface of the adhesive layer at 120 ° C.
  • a release layer having a thickness of 60 nm was formed, and an adhesive support 1 having a laminate for temporary bonding was produced.
  • the surface of the adhesive support 1 on which the laminated body for temporary bonding is formed and the device surface of a 100 mm Si wafer (device wafer) are pressure-bonded under vacuum at 190 ° C. and a pressure of 0.11 MPa for 3 minutes.
  • a test piece was prepared.
  • ⁇ Flatness> The average thickness of the temporary adhesive laminate was measured by ellipsometry at five locations at equal intervals from one end face of the adhesive support to the other end face (average film) Thickness) and the maximum or minimum thickness were measured and evaluated according to the following criteria.
  • 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.
  • the 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 of the adhesive layer under the condition of 500 mm / min to confirm the peelability.
  • the prepared test piece was heated at 250 ° C. for 30 minutes, similarly, it was pulled in the vertical direction of the adhesive layer under the condition of 250 mm / min, and the peelability after the thermal process was confirmed, and evaluated according to the following criteria. .
  • a peeling tape (manufactured by LINTEC Co., Ltd.) is applied to a part of the outer periphery of the Si wafer on the Si wafer with an adhesive film after the peelability test is completed, and the peeling tape is pulled in the vertical direction, and the adhesive film is formed on the Si wafer.
  • the machine was peeled off. Thereafter, the appearance was observed, and the presence or absence of a peeling residue of the adhesive film remaining on the thin device wafer was visually checked and evaluated according to the following criteria.
  • B It broke in the middle of peeling. Alternatively, the adhesive film could be removed but the residue remained.
  • Examples 1 to 18 had good flatness, adhesiveness and peelability. Furthermore, the removability of the adhesive layer was good in both dissolution removal and film removal. On the other hand, Comparative Examples 1 to 3 were inferior in any of flatness, adhesiveness and peelability.
  • Adhesion layer 12 Support body 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 body

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Abstract

Provided are: a temporary adhesion laminate which has excellent flatness of an adhesive surface for adhesion to a device wafer or a support, is capable of stabilising and temporarily adhering to a device wafer and a support, and can easily be released from the temporary adhesion to the device wafer and the support; a temporary adhesion laminate manufacturing method; and a laminate equipped with a device wafer. This temporary adhesion laminate has: a film that includes at least one substance selected from a polystyrene-based elastomer, a polyester-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyamide-based elastomer, a polyacrylic-based elastomer, a silicone-based elastomer, a polyimide-based elastomer, polyether ether ketone, polyphenylene sulphide, a polyphenylene ether, and polyether sulphone; and a release layer on at least one surface of the film, said release layer including a release agent that contains a fluorine atom and/or a silicon atom.

Description

仮接着用積層体、仮接着用積層体の製造方法およびデバイスウエハ付き積層体Laminated body for temporary bonding, manufacturing method of laminated body for temporary bonding, and laminated body with device wafer
　本発明は、仮接着用積層体、仮接着用積層体の製造方法およびデバイスウエハ付き積層体に関する。より詳細には、半導体装置などの製造に好ましく用いることができる、仮接着用積層体、仮接着用積層体の製造方法およびデバイスウエハ付き積層体に関する。 The present invention relates to a temporary adhesion laminate, a method for producing a temporary adhesion laminate, and a laminate with a device wafer. More specifically, the present invention relates to a temporary bonding laminate, a method for producing a temporary adhesion laminate, and a laminate with a device wafer, which can be preferably used for manufacturing a semiconductor device or the like.
　ＩＣ（集積回路）やＬＳＩ（大規模集積回路）などの半導体デバイスの製造プロセスにおいては、デバイスウエハ上に多数のＩＣチップが形成され、ダイシングにより個片化される。
　電子機器の更なる小型化および高性能化のニーズに伴い、電子機器に搭載されるＩＣチップについても更なる小型化および高集積化が求められているが、デバイスウエハの面方向における集積回路の高集積化は限界に近づいている。 In a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated Circuit), a large number of IC chips are formed on a device wafer and separated into pieces by dicing.
With the need for further miniaturization and higher performance of electronic equipment, further miniaturization and higher integration are required for IC chips mounted on electronic equipment. High integration is approaching its limit.
　ＩＣチップ内の集積回路から、ＩＣチップの外部端子への電気的な接続方法としては、従来より、ワイヤーボンディング法が広く知られているが、ＩＣチップの小型化を図るべく、近年、デバイスウエハに貫通孔を設け、外部端子としての金属プラグを貫通孔内を貫通するように集積回路に接続する方法（いわゆる、シリコン貫通電極（ＴＳＶ）を形成する方法）が知られている。しかしながら、シリコン貫通電極を形成する方法のみでは、上記した近年のＩＣチップに対する更なる高集積化のニーズに充分応えられるものではない。 As an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known. However, in recent years, in order to reduce the size of 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). However, only the method of forming the through silicon vias cannot sufficiently meet the above-described needs for higher integration of the recent IC chip.
　以上を鑑み、ＩＣチップ内の集積回路を多層化することにより、デバイスウエハの単位面積当たりの集積度を向上させる技術が知られている。しかしながら、集積回路の多層化は、ＩＣチップの厚みを増大させるため、ＩＣチップを構成する部材の薄型化が必要である。このような部材の薄型化としては、例えば、デバイスウエハの薄型化が検討されており、ＩＣチップの小型化につながるのみならず、シリコン貫通電極の製造におけるデバイスウエハの貫通孔製造工程を省力化できることから、有望視されている。また、パワーデバイス・イメージセンサーなどの半導体デバイスにおいても、上記集積度の向上やデバイス構造の自由度向上の観点から、薄型化が試みられている。 In view of the above, 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. However, since the multilayered integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the members constituting the IC chip. For example, the thinning of the 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. In addition, 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.
　デバイスウエハとしては、約７００～９００μｍの厚さを有するものが広く知られているが、近年、ＩＣチップの小型化等を目的に、デバイスウエハの厚さを２００μｍ以下となるまで薄くすることが試みられている。
　しかしながら、厚さ２００μｍ以下のデバイスウエハは非常に薄く、これを基材とする半導体デバイス製造用部材も非常に薄いため、このような部材に対して更なる処理を施したり、あるいは、このような部材を単に移動したりする場合等において、部材を安定的に、かつ、損傷を与えることなく支持することは困難である。 A device wafer having a thickness of about 700 to 900 μm 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 μm or less. Has been tried.
However, since a device wafer having a thickness of 200 μm 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.
　上記のような問題を解決すべく、表面にデバイスが設けられた薄型化前のデバイスウエハと加工用支持基板とをシリコーン粘着剤により仮接着し、デバイスウエハの裏面を研削して薄型化した後に、デバイスウエハを穿孔してシリコン貫通電極を設け、その後、デバイスウエハから加工用支持基板を脱離させる技術が知られている（特許文献１参照）。この技術によれば、デバイスウエハの裏面研削時の耐研削抵抗、異方性ドライエッチング工程などにおける耐熱性、メッキやエッチング時の耐薬品性、最終的な加工用支持基板とのスムースな剥離と低披着体汚染性を同時に達成することが可能であるとされている。 In order to solve the above-mentioned problems, after pre-thinning the device wafer with the device provided on the surface and the supporting substrate for processing with a silicone adhesive, the back surface of the device wafer is ground and thinned. A technique is known in which a device wafer is drilled to provide a silicon through electrode, and then a processing support substrate is detached from the device wafer (see Patent Document 1). According to this technology, resistance to grinding during back grinding of device wafers, heat resistance in anisotropic dry etching processes, chemical resistance during plating and etching, smooth peeling from the final supporting substrate for processing, It is said that it is possible to simultaneously achieve low plastid contamination.
　また、ウエハの支持方法としては、ウエハを支持層システムにより支持する方法であって、ウエハと支持層システムとの間に、プラズマ堆積法により得られるプラズマポリマー層を分離層として介装させて、支持層システムと分離層との間の接着結合を、ウエハと分離層との間の接合結合より大きくなるようにし、ウエハを支持層システムから脱離する際に、ウエハが分離層から容易に脱離するように構成した技術も知られている（特許文献２参照）。 Further, as a method for supporting the wafer, the wafer is supported by a support layer system, and a plasma polymer layer obtained by a plasma deposition method is interposed as a separation layer between the wafer and the support layer system. The adhesive bond between the support layer system and the separation layer is made larger than the bond bond between the wafer and the separation layer, so that when the wafer is detached from the support layer system, the wafer is easily detached from the separation layer. A technique configured to be separated is also known (see Patent Document 2).
　また、ポリエーテルスルホンと粘性付与剤を使用して、仮接着を行い、加熱により仮接着を解除する技術が知られている（特許文献３参照）。
　また、カルボン酸類とアミン類からなる混合物により、仮接着を行い、加熱により仮接着を解除する技術も知られている（特許文献４参照）。
　また、セルロースポリマー類等からなる接合層を加温した状態で、デバイスウエハと支持基板を圧着することで接着させて、加温して横方向にスライドすることによりデバイスウエハを支持基板から脱離する技術が知られている（特許文献５参照）。 Moreover, the technique which performs temporary adhesion | attachment using a polyether sulfone and a viscosity imparting agent, and cancels | releases temporary adhesion by heating is known (refer patent document 3).
There is also known a technique in which temporary adhesion is performed with a mixture of carboxylic acids and amines and the temporary adhesion is released by heating (see Patent Document 4).
In addition, the device wafer and the support substrate are bonded together by pressure bonding with the bonding layer made of cellulose polymers heated, and the device wafer is detached from the support substrate by heating and sliding in the lateral direction. The technique which performs is known (refer patent document 5).
　また、シンジオタクチック１，２－ポリブタジエンと光重合開始剤からなり、放射線の照射により接着力が変化する粘着フィルムが知られている（特許文献６参照）。
　さらに、ポリカーボネート類からなる接着剤により、支持基板とデバイスウエハとを仮接着し、デバイスウエハに対して処理を行った後、照射線を照射し、次いで、加熱することにより、処理済のデバイスウエハを支持基板から脱離する技術が知られている（特許文献７参照）。 Further, a pressure-sensitive adhesive film made of syndiotactic 1,2-polybutadiene and a photopolymerization initiator and having an adhesive force that changes by irradiation with radiation is known (see Patent Document 6).
Further, the support substrate and the 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 the substrate from the support substrate is known (see Patent Document 7).
　また、軟化点の異なる２層で、支持基板とデバイスウエハを仮接着し、デバイスウエハに対して処理を行った後、加温して横方向にスライドすることで支持基板とデバイスウエハを脱離する技術が知られている（特許文献８参照）。 In addition, the support substrate and device wafer are temporarily bonded with two layers with different softening points, and after processing the device wafer, the support substrate and device wafer are detached by heating and sliding laterally. The technique to do is known (refer patent document 8).
　また、特許文献９には、シクロオレフィン重合体と、シリコーン構造、フッ素化アルキル基構造、フッ素化アルケニル構造および炭素数８以上のアルキル構造の少なくとも１種の構造、ならびにポリオキシアルキレン構造、リン酸基を有する構造およびスルホ基を有する構造の少なくとも１種の構造、を有する化合物を含む仮固定材を介して、支持体と基材とを仮固定することが開示されている。 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.
　また、特許文献１０には、主鎖の構成単位としてスチレン単位を含むエラストマーと、ワックスとを含む接着剤組成物を用いて、デバイスウエハと支持体とを接着することが開示されている。 Further, Patent Document 10 discloses that a device wafer and a support are bonded using an adhesive composition containing a styrene unit as a main chain constituent unit and a wax.
　また、特許文献１１には、デバイスウエハのデバイス面に接着層を塗布形成し、支持体の表面にフッ化シラン化合物を含む離型層を塗布形成し、デバイスウエハ上の接着層と支持体上の離型層とを接着させて、デバイスウエハと支持体とを接着することが開示されている。 Further, in Patent Document 11, an adhesive layer is applied and formed on the device surface of a device wafer, and a release layer containing a fluorinated silane compound is applied and formed on the surface of the support. It is disclosed that the device wafer and the support are bonded by bonding the release layer of the device.
　また、特許文献１２には、特定のポリイミド樹脂を含んでなる仮固定用フィルムの両面または片面に、低接着力層を有する仮固定用フィルムシートを用いて、デバイスウエハと支持体とを接着することが開示されている。 Further, in Patent Document 12, a device wafer and a support are bonded using a temporary fixing film sheet having a low adhesion layer on both sides or one side of a temporary fixing film containing a specific polyimide resin. It is disclosed.
特開２０１１－１１９４２７号公報JP 2011-119427 A 特表２００９－５２８６８８号公報Special table 2009-528688 特開２０１１－２２５８１４号公報JP 2011-225814 A 特開２０１１－０５２１４２号公報Japanese Unexamined Patent Publication No. 2011-052142 特表２０１０－５０６４０６号公報Special table 2010-506406 gazette 特開２００７－０４５９３９号公報JP 2007-045939 A 米国特許公開２０１１／０３１８９３８号明細書US Patent Publication No. 2011/0318938 米国特許公報２０１２／００３４４３７号明細書US Patent Publication 2012/0034437 特開２０１３－２４１５６８号公報JP 2013-241568 A 特開２０１４－３４６３２号公報JP 2014-34632 A 国際公開ＷＯ２０１３／１１９９７６号パンフレットInternational publication WO2013 / 119976 pamphlet 特開２０１４－２９９９９号公報JP 2014-29999 A
　ところで、デバイスが設けられたデバイスウエハの表面（すなわち、デバイスウエハのデバイス面）と支持基板（キャリア基板）とを、特許文献１等で知られている粘着剤からなる層を介して仮接着する場合には、デバイスウエハを安定的に支持するべく、接着層には一定の強さの粘着度が要求される。
　そのため、デバイスウエハのデバイス面の全面と支持体とを粘着剤層を介して仮接着する場合においては、デバイスウエハと支持体との仮接着を充分なものとし、デバイスウエハを安定的に、かつ、損傷を与えることなく支持しようとする程、反面、デバイスウエハと支持体との仮接着が強すぎることにより、支持体からデバイスウエハを脱離する際に、デバイスが破損したり、デバイスウエハからデバイスが脱離してしまうという不具合が生じやすい。 By the way, the surface of the device wafer on which the device is provided (that is, the device surface of the device wafer) and the support substrate (carrier substrate) are temporarily bonded via a layer made of an adhesive known in Patent Document 1 or the like. In some cases, the adhesive layer is required to have a certain degree of adhesion to stably support the device wafer.
Therefore, in the case where the entire device surface of the device wafer and the support are temporarily bonded via the pressure-sensitive adhesive layer, the temporary bonding between the device wafer and the support is sufficient, and the device wafer is stably and However, the temporary adhesion between the device wafer and the support is too strong, so that the device may be damaged or detached from the device wafer. There is a tendency for the device to be detached.
　また、特許文献２のように、ウエハと支持層システムとの接着が強くなりすぎることを抑制すべく、ウエハと支持層システムとの間に、分離層としてのプラズマポリマー層を、プラズマ堆積法により形成する方法は、（１）通常、プラズマ堆積法を実施するための設備コストは大きい；（２）プラズマ堆積法による層形成は、プラズマ装置内の真空化やモノマーの堆積に時間を要する；および（３）プラズマポリマー層からなる分離層を設けても、加工に供されるウエハを支持する場合においては、ウエハと分離層との接着結合を充分なものとしながら、反面、ウエハの支持を解除する場合においては、ウエハが容易に分離層から脱離するような接着結合にコントロールすることは容易ではない；等の問題がある。 Further, as in Patent Document 2, in order to suppress the adhesion between the wafer and the support layer system from becoming too strong, a plasma polymer layer as a separation layer is formed between the wafer and the support layer system by a plasma deposition method. The forming method is (1) the equipment cost for carrying out the plasma deposition method is usually high; (2) the layer formation by the plasma deposition method requires time for vacuuming and monomer deposition in the plasma apparatus; and (3) Even when a separation layer composed of a plasma polymer layer is provided, when supporting a wafer to be processed, the wafer is released from support while the adhesive bond between the wafer and the separation layer is sufficient. In such a case, it is not easy to control the adhesive bond so that the wafer is easily detached from the separation layer;
　また、特許文献３、４、５記載のように、加熱により仮接着を解除する方法では、支持体からデバイスウエハを脱離する際にデバイスが破損する不具合が生じやすい。 Also, as described in Patent Documents 3, 4, and 5, in the method of releasing the temporary adhesion by heating, there is a tendency that the device is damaged when the device wafer is detached from the support.
　また、特許文献６、７のように、照射線を照射して仮接着を解除する方法では、照射線を透過する支持体を使用する必要がある。 Also, as disclosed in Patent Documents 6 and 7, in the method of releasing the temporary adhesion by irradiating the irradiation line, it is necessary to use a support that transmits the irradiation line.
　また、特許文献８のように、デバイスウエハ側の接合層の軟化点が基板側の接合層の軟化点よりも２０℃以上大きい場合は、剥離後に基板側の接合層がデバイスウエハ側の接合層に転写し、デバイスウエハの洗浄性が低下する問題が発生する。 In addition, as in Patent Document 8, when the softening point of the bonding layer on the device wafer side is 20 ° C. or more higher than the softening point of the bonding layer on the substrate side, the bonding layer on the substrate side becomes the bonding layer on the device wafer side after peeling. This causes a problem that the cleaning performance of the device wafer deteriorates.
　また、特許文献９の接着剤を仮固定材として使用した場合、剥離性が不十分なため、デバイスウエハを剥離する際にデバイスが破損する不具合が生じやすい問題があった。 Further, when the adhesive of Patent Document 9 is used as a temporary fixing material, there is a problem that the device is easily damaged when the device wafer is peeled because the peelability is insufficient.
　また、特許文献１０では、接着剤組成物を、デバイスウエハまたは支持体に塗布して接着層を形成している。接着層を塗布形成した場合、厚みムラが生じ易かった。接着層に厚みムラが生じると、デバイスウエハや支持体に対する接着性が劣る傾向にある。また、特許文献１０に開示された方法では、デバイスウエハからの支持体の剥離性が不十分であった。 In Patent Document 10, an adhesive composition is formed by applying an adhesive composition to a device wafer or a support. When the adhesive layer was applied and formed, uneven thickness was likely to occur. When the thickness unevenness occurs in the adhesive layer, the adhesion to the device wafer or the support tends to be inferior. Moreover, in the method disclosed in Patent Document 10, the peelability of the support from the device wafer was insufficient.
　また、特許文献１１では、接着層や離型層をデバイスウエハや支持体にそれぞれ塗布形成しているので、接着層や離型層に厚みムラが生じ易く、接着性が劣る傾向にあることや、厚みムラが生じた結果デバイスウエハの裏面を均一に処理ができない問題があった。 Moreover, in patent document 11, since the adhesive layer and the release layer are respectively applied and formed on the device wafer and the support, thickness unevenness easily occurs in the adhesive layer and the release layer, and the adhesiveness tends to be inferior. As a result of the uneven thickness, the back surface of the device wafer cannot be uniformly processed.
　また、特許文献１２に開示された方法では、デバイス表面の形状に対する追従性が不十分であり、接着性が十分ではなく、空孔が発生する問題が生じた。デバイス裏面を研削して薄化すると、均一な厚みに薄化できない問題もあった。 Also, the method disclosed in Patent Document 12 has a problem in that the followability to the shape of the device surface is insufficient, the adhesiveness is not sufficient, and voids are generated. When the back surface of the device is ground and thinned, there is a problem that it cannot be thinned to a uniform thickness.
　本発明は、上記背景を鑑みてなされたものであり、その目的は、デバイスウエハや支持体との接着面における平坦性が良好で、デバイスウエハと支持体とを安定して仮接着できるとともに、デバイスウエハと支持体との仮接着を容易に解除できる仮接着用積層体、仮接着用積層体の製造方法およびデバイスウエハ付き積層体を提供することにある。 The present invention has been made in view of the above background, and its purpose is that the flatness of the bonding surface between the device wafer and the support is good, and the device wafer and the support can be stably temporarily bonded together. An object of the present invention is to provide a laminated body for temporary bonding that can easily release temporary bonding between a device wafer and a support, a manufacturing method of the laminated body for temporary bonding, and a laminated body with a device wafer.
　本発明者らは、上記課題を解決すべく鋭意検討した結果、後述する特定のフィルムの片面または両面に、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を有する仮接着用積層体を使用したところ、平坦性が良好で、高い接着力によりデバイスウエハと支持体を仮接着できるとともに、デバイスウエハと支持体との仮接着を容易に解除できることを見出し、本発明を完成するに至った。本発明は、以下を提供する。
＜１＞　デバイスウエハのデバイス面と支持体とを、剥離可能に仮接着するために用いる仮接着用積層体であって、ポリスチレン系エラストマー、ポリエステル系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマー、ポリアクリル系エラストマー、シリコーン系エラストマー、ポリイミド系エラストマー、ポリエーテルエーテルケトン、ポリフェニレンスルファイド、ポリフェニレンエーテルおよびポリエーテルスルホンから選ばれる少なくとも１種を含むフィルムと、フィルムの少なくとも一方の表面に、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を有する、仮接着用積層体。
＜２＞　フィルムが、ポリスチレン系エラストマーおよびポリエーテルスルホンから選ばれる少なくとも１種を含む＜１＞記載の仮接着用積層体。
＜３＞　フィルムが、ポリスチレン系エラストマーを含む＜１＞に記載の仮接着用積層体。
＜４＞　ポリスチレン系エラストマーが、水添物である＜１＞～＜３＞のいずれかに記載の仮接着用積層体。
＜５＞　ポリスチレン系エラストマーの、２５℃から、２０℃／分で昇温した５％熱質量減少温度が２５０℃以上である＜１＞～＜４＞のいずれかに記載の仮接着用積層体。
＜６＞　離型剤が、シランカップリング剤である＜１＞～＜５＞のいずれかに記載の仮接着用積層体。
＜７＞　フィルムの両方の表面に離型層を有する＜１＞～＜６＞のいずれかに記載の仮接着用積層体。
＜８＞　フィルムの片方の表面のみに離型層を有する＜１＞～＜６＞のいずれかに記載の仮接着用積層体。
＜９＞　ポリスチレン系エラストマー、ポリエステル系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマー、ポリアクリル系エラストマー、シリコーン系エラストマー、ポリイミド系エラストマー、ポリエーテルエーテルケトン、ポリフェニレンエーテルおよびポリエーテルスルホンから選ばれる少なくとも１種を含むフィルムの表面に、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を形成する工程を含む、仮接着用積層体の製造方法。
＜１０＞　デバイスウエハと支持体との間に、＜１＞～＜８＞のいずれかに記載の仮接着用積層体を有し、仮接着用積層体の一方の表面がデバイスウエハのデバイス面に接し、他方の表面が支持体の表面に接している、デバイスウエハ付き積層体。
＜１１＞　仮接着用積層体は、フィルムの両方の表面に離型層を有する、＜１０＞に記載のデバイスウエハ付き積層体。
＜１２＞　仮接着用積層体は、フィルムの片方の表面のみに離型層を有し、離型層がデバイスウエハの表面に接している、＜１０＞に記載のデバイスウエハ付き積層体。
＜１３＞　仮接着用積層体は、フィルムの片方の表面のみに離型層を有し、離型層が支持体に接している、＜１０＞に記載のデバイスウエハ付き積層体。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have provided a release layer containing a release agent containing at least one selected from a fluorine atom and a silicon atom on one or both sides of a specific film described later. As a result of using the laminate for temporary bonding, it was found that the flatness is good, the device wafer and the support can be temporarily bonded with high adhesive force, and the temporary bonding between the device wafer and the support can be easily released. The invention has been completed. The present invention provides the following.
<1> A laminate for temporary bonding used to temporarily bond a device surface of a device wafer and a support so as to be peelable, and includes a polystyrene-based elastomer, a polyester-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, and a polyamide-based material. A film containing at least one selected from an elastomer, a polyacrylic elastomer, a silicone elastomer, a polyimide elastomer, polyether ether ketone, polyphenylene sulfide, polyphenylene ether, and polyether sulfone, and fluorine on at least one surface of the film A laminate for temporary bonding, having a release layer containing a release agent containing at least one selected from atoms and silicon atoms.
<2> The laminate for temporary adhesion according to <1>, wherein the film includes at least one selected from polystyrene-based elastomers and polyethersulfone.
<3> The laminate for temporary adhesion according to <1>, wherein the film includes a polystyrene-based elastomer.
<4> The laminate for temporary adhesion according to any one of <1> to <3>, wherein the polystyrene elastomer is a hydrogenated product.
<5> The temporary adhesive laminate according to any one of <1> to <4>, wherein the 5% thermal mass reduction temperature of the polystyrene-based elastomer raised from 25 ° C. at 20 ° C./min is 250 ° C. or more. .
<6> The temporary adhesive laminate according to any one of <1> to <5>, wherein the release agent is a silane coupling agent.
<7> The temporary adhesive laminate according to any one of <1> to <6>, wherein a release layer is provided on both surfaces of the film.
<8> The temporary bonding laminate according to any one of <1> to <6>, wherein the release layer is provided only on one surface of the film.
<9> Polystyrene elastomer, polyester elastomer, polyolefin elastomer, polyurethane elastomer, polyamide elastomer, polyacryl elastomer, silicone elastomer, polyimide elastomer, polyether ether ketone, polyphenylene ether, and polyether sulfone The manufacturing method of the laminated body for temporary attachment including the process of forming the mold release layer containing the mold release agent containing the at least 1 sort (s) chosen from a fluorine atom and a silicon atom on the surface of the film containing at least 1 sort (s).
<10> The temporary adhesion laminate according to any one of <1> to <8> is provided between the device wafer and the support, and one surface of the temporary adhesion laminate is a device surface of the device wafer. A laminated body with a device wafer in which the other surface is in contact with the surface of the support.
<11> The laminated body with a device wafer according to <10>, wherein the temporary bonding laminate has release layers on both surfaces of the film.
<12> The laminated body with a device wafer according to <10>, wherein the temporary bonding laminate has a release layer only on one surface of the film, and the release layer is in contact with the surface of the device wafer.
<13> The laminated body with a device wafer according to <10>, wherein the temporary bonding laminate has a release layer only on one surface of the film, and the release layer is in contact with the support.
　本発明によれば、デバイスウエハや支持体との接着面における平坦性が良好で、デバイスウエハと支持体とを安定して仮接着できるとともに、デバイスウエハと支持体との仮接着を容易に解除できる仮接着用積層体、仮接着用積層体の製造方法およびデバイスウエハ付き積層体を提供可能になった。 According to the present invention, the flatness on the bonding surface between the device wafer and the support is good, the device wafer and the support can be stably temporarily bonded, and the temporary bonding between the device wafer and the support is easily released. It has become possible to provide a laminate for temporary bonding, a method for producing a laminate for temporary adhesion, and a laminate with a device wafer.
半導体装置の製造方法を示す一実施形態の概略図である。It is the schematic of one Embodiment which shows the manufacturing method of a semiconductor device. 従来の接着性支持体とデバイスウエハとの仮接着状態の解除を説明する概略断面図である。It is a schematic sectional drawing explaining cancellation | release of the temporary adhesion state of the conventional adhesive support body and a device wafer.
　以下、本発明の実施形態を詳細に説明する。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書中における「活性光線」または「放射線」は、例えば、可視光線、紫外線、遠紫外線、電子線、Ｘ線等を含むものを意味する。
　本明細書において、「光」とは、活性光線または放射線を意味している。
　本明細書において、「露光」とは、特に断らない限り、水銀灯、紫外線、エキシマレーザーに代表される遠紫外線、Ｘ線、ＥＵＶ光等による露光のみならず、電子線およびイオンビーム等の粒子線による描画をも意味している。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタアクリレートを表し、「（メタ）アクリル」は、アクリルおよびメタアクリルを表し、「（メタ）アクリロイル」は、「アクリロイル」および「メタクリロイル」を表す。
　本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ Ｓｕｐｅｒ　ＡＷＭ―Ｈ（東ソー（株）製、６．０ｍｍＩＤ×１５．０ｃｍを、溶離液として１０ｍｍｏｌ／Ｌ　リチウムブロミドＮＭＰ(Ｎ－メチルピロリジノン)溶液を用いることによって求めることができる。
　なお、以下に説明する実施の形態において、既に参照した図面において説明した部材等については、図中に同一符号あるいは相当符号を付すことにより説明を簡略化あるいは省略化する。 Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
“Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
In this specification, “light” means actinic rays or radiation.
In this specification, unless otherwise specified, “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.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, “(meth) acryloyl” represents “acryloyl” and “methacryloyl”. Represents.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement. In this specification, 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 ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
In the embodiments described below, the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.
＜仮接着用積層体＞
　本発明の仮接着用積層体は、デバイスウエハのデバイス面と支持体とを、剥離可能に仮接着するために用いる仮接着用積層体であって、ポリスチレン系エラストマー、ポリエステル系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマー、ポリアクリル系エラストマー、シリコーン系エラストマー、ポリイミド系エラストマー、ポリエーテルエーテルケトン、ポリフェニレンスルファイド、ポリフェニレンエーテルおよびポリエーテルスルホンから選ばれる少なくとも１種を含むフィルム（以下、接着フィルムともいう）と、フィルムの少なくとも一方の表面に、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を有する。 <Laminated body for temporary bonding>
The laminate for temporary adhesion of the present invention is a laminate for temporary adhesion used for temporarily adhering a device surface of a device wafer and a support, which is a polystyrene-based elastomer, a polyester-based elastomer, and a polyolefin-based elastomer. A film containing at least one selected from polyurethane elastomer, polyamide elastomer, polyacryl elastomer, silicone elastomer, polyimide elastomer, polyether ether ketone, polyphenylene sulfide, polyphenylene ether and polyether sulfone (hereinafter referred to as adhesive) And a release layer containing a release agent containing at least one selected from a fluorine atom and a silicon atom on at least one surface of the film.
　本発明の仮接着用積層体は、フィルムを用いるので、デバイスウエハや支持体との接着面における平坦性が良好である。すなわち、塗布によって形成される塗布膜等を接着層として用いると、接着層中に溶剤を含むため、乾燥収縮などにより膜厚が均一になりにくく、接着性が劣るが、フィルムとして成型されたものを接着層として用いることにより、接着層中の溶剤の含有量を少なくでき、接着層の厚さの不均一性を抑制でき、結果として接着性を向上させることができる。さらに、接着フィルムが上述した材料を含むので、デバイスウエハや支持体の微細な凹凸にも追従し適度なアンカー効果により、より優れた接着性を達成できる。そして、接着フィルムの表層には、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を有するので、優れた剥離性を達成できる。このため、本発明の仮接着用積層体は、平坦性、接着性、剥離性に優れる。
　なお、本明細書において、「デバイスウエハのデバイス面と支持体とを、剥離可能に仮接着する」とは、デバイスウエハと支持体とを仮接着して一体化した状態（デバイスウエハ付き積層体）から、デバイスウエハと支持体との仮接着状態を解除して、両者を分離することを意味する。仮接着状態の解除は、機械剥離による解除が好ましい。
　本明細書において、「フィルム」とは、平坦な膜状または板状のものを意味する。「平坦」とは、例えば、後述するフィルムの一方向に沿った断面において、最大膜厚と最小膜厚の差が、フィルムの平均膜厚の２０％以下であることが好ましく、５％以下であることがより好ましい。なお、塗布膜は、厚みムラが生じやすく、更には、塗布膜は溶剤を含むため、乾燥収縮などにより膜厚が均一になりにくい。
　フィルムの溶剤含有率は、例えば、２０質量％以下が好ましく、５質量％以下がより好ましく、含有しないことが特に好ましい。フィルムの溶剤含有量は、ガスクロマトグラフィーで測定できる。
　フィルムは、例えば、後述する溶融製膜法、溶液製膜法などの方法で製造できる。
　以下、本発明の仮接着用積層体について具体的に説明する。 Since the laminate for temporary bonding of the present invention uses a film, the flatness on the bonding surface with the device wafer and the support is good. That is, when a coating film formed by coating is used as an adhesive layer, the adhesive layer contains a solvent, so the film thickness is difficult to be uniform due to drying shrinkage, etc. By using as the adhesive layer, the content of the solvent in the adhesive layer can be reduced, the non-uniformity of the thickness of the adhesive layer can be suppressed, and as a result, the adhesiveness can be improved. Furthermore, since the adhesive film includes the above-described material, it is possible to achieve even better adhesiveness by following the fine irregularities of the device wafer and the support body and by an appropriate anchor effect. And since it has a mold release layer containing the mold release agent containing at least 1 type chosen from a fluorine atom and a silicon atom in the surface layer of an adhesive film, the outstanding peelability can be achieved. For this reason, the laminated body for temporary adhesion of this invention is excellent in flatness, adhesiveness, and peelability.
In this specification, “the device surface of the device wafer and the support are temporarily bonded so as to be peelable” means that the device wafer and the support are temporarily bonded and integrated (a laminated body with a device wafer) ) To release the temporarily bonded state between the device wafer and the support and separate them. The temporary adhesive state is preferably released by mechanical peeling.
In the present specification, the “film” means a flat film or plate. “Flat” means, for example, that the difference between the maximum film thickness and the minimum film thickness is preferably 20% or less of the average film thickness in a cross section along one direction of the film, which will be described later, and is 5% or less. More preferably. Note that the coating film is likely to have thickness unevenness, and furthermore, since the coating film contains a solvent, the film thickness is difficult to be uniform due to drying shrinkage or the like.
The solvent content of the film is, for example, preferably 20% by mass or less, more preferably 5% by mass or less, and particularly preferably not contained. The solvent content of the film can be measured by gas chromatography.
The film can be produced by a method such as a melt film forming method or a solution film forming method described later.
Hereinafter, the laminated body for temporary adhesion of this invention is demonstrated concretely.
＜＜接着フィルム＞＞
　本発明の仮接着用積層体において、接着フィルムの平均厚みは、特に限定されるものではないが、例えば、０．１～５００μｍが好ましく、０．１～２００μｍがより好ましく、１０～２００μｍが更に好ましく、５０～２００μｍが特に好ましい。接着フィルムの平均厚みが上記範囲であれば、平坦性が良好である。なお、塗布膜の場合、厚みが大きくなるに伴い（例えば、１０μｍ以上）、平坦性が低下する傾向にあったが、フィルムであれば、厚みが大きくても平坦性に優れる。
　本発明において、接着フィルムの平均厚みは、接着フィルムの一方向に沿った断面において、一方の端面から他方の端面に向かって、等間隔で５か所の場所における厚みを、エリプソメトリーにより測定した値の平均値と定義する。
　なお、本発明において、「接着フィルムの一方向に沿った断面」とは、接着フィルムが矩形状である場合は、長辺方向に直交する断面とする。また、接着フィルムが正方形状である場合は、いずれか一方の辺に直交する断面とする。また、接着フィルムが円形または楕円形である場合は、重心を通過する断面とする。
　本発明の接着フィルムは、接着フィルムの一方向に沿った断面において、最大膜厚と最小膜厚の差が、平均膜厚の２０％以下であることが好ましく、５％以下であることがより好ましい。
　本発明の仮接着用積層体において、接着フィルムは、熱可塑性フィルムであってもよく、熱硬化性フィルムであってもよい。好ましくは、熱可塑性フィルムである。熱可塑性フィルムであることにより、優れた接着性が得られる。また、デバイスウエハの表面に凹凸が有していても、凹凸形状に対する追従性が良好である。
　なお、本発明において、熱可塑性フィルムは、例えば、ガラス転移温度が－５０～３００℃であり、１５０～３００℃における貯蔵弾性率が、１０1～１０9Ｐａであることが好ましく、１０2～１０8Ｐａであることがより好ましく、１０3～１０7Ｐａであることが最も好ましい。貯蔵弾性率は、一定昇温条件下で粘弾性測定装置を用いて測定した値である。動的粘弾性装置としては、例えば、Ｒｈｅｏｇｅｌ－Ｅ４０００（ユービーエム社製）を用いることができる。 << Adhesive film >>
In the laminate for temporary bonding of the present invention, the average thickness of the adhesive film is not particularly limited, but is preferably 0.1 to 500 μm, more preferably 0.1 to 200 μm, and further preferably 10 to 200 μm. A thickness of 50 to 200 μm is preferable. If the average thickness of the adhesive film is within the above range, the flatness is good. In the case of a coating film, the flatness tends to decrease as the thickness increases (for example, 10 μm or more), but the film is excellent in flatness even if the thickness is large.
In the present invention, the average thickness of the adhesive film was measured by ellipsometry at five locations at regular intervals from one end face to the other end face in a cross section along one direction of the adhesive film. It is defined as the average value.
In the present invention, the “cross section along one direction of the adhesive film” is a cross section orthogonal to the long side direction when the adhesive film is rectangular. Moreover, when an adhesive film is square shape, it is set as the cross section orthogonal to any one side. Moreover, when an adhesive film is circular or elliptical, it is set as the cross section which passes a gravity center.
In the adhesive film of the present invention, in the cross section along one direction of the adhesive film, the difference between the maximum film thickness and the minimum film thickness is preferably 20% or less of the average film thickness, and more preferably 5% or less. preferable.
In the laminate for temporary bonding according to the present invention, the adhesive film may be a thermoplastic film or a thermosetting film. Preferably, it is a thermoplastic film. By being a thermoplastic film, excellent adhesiveness can be obtained. Moreover, even if the surface of the device wafer has irregularities, the followability to the irregularities is good.
In the present invention, thermoplastic film, for example, the glass transition temperature is the -50 ~ 300 ° C., a storage elastic modulus at 0.99 ~ 300 ° C. is preferably from 10 1 ~ 10 9 Pa, 10 2 ~ 10 8 Pa is more preferable, and 10 3 to 10 7 Pa is most preferable. The storage elastic modulus is a value measured using a viscoelasticity measuring device under a constant temperature rise condition. As the dynamic viscoelastic device, for example, Rheogel-E4000 (manufactured by UBM) can be used.
＜＜＜ポリマー成分＞＞＞
　本発明の仮接着用積層体において、接着フィルムは、ポリスチレン系エラストマー、ポリエステル系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマー、ポリアクリル系エラストマー、シリコーン系エラストマー、ポリイミド系エラストマー、ポリエーテルエーテルケトン、ポリフェニレンスルファイド、ポリフェニレンエーテルおよびポリエーテルスルホンから選ばれる１種以上のポリマー成分を含む。ポリマー成分は、ポリスチレン系エラストマー、ポリエステル系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマー、ポリアクリル系エラストマー、シリコーン系エラストマーおよびポリイミド系エラストマーから選ばれる１種以上のエラストマーが好ましく、ポリスチレン系エラストマーが特に好ましい。また、エラストマーは、水添物であることが好ましい。特に、ポリスチレン系エラストマーの水添物が好ましい。
　上記ポリマー成分を含む接着フィルムは、支持体やデバイスウエハの微細な凹凸にも追従し適度なアンカー効果により、接着性に優れた接着層を形成できる。また、支持体をデバイスウエハから剥離する際に、デバイスウエハなどに応力をかけることなく、支持体をデバイスウエハから剥離でき、デバイス等の破損や剥落を防止できる。特にエラストマー、さらには、ポリスチレン系エラストマーを使用した場合上記効果が顕著である。
　また、エラストマーが水添物であると、熱安定性や保存安定性が向上する。さらには、剥離性および剥離後の仮接着用積層体の洗浄除去性が向上する。ポリスチレン系エラストマーの水添物を使用した場合上記効果が顕著である。
　なお、本明細書において、エラストマーとは、弾性変形を示す高分子化合物を表す。すなわち外力を加えたときに、その外力に応じて瞬時に変形し、かつ外力を除いたときには、短時間に元の形状を回復する性質を有する高分子化合物と定義する。
　本発明のエラストマーは、元の大きさを１００％としたときに、室温（２０℃）において小さな外力で２００％まで変形させることができ、かつ外力を除いたときに、短時間で１３０％以下に戻る性質を有することが好ましい。 <<< Polymer component >>>
In the laminate for temporary bonding of the present invention, the adhesive film is made of polystyrene elastomer, polyester elastomer, polyolefin elastomer, polyurethane elastomer, polyamide elastomer, polyacryl elastomer, silicone elastomer, polyimide elastomer, polyether ether. It contains one or more polymer components selected from ketones, polyphenylene sulfide, polyphenylene ethers and polyether sulfones. The polymer component is preferably one or more elastomers selected from polystyrene elastomers, polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, polyacryl elastomers, silicone elastomers and polyimide elastomers, and polystyrene elastomers. Is particularly preferred. The elastomer is preferably a hydrogenated product. In particular, a hydrogenated product of a polystyrene-based elastomer is preferable.
The adhesive film containing the polymer component can follow a fine unevenness of a support or a device wafer, and can form an adhesive layer having excellent adhesiveness by an appropriate anchor effect. Further, when the support is peeled from the device wafer, the support can be peeled from the device wafer without applying stress to the device wafer or the like, and damage or peeling of the device or the like can be prevented. In particular, when an elastomer, and further, a polystyrene-based elastomer is used, the above effect is remarkable.
Further, when the elastomer is a hydrogenated product, the thermal stability and the storage stability are improved. Furthermore, the releasability and the cleaning / removability of the laminated body for temporary adhesion after peeling are improved. When a hydrogenated product of polystyrene elastomer is used, the above effect is remarkable.
In addition, in this specification, 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 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.
　上記ポリマー成分のガラス転移温度（以下、Ｔｇともいう）は、－５０～３００℃が好ましく、０～２００℃がより好ましい。Ｔｇが上記範囲であれば、接着時にデバイスウエハ表面への追従性がよく、ボイドのない良好な接着力の仮接着用積層体を作成することができる。なお、ポリマー成分がＴｇを２種類以上有する場合は、上記Ｔｇの値は、低い方のガラス転移温度を意味する。
　上記ポリマー成分の融点は、－５０～３００℃が好ましく、０～２００℃がより好ましい。融点が上記範囲であれば接着時にデバイスウエハ表面への追従性がよく、ボイドのない良好な接着力の仮接着用積層体を作成することができる。なお、ポリマー成分が融点を２種類以上有する場合は、上記融点の値は、低い方の融点を意味する。
　上記ポリマー成分の重量平均分子量は、２０００～２００、０００が好ましく、１００００～２００、０００がより好ましく、５０、０００～１００、０００が最も好ましい。この範囲にあることで、支持体をデバイスウエハから剥離後、デバイスウエハおよび／または支持体に残存する仮接着用積層体を除去する際にも、溶剤への溶解性が優れるため、デバイスウエハや支持体に残渣が残らないなど利点がある。 The glass transition temperature (hereinafter also referred to as Tg) of the polymer component is preferably −50 to 300 ° C., more preferably 0 to 200 ° C. When Tg is in the above range, a followable adhesion to the surface of the device wafer at the time of bonding can be obtained, and a laminate for temporary bonding having a good adhesion without voids can be produced. In addition, when a polymer component has 2 or more types of Tg, the value of the said Tg means the lower glass transition temperature.
The melting point of the polymer component is preferably −50 to 300 ° C., more preferably 0 to 200 ° C. When the melting point is in the above range, the followability to the surface of the device wafer at the time of bonding is good, and a laminate for temporary bonding having a good adhesive force without voids can be produced. When the polymer component has two or more melting points, the melting point value means the lower melting point.
The polymer component has a weight average molecular weight of preferably 2000 to 200,000, more preferably 10,000 to 200,000, and most preferably 50,000 to 100,000. By being in this range, after removing the support from the device wafer, when removing the device wafer and / or the temporary adhesion laminate remaining on the support, the solubility in a solvent is excellent. There are advantages such as no residue remaining on the support.
　上記ポリマー成分は、２５℃から、２０℃／分で昇温した５％熱質量減少温度が、２５０℃以上であることが好ましく、３００℃以上であることがより好ましく、３５０℃以上であることがさらに好ましく、４００℃以上であることが最も好ましい。また、上限値は特に限定はないが、例えば１０００℃以下が好ましく、８００℃以下がより好ましい。この態様によれば、耐熱性に優れた仮接着用積層体を形成しやすい。特に、２５０℃以上の環境で使用可能な仮接着用積層体を形成しやすい。なお、質量減少温度とは、熱重量測定装置（ＴＧＡ）により、窒素気流下において、上記昇温条件で測定した値である。 The polymer component has a 5% thermal mass reduction temperature of 25 ° C. raised at 20 ° C./min, preferably 250 ° C. or higher, more preferably 300 ° C. or higher, and 350 ° C. or higher. Is more preferable, and most preferably 400 ° C. or higher. Moreover, although 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 a temporary adhesive laminate having excellent heat resistance. In particular, it is easy to form a temporary bonding laminate that can be used in an environment of 250 ° C. or higher. In addition, mass decreasing temperature is a value measured on the said temperature rising conditions in nitrogen stream by the thermogravimetry apparatus (TGA).
＜＜＜＜ポリスチレン系エラストマー＞＞＞＞
　ポリスチレン系エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができる。例えば、スチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、スチレン－エチレン－ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－ブタジエン－ブチレン－スチレン共重合体（ＳＢＢＳ）およびこれらの水添物、スチレン－エチレン－ブチレンスチレンブロックコポリマー（ＳＥＢＳ）、スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ）、スチレン－エチレン－エチレン－プロピレン－スチレンブロック共重合体等が挙げられる。 <<<<< Polystyrene Elastomer >>>>
There is no restriction | limiting in particular as a polystyrene-type elastomer, According to the objective, it can select suitably. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butylene-styrene. Copolymer (SBBS) and hydrogenated products thereof, styrene-ethylene-butylene styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block A copolymer etc. are mentioned.
　ポリスチレン系エラストマーにおける、スチレン由来の繰り返し単位の含有量は１０～９０質量％が好ましい。易剥離性の観点から、下限値は、２５質量％以上が好ましく、５１質量％以上がより好ましい。 The content of the repeating unit derived from styrene in the polystyrene elastomer is preferably 10 to 90% by mass. From the viewpoint of easy peelability, the lower limit is preferably 25% by mass or more, and more preferably 51% by mass or more.
　ポリスチレン系エラストマーは、スチレンと他の樹脂のブロック共重合体であることが好ましく、片末端または両末端がスチレンのブロック重合体であることがより好ましく、両末端がスチレンのブロック重合体であることが特に好ましい。ポリスチレン系エラストマーの両端を、スチレンのブロック重合体（スチレン由来の繰り返し単位）とすると、熱安定性がより向上する傾向にある。これは、耐熱性の高いスチレン由来の繰り返し単位が末端に存在することとなるためである。特に、スチレン由来の繰り返し単位のブロック部位が反応性のポリスチレン系ハードブロックであることにより、耐熱性、耐薬品性により優れる傾向にあり好ましい。また、これらをブロック共重合体とすると、２００℃以上においてハードブロックとソフトブロックでの相分離を行うと考えられる。その相分離の形状はデバイスウェハの基板表面の凹凸の発生の抑制に寄与すると考えられる。加えて、このような樹脂は、溶剤への溶解性およびレジスト溶剤への耐性の観点からもより好ましい。
　また、ポリスチレン系エラストマーは水添物であると、熱に対する安定性が向上し、分解や重合等の変質が起こりにくい。さらに、溶剤への溶解性およびレジスト溶剤への耐性の観点からもより好ましい。
　なお、本明細書において「スチレン由来の繰り返し単位」とは、スチレンまたはスチレン誘導体を重合した際に重合体に含まれるスチレン由来の構成単位であり、置換基を有していてもよい。スチレン誘導体としては、例えば、α－メチルスチレン、３－メチルスチレン、４－プロピルスチレン、４－シクロヘキシルスチレン等が挙げられる。置換基としては、例えば、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基、炭素数１～５のアルコキシアルキル基、アセトキシ基、カルボキシル基等が挙げられる。 The polystyrene elastomer is preferably a block copolymer of styrene and another resin, more preferably a block polymer of styrene at one or both ends, and a block polymer of styrene at both ends. Is particularly preferred. When both ends of the polystyrene-based elastomer are made of a styrene block polymer (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. In particular, 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. Moreover, when these are made into a block copolymer, it is thought that 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. In addition, such a resin is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.
In addition, when the polystyrene elastomer is a hydrogenated product, the stability to heat is improved, and degradation such as decomposition and polymerization hardly occurs. Furthermore, it is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.
In the present specification, “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. Examples of the styrene derivative include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and the like. Examples of the 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.
　エラストマーは、２５℃から、２０℃／分で昇温した５％熱質量減少温度が、２５０℃以上であることが好ましく、３００℃以上であることがより好ましく、３５０℃以上であることがさらに好ましく、４００℃以上であることが最も好ましい。また、上限値は特に限定はないが、例えば１０００℃以下が好ましく、８００℃以下がより好ましい。この態様によれば、耐熱性に優れた仮接着用積層体を形成しやすい。 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. Preferably, the temperature is 400 ° C. or higher. Moreover, although 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 a temporary adhesive laminate having excellent heat resistance.
　ポリスチレン系エラストマーの市販品としては、例えば、タフプレンＡ、タフプレン１２５、タフプレン１２６Ｓ、ソルプレンＴ、アサプレンＴ－４１１、アサプレンＴ－４３２、アサプレンＴ－４３７、アサプレンＴ－４３８、アサプレンＴ－４３９、タフテックＨ１２７２、タフテックＰ１５００、タフテックＨ１０５２、タフテックＨ１０６２、タフテックＭ１９４３、タフテックＭ１９１１、タフテックＨ１０４１、タフテックＭＰ１０、タフテックＭ１９１３、タフテックＨ１０５１、タフテックＨ１０５３、タフテックＰ２０００、タフテックＨ１０４３（以上、旭化成（株）製）、エラストマーＡＲ－８５０Ｃ、エラストマーＡＲ８１５Ｃ、エラストマーＡＲ－８４０Ｃ、エラストマーＡＲ－８３０Ｃ、エラストマーＡＲ８６０Ｃ、エラストマーＡＲ－８７５Ｃ、エラストマーＡＲ－８８５Ｃ、エラストマーＡＲ－ＳＣ－１５、エラストマーＡＲ－ＳＣ－０、エラストマーＡＲ－ＳＣ－５、エラストマーＡＲ－７１０、エラストマーＡＲ－ＳＣ－６５、エラストマーＡＲ－ＳＣ－３０、エラストマーＡＲ－ＳＣ－７５、エラストマーＡＲ－ＳＣ－４５、エラストマーＡＲ－７２０、エラストマーＡＲ－７４１、エラストマーＡＲ－７３１、エラストマーＡＲ－７５０、エラストマーＡＲ－７６０、エラストマーＡＲ－７７０、エラストマーＡＲ－７８１、エラストマーＡＲ－７９１、エラストマーＡＲ－ＦＬ－７５Ｎ、エラストマーＡＲ－ＦＬ－８５Ｎ、エラストマーＡＲ－ＦＬ－６０Ｎ、エラストマーＡＲ－１０５０、エラストマーＡＲ－１０６０、エラストマーＡＲ－１０４０（アロン化成製）、クレイトンＤ１１１１、クレイトンＤ１１１３、クレイトンＤ１１１４、クレイトンＤ１１１７、クレイトンＤ１１１９、クレイトンＤ１１２４、クレイトンＤ１１２６、クレイトンＤ１１６１、クレイトンＤ１１６２、クレイトンＤ１１６３、クレイトンＤ１１６４、クレイトンＤ１１６５、クレイトンＤ１１８３、クレイトンＤ１１９３、クレイトンＤＸ４０６、クレイトンＤ４１４１、クレイトンＤ４１５０、クレイトンＤ４１５３、クレイトンＤ４１５８、クレイトンＤ４２７０、クレイトンＤ　４２７１、クレイトンＤ　４４３３、クレイトンＤ　１１７０、クレイトンＤ　１１７１、クレイトンＤ　１１７３、カリフレックスＩＲ０３０７、カリフレックスＩＲ　０３１０、カリフレックスＩＲ　０４０１、クレイトンＤ０２４２、クレイトンＤ１１０１、クレイトンＤ１１０２、クレイトンＤ１１１６、クレイトンＤ１１１８、クレイトンＤ１１３３、クレイトンＤ１１５２、クレイトンＤ１１５３、クレイトンＤ１１５５、クレイトンＤ１１８４、クレイトンＤ１１８６、クレイトンＤ１１８９、クレイトンＤ１１９１、クレイトンＤ１１９２、クレイトンＤＸ４０５、クレイトンＤＸ４０８、クレイトンＤＸ４１０、クレイトンＤＸ４１４、クレイトンＤＸ４１５、クレイトンＡ１５３５、クレイトンＡ１５３６、クレイトンＦＧ１９０１、クレイトンＦＧ１９２４、クレイトンＧ１６４０、クレイトンＧ１６４１、クレイトンＧ１６４２、クレイトンＧ１６４３、クレイトンＧ１６４５、クレイトンＧ１６３３、クレイトンＧ１６５０、クレイトンＧ１６５１、クレイトンＧ１６５２、クレイトンＧ１６５４、クレイトンＧ１６５７、クレイトンＧ１６６０、クレイトンＧ１７２６、クレイトンＧ１７０１、クレイトンＧ１７０２、クレイトンＧ１７３０、クレイトンＧ１７５０、クレイトンＧ１７６５、クレイトンＧ４６０９、クレイトンＧ４６１０（Ｋｒａｔｏｎ製）、ＴＲ２０００、ＴＲ２００１、ＴＲ２００３、ＴＲ２２５０、ＴＲ２５００、ＴＲ２６０１、ＴＲ２６３０、ＴＲ２７８７、ＴＲ２８２７、ＴＲ１０８６、ＴＲ１６００、ＳＩＳ５００２、ＳＩＳ５２００、ＳＩＳ５２５０、ＳＩＳ５４０５、ＳＩＳ５５０５、ダイナロン６１００Ｐ、ダイナロン４６００Ｐ、ダイナロン６２００Ｐ、ダイナロン４６３０Ｐ、ダイナロン８６０１Ｐ、ダイナロン８６３０Ｐ、ダイナロン８６００Ｐ、ダイナロン８９０３Ｐ、ダイナロン６２０１Ｂ、ダイナロン１３２１Ｐ、ダイナロン１３２０Ｐ、ダイナロン２３２４Ｐ、ダイナロン９９０１Ｐ（ＪＳＲ（株）製）、デンカＳＴＲシリーズ（電気化学工業（株）製）、クインタック３５２０、クインタック３４３３Ｎ、クインタック３４２１、クインタック３６２０、クインタック３４５０、クインタック３４６０（日本ゼオン製）、ＴＰＥ－ＳＢシリーズ（住友化学（株）製）、ラバロンシリーズ（三菱化学（株）製）、セプトン１００１、セプトン、８００４、セプトン４０３３、セプトン２１０４、セプトン８００７、セプトン２００７、セプトン２００４、セプトン２０６３、セプトンＨＧ２５２、セプトン８０７６、セプトン２００２、セプトン１０２０、セプトン８１０４、セプトン２００５、セプトン２００６、セプトン４０５５、セプトン４０４４、セプトン４０７７、セプトン４０９９、セプトン８００６、セプトンＶ９４６１、ハイブラー７３１１、ハイブラー７１２５、ハイブラー５１２７、ハイブラー５１２５（以上、クラレ製）、スミフレックス（住友ベークライト（株）製）、レオストマー、アクティマー（以上、理研ビニル工業製）などが挙げられる。 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, Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer AR-710, Elastomer AR-SC-65, Elastomer AR-SC- 30, Elastomer AR-SC-75, Elastomer AR-SC-45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer AR-770, Elastomer AR-781 , Elastomer AR-791, Elastomer AR-FL-75N, Elastomer AR-FL-85N, Elastomer AR-FL-60N, Elastomer AR-1050, Elastomer AR-1060, Elastomer AR-1040 (Aron Kasei), Clayton D1111, Clayton D1113, Clayton D1114, Clayton D1117, Clayton D1119, Clayton D1124, Clayton D1126, Clayton D1161, Clayton D1162, Clayton D1163, Clayton D1164, Clayton D1165, Clayton D1183, Clayton D1193 Clayton DX406, Clayton D4141, Clayton D4150, Clayton D4153, Clayton D4158, Clayton D4270, Clayton D 4271, Clayton D 4433, Clayton D 1170, Clayton D 1171, Clayton D 1173, Califlex IR0307, Califlex IR 0310, Califlex I R 0401, Clayton D0242, Clayton D1101, Clayton D1102, Clayton D1116, Clayton D1118, Clayton D1133, Clayton D1152, Clayton D1153, Clayton D1155, Clayton D1184, Clayton D1186, Clayton D1189, Clayton D1192, Clayton DX405, Clayton DX405 Clayton DX410, Clayton DX414, Clayton DX415, Clayton A1535, Clayton A1536, Clayton FG1901, Clayton FG1924, Clayton G1640, Clayton G1641, Clayton G1642, Clayton G1643, Clayton G1645, Clayton G1633, Clayton 1650, Clayton G1651, Clayton G1652, Clayton G1654, Clayton G1657, Clayton G1660, Clayton G1726, Clayton G1701, Clayton G1702, Clayton G1750, Clayton G1765, Clayton G4609, Clayton G4610 (manufactured by Kraton), TR2000, TR2001, TR3 , TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynalon 6100P, Dynalon 4600P, Dynalon 6200P, Dynalon 4630P, Dynalon 8601P 8630P, Dynalon 8600P, Dynalon 8903P, Dynalon 6201B, Dynalon 1321P, Dynalon 1320P, Dynalon 2324P, Dynalon 9901P (manufactured by JSR Corporation), Denka STR series (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac 3520, Quinc 3433N, QUINTAC 3421, QUINTAC 3620, QUINTAC 3450, QUINTAC 3460 (manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Lavalon series (manufactured by Mitsubishi Chemical Corporation), Septon 1001, Septon, 8004, Septon 4033, Septon 2104, Septon 8007, Septon 2007, Septon 2004, Septon 2063, Septon HG252, Septon 8076, Septon 2002, Septon Septon 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Septon 4077, Septon 4099, Septon 8006, Septon V9461, Hibler 7311, Hibler 7125, Hibler 5127, Hybler 5125 (above, made by Kuraray), Sumiflex (Manufactured by Sumitomo Bakelite Co., Ltd.), rheomers, actimators (manufactured by Riken Vinyl Industry), and the like.
＜＜＜＜ポリエステル系エラストマー＞＞＞＞
　ポリエステル系エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができる。例えば、ジカルボン酸又はその誘導体と、ジオール化合物又はその誘導体とを重縮合して得られるものが挙げられる。
　ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸及びこれらの芳香核の水素原子がメチル基、エチル基、フェニル基等で置換された芳香族ジカルボン酸、アジピン酸、セバシン酸、ドデカンジカルボン酸等の炭素数２～２０の脂肪族ジカルボン酸、及びシクロヘキサンジカルボン酸などの脂環式ジカルボン酸などが挙げられる。これらは、１種単独で使用してもよく、２種以上併用してもよい。
　ジオール化合物としては、例えば、エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、１，１０－デカンジオール、１，４－シクロヘキサンジオールなどの脂肪族ジオール、脂環式ジオール、下記構造式で表される２価のフェノールなどが挙げられる。 <<<<< Polyester elastomer >>>>
There is no restriction | limiting in particular as 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.
Examples of 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.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記式中、ＹDOは、炭素原子数１～１０のアルキレン基、炭素原子数４～８のシクロアルキレン基、－Ｏ－、－Ｓ－、及び－ＳＯ2－のいずれかを表すか、ベンゼン環同士の直接結合（単結合）を表す。ＲDO1及びＲDO2は各々独立に、ハロゲン原子又は炭素原子数１～１２のアルキル基を表す。ｐdo1及びｐdo2は各々独立に、０～４の整数を表し、ｎdo1は、０又は１を表す。 In the above formula, 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. Represents a direct bond (single bond) between rings. 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.
　ポリエステル系エラストマーの具体例としては、ビスフェノールＡ、ビス－（４－ヒドロキシフェニル）メタン、ビス－（４－ヒドロキシ－３－メチルフェニル）プロパン、レゾルシンなどが挙げられる。これらは、１種単独で使用してもよく、２種以上併用して用いてもよい。
　また、ポリエステル系エラストマーとして、芳香族ポリエステル（例えば、ポリブチレンテレフタレート）部分をハードセグメント成分に、脂肪族ポリエステル（例えば、ポリテトラメチレングリコール）部分をソフトセグメント成分にしたマルチブロック共重合体を用いることもできる。マルチブロック共重合体としては、ハードセグメントとソフトセグメントとの種類、比率、及び分子量の違いによりさまざまなグレードのものが挙げられる。具体例としては、ハイトレル（東レデュポン（株）製）、ペルプレン（東洋紡績（株）製）、プリマロイ（三菱化学製）、ヌーベラン（帝人化成製）、エスペル１６１２、１６２０（日立化成工業（株）製）、プリマロイＣＰ３００（三菱化学社製）などが挙げられる。 Specific examples of the polyester elastomer 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.
Also, as the polyester elastomer, 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. Specific examples include Hytrel (manufactured by Toray DuPont), Perprene (manufactured by Toyobo Co., Ltd.), Primalloy (manufactured by Mitsubishi Chemical), Nouvelan (manufactured by Teijin Chemicals), Espel 1612, 1620 (Hitachi Chemical Industries, Ltd.) Product), Primalloy CP300 (manufactured by Mitsubishi Chemical Corporation), and the like.
＜＜＜＜ポリオレフィン系エラストマー＞＞＞＞
　ポリオレフィン系エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができり。例えば、エチレン、プロピレン、１－ブテン、１－ヘキセン、４－メチル－ペンテン等の炭素数２～２０のα－オレフィンの共重合体などが挙げられる。例えば、エチレン－プロピレン共重合体（ＥＰＲ）、エチレン－プロピレン－ジエン共重合体（ＥＰＤＭ）等が挙げられる。また、ジシクロペンタジエン、１，４－ヘキサジエン、シクロオクタジエン、メチレンノルボルネン、エチリデンノルボルネン、ブタジエン、イソプレンなどの炭素数２～２０の非共役ジエンとα－オレフィン共重合体などが挙げられる。また、ブタジエン－アクリロニトリル共重合体にメタクリル酸を共重合したカルボキシ変性ニトリルゴムが挙げられる。具体的には、エチレン・α－オレフィン共重合体ゴム、エチレン・α－オレフィン・非共役ジエン共重合体ゴム、プロピレン・α－オレフィン共重合体ゴム、ブテン・α－オレフィン共重合体ゴムなどが挙げられる。
　市販品として、ミラストマー（三井化学（株）製）、サーモラン（三菱化学製）ＥＸＡＣＴ（エクソン化学製）、ＥＮＧＡＧＥ（ダウケミカル製）、エスポレックス（住友化学製）、Ｓａｒｌｉｎｋ（東洋紡製）、ニューコン（日本ポリプロ製）、ＥＸＣＥＬＩＮＫ（ＪＳＲ製）などが挙げられる。 <<<<< Polyolefin Elastomer >>>>
There is no restriction | limiting in particular as polyolefin-type elastomer, According to the objective, it can select suitably. Examples thereof include copolymers of α-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). Further, non-conjugated dienes having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene, and α-olefin copolymers can be used. Further, a carboxy-modified nitrile rubber obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer can be mentioned. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber, etc. Can be mentioned.
As commercial products, Miralastomer (Mitsui Chemicals), Thermoran (Mitsubishi Chemical) EXACT (Exxon Chemical), ENGAGE (Dow Chemical), Espolex (Sumitomo Chemical), Sarlink (Toyobo), Newcon (Nippon Polypro), EXCELLINK (JSR) and the like.
＜＜＜＜ポリウレタン系エラストマー＞＞＞＞
　ポリウレタン系エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができる。例えば、低分子のグリコールおよびジイソシアネートからなるハードセグメントと、高分子（長鎖）ジオールおよびジイソシアネートからなるソフトセグメントとの構造単位を含むエラストマーなどが挙げられる。
　高分子（長鎖）ジオールとしては、ポリプロピレングリコール、ポリテトラメチレンオキサイド、ポリ（１，４－ブチレンアジペート）、ポリ（エチレン・１，４－ブチレンアジペート）、ポリカプロラクトン、ポリ（１，６－ヘキシレンカーボネート）、ポリ（１，６－ヘキシレン・ネオペンチレンアジペート）などが挙げられる。高分子（長鎖）ジオールの数平均分子量は、５００～１０，０００が好ましい。
　低分子のグリコールとしては、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、ビスフェノールＡ等の短鎖ジオールを用いることができる。短鎖ジオールの数平均分子量は、４８～５００が好ましい。
ポリウレタン系エラストマーの市販品としては、ＰＡＮＤＥＸ　Ｔ－２１８５、Ｔ－２９８３Ｎ（ＤＩＣ（株）製）、ミラクトラン（日本ミラクトラン製）、エラストラン（ＢＡＳＦ製）、レゼミン（大日精化工業製）、ペレセン（ダウ・ケミカル製）、アイアンラバー（ＮＯＫ社製）、モビロン（日清紡ケミカル製）などが挙げられる。 <<<<< Polyurethane Elastomer >>>>
There is no restriction | limiting in particular as a polyurethane-type elastomer, According to the objective, it can select suitably. For example, 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.
Examples of 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). Xylene carbonate), poly (1,6-hexylene neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000.
As 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.
＜＜＜＜ポリアミド系エラストマー＞＞＞＞
　ポリアミド系エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができる。例えば、ポリアミド－６、１１、１２などのポリアミドをハードセグメントに用い、ポリオキシエチレン、ポリオキシプロピレン、ポリテトラメチレングリコールなどのポリエーテルおよび／またはポリエステルをソフトセグメントに用いたエラストマーなどが挙げられる。このエラストマーは、ポリエーテルブロックアミド型、ポリエーテルエステルブロックアミド型の２種類に大別される。
　市販品として、ＵＢＥポリアミドエラストマ、ＵＢＥＳＴＡ　ＸＰＡ（宇部興産（株）製）、ダイアミド（ダイセルヒュルス（株）製）、ＰＥＢＡＸ（東レ（株）製）、グリロンＥＬＹ（エムスジャパン（株）製）、ノパミッド（三菱化学（株）製）、グリラックス（ＤＩＣ（株）製）、ポリエーテルエステルアミドＰＡ－２００、ＰＡ－２０１、ＴＰＡＥ－１２、ＴＰＡＥ－３２、ポリエステルアミドＴＰＡＥ－６１７、ＴＰＡＥ－６１７Ｃ（（株）Ｔ＆Ｋ　ＴＯＫＡ製）などが挙げられる。 <<<<< Polyamide Elastomer >>>>
There is no restriction | limiting in particular as a polyamide-type elastomer, According to the objective, it can select suitably. For example, 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.
As commercially available products, UBE polyamide elastomer, UBESTA XPA (manufactured by Ube Industries), Daiamide (manufactured by Daicel Huls), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MS Japan), Nopamid (manufactured by Mitsubishi Chemical Corporation), Glais (manufactured by DIC Corporation), polyether ester amide PA-200, PA-201, TPAE-12, TPAE-32, polyester amide TPAE-617, TPAE-617C ( (T & K TOKA Co., Ltd.).
＜＜＜＜ポリイミド系エラストマー＞＞＞＞
　ポリイミド系エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができる。例えば、芳香族ポリイミド等のエンジニアリングプラスチックと、ソフトセグメントである分子量が数百～千のポリエーテルやポリエステルやポリオレフィン等のゴム成分とからなり、ハードセグメントとソフトセグメントが交互に重縮合したブロックポリマーが好ましく使用できる。市販品の具体例としては、例えば、ＵＢＥＳＴＡ　ＸＰＡ９０４０Ｆ１（宇部興産（株）製）などが挙げられる。 <<<<< Polyimide elastomer >>>>
There is no restriction | limiting in particular as a polyimide-type elastomer, According to the objective, it can select suitably. For example, a block polymer consisting of engineering plastics such as aromatic polyimide and rubber segments such as polyether, polyester, and polyolefin with a molecular weight of several hundred to 1,000, which are soft segments. It can be preferably used. Specific examples of the commercially available product include UBESTA XPA9040F1 (manufactured by Ube Industries).
＜＜＜＜ポリアクリル系エラストマー＞＞＞＞
　ポリアクリル系エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができる。例えば、エチルアクリレート、ブチルアクリレート、メトキシエチルアクリレート、エトキシエチルアクリレートなどのアクリル酸エステルを主成分としたものや、
アクリル酸エステルと、グリシジルメタクリレート、アリルグリシジルエーテルなどが挙げられる。さらに、アクリロニトリルやエチレンなどの架橋点モノマーとを共重合してなるものなどが挙げられる。具体的には、アクリロニトリル－ブチルアクリレート共重合体、アクリロニトリル－ブチルアクリレート－エチルアクリレート共重合体、アクリロニトリル－ブチルアクリレート－グリシジルメタクリレート共重合体などが挙げられる。 <<<<< Polyacrylic elastomer >>>>
There is no restriction | limiting in particular as a polyacrylic-type elastomer, According to the objective, it can select suitably. For example, 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. Furthermore, the thing etc. which copolymerize with crosslinking point monomers, such as acrylonitrile and ethylene, etc. are mentioned. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.
＜＜＜＜シリコーン系エラストマー＞＞＞＞
　シリコーン系エラストマーとしては、特に制限はなく、目的に応じて適宜選択することができる。例えば、オルガノポリシロキサンを主成分としたもので、ポリジメチルシロキサン系、ポリメチルフェニルシロキサン系、ポリジフェニルシロキサンなどが挙げられる。市販品の具体例としては、ＫＥシリーズ（信越化学工業（株）製）、ＳＥシリーズ、ＣＹシリーズ、ＳＨシリーズ（以上、東レダウコーニングシリコーン（株）製）などが挙げられる。 <<<<< Silicone Elastomer >>>>
There is no restriction | limiting in particular as a silicone type elastomer, According to the objective, it can select suitably. For example, 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.
＜＜＜＜その他エラストマー＞＞＞＞
　本発明では、エラストマーとして、ゴム変性したエポキシ樹脂（エポキシ系エラストマー）を用いることができる。エポキシ系エラストマーは、例えば、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、サリチルアルデヒド型エポキシ樹脂、フェノールノボラック型エポキシ樹脂あるいはクレゾールノボラック型エポキシ樹脂の一部又は全部のエポキシ基を、両末端カルボン酸変性型ブタジエン－アクリロニトリルゴム、末端アミノ変性シリコーンゴム等で変性することによって得られる。 <<<<< Other elastomers >>>>
In the present invention, a rubber-modified epoxy resin (epoxy elastomer) can be used as the elastomer. 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.
＜＜＜＜ポリエーテルエーテルケトン＞＞＞＞
　ポリエーテルエーテルケトンとしては、特に制限なく使用することができ、例えば、ケトロン１０００　ＰＥＥＫシリーズ、ケトロンＨＰＶ　ＰＥＥＫシリーズ、ケトロンＧＦ３０ＰＥＥＫシリーズ、ケトロンＧＡ３０ＰＥＥＫシリーズ（クオドラントポリペンコジャパン製）が挙げられる。 <<<<< Polyetheretherketone >>>>
The polyether ether ketone can be used without particular limitation, and examples thereof include Ketron 1000 PEEK series, Ketron HPV PEEK series, Ketron GF30PEEK series, and Ketron GA30PEEK series (manufactured by Quadrant Polypenco Japan).
＜＜＜＜ポリフェニレンスルファイド＞＞＞＞
　ポリフェニレンスルファイドとしては、特に制限なく使用することができ、例えば、テクトロン１０００ＰＰＳ、テクトロンＨＰＶＰＰＳ（クオドラントポリペンコジャパン製）が挙げられる。 <<<<< Polyphenylenesulfide >>>>
The polyphenylene sulfide can be used without particular limitation, and examples thereof include Tektron 1000PPS and Tektron HPVPPS (manufactured by Quadrant Polypenco Japan).
＜＜＜＜ポリフェニレンエーテル＞＞＞＞
　ポリフェニレンエーテルとしては、特に制限なく使用することができ、例えば、ユピエースシリーズ、レマロイシリーズ（三菱エンジニアリングプラスチック社製）、ＸＹＲＯＮシリーズ（ＸＹＲＯＮ　Ｓ２０１Ａなど）（旭化成ケミカルズ社製）、ＮＯＲＹＬシリーズ（ＳＡＢＩＣイノベーティブプラスチックスジャパン製）が挙げられる。 <<<<< Polyphenylene ether >>>>
The polyphenylene ether can be used without any particular limitation. For example, Iupiace series, Remalloy series (Mitsubishi Engineering Plastics), XYRON series (XYRON S201A, etc.) (Asahi Kasei Chemicals), NORYL series (SABIC Innovative) Plastics Japan).
＜＜＜ポリエーテルスルホン＞＞＞
　ポリエーテルスルホンとしては、例えば、特開２００６－８９５９５号公報、特開２００４－３５２９２０号公報、特開２００２－３３８６８８号公報、特開平０７－９７４４７号公報および特開平０４－２０５３０号公報に記載のポリエーテルスルホンが挙げられる。
　ポリエーテルスルホンの中でもポリマー中にアレーン構造を有するポリエーテルスルホンを用いることにより、フィルムの結晶性が上昇し、ある一定温度以上の高温環境下においてもデバイスウエハの処理時に付加される剪断力に対してデバイスウエハを保持しうる剪断接着力を維持することが可能な仮接着用積層体が得られやすい。アレーン構造を有するポリエーテルスルホンとしては、例えば、式（ＩＶ）で表される構成単位を有するポリエーテルスルホンが挙げられる。 <<<< Polyethersulfone >>>>
Examples of the polyethersulfone include those described in JP-A-2006-89595, JP-A-2004-352920, JP-A-2002-338688, JP-A-07-97447, and JP-A-4-20530. Examples include polyethersulfone.
Among polyethersulfones, the use of polyethersulfone having an arene structure in the polymer increases the crystallinity of the film, and the shear force applied during processing of device wafers even in high temperature environments above a certain temperature. Thus, it is easy to obtain a laminate for temporary bonding that can maintain a shearing adhesive force capable of holding a device wafer. Examples of the polyethersulfone having an arene structure include polyethersulfone having a structural unit represented by the formula (IV).
Figure JPOXMLDOC01-appb-C000002
 　式（ＩＶ）中、Ｒ1～Ｒ3は、アレーン構造を有する２価の有機基であって、ただし式（ＩＶ）中の結合手はＲ1～Ｒ3中のアレーン構造に直結している（すなわち、式（ＩＶ）中の－Ｏ－Ｒ1－Ｏ－、－Ｏ－Ｒ2－ＳＯ2－および－ＳＯ2－Ｒ3－Ｏ－における－Ｏ－および－ＳＯ2－は、Ｒ1～Ｒ3中のアレーン構造に直結している）。Ｒ1～Ｒ3は、それぞれ同一であっても異なってもよい。
　２価の有機基としては、例えば、フェニレン基、ナフタレンジイル基、アントラセンジイル基およびピレンジイル基等のアリーレン基；－Ｃ6Ｈ4－Ｃ6Ｈ4－等の２つのアリーレン基が直接結合してなる基；式（ＩＶ－１）～（ＩＶ－３）で示される２つのアリーレン基の間に２価の炭化水素基を有する基などが挙げられる。
Figure JPOXMLDOC01-appb-C000002
 In formula (IV), R 1 to R 3 are divalent organic groups having an arene structure, provided that the bond in formula (IV) is directly connected to the arene structure in R 1 to R 3 . (That is, —O— and —SO 2 — in —O—R 1 —O—, —O—R 2 —SO 2 — and —SO 2 —R 3 —O— in Formula (IV) are R 1 Is directly connected to the arene structure in R 3 ). R 1 to R 3 may be the same or different.
Examples of the divalent organic group include arylene groups such as a phenylene group, a naphthalenediyl group, an anthracenediyl group, and a pyrenediyl group; and two arylene groups such as —C 6 H 4 —C 6 H 4 — A group having a divalent hydrocarbon group between two arylene groups represented by formulas (IV-1) to (IV-3), and the like.
Figure JPOXMLDOC01-appb-C000003
 式（ＩＶ－１）～（ＩＶ－３）中、＊は結合手を示す。
Figure JPOXMLDOC01-appb-C000003
 In formulas (IV-1) to (IV-3), * represents a bond.
　ポリエーテルスルホンの重量平均分子量（Ｍｗ）は、１，０００～１，０００，０００が好ましく、５，０００～５００，０００がより好ましい。ポリエーテルスルホンの数平均分子量をＭｎとするとき、Ｍｗ／Ｍｎで示される分子量分布は、１～５が好ましく、１～３．５がより好ましい。
　ポリエーテルスルホンとしては、市販品を用いることもできる。ポリエーテルスルホンの市販品としては、例えば、ＢＡＳＦ社製の「ＵｌｔｒａｓｏｎＥシリーズ」（ＵｌｔｒａｓｏｎＥ６０２０など）、ソルベイアドバンストポリマー社製の「レーデルＡシリーズ」、住友化学社製の「スミカエクセルシリーズ」が挙げられる。「スミカエクセルシリーズ」としては、例えば、スミカエクセル（登録商標）ＰＥＳ３６００Ｐ、スミカエクセル（登録商標）ＰＥＳ４１００Ｐ、スミカエクセル（登録商標）ＰＥＳ４１００ＭＰ、スミカエクセル（登録商標）ＰＥＳ４８００Ｐ、スミカエクセル（登録商標）ＰＥＳ５００３Ｐ、スミカエクセル（登録商標）ＰＥＳ５２００Ｐ、スミカエクセル（登録商標）ＰＥＳ５４００Ｐが挙げられる。 The weight average molecular weight (Mw) of the polyethersulfone is preferably 1,000 to 1,000,000, and more preferably 5,000 to 500,000. When the number average molecular weight of the polyethersulfone is Mn, the molecular weight distribution represented by Mw / Mn is preferably 1 to 5, and more preferably 1 to 3.5.
A commercially available product can also be used as the polyethersulfone. Examples of commercially available polyethersulfone include “Ultrason E series” (such as Ultrason E6020) manufactured by BASF, “Radel A series” manufactured by Solvay Advanced Polymer, and “Sumika Excel series” manufactured by Sumitomo Chemical. Examples of the “Sumika Excel series” include Sumika Excel (registered trademark) PES 3600P, Sumika Excel (registered trademark) PES 4100P, Sumika Excel (registered trademark) PES 4100MP, Sumika Excel (registered trademark) PES 4800P, Sumika Excel (registered trademark) PES 5003P, SUMIKAEXCEL (registered trademark) PES5200P, SUMIKAEXCEL (registered trademark) PES5400P, and the like.
　接着フィルムは、上記ポリマー成分をフィルムの全固形分に対して、５０～１００質量％含有することが好ましく、７０～１００質量％がより好ましく、８８～１００質量％が特に好ましい。この態様によれば、接着性および剥離性に優れた仮接着用積層体を得やすい。ポリマー成分は上記に挙げた種類を複数含んでいてもよい。
　また、ポリマー成分は、スチレン系エラストマーを５０～１００質量％含有することが好ましく、８０～１００質量％含有することがより好ましく、９０～１００質量％含有することがさらに好ましく、スチレン系エラストマーのみで構成されていることが特に好ましい。この態様によれば、接着性および剥離性に優れた仮接着用積層体を得やすい。 The adhesive film preferably contains the polymer component in an amount of 50 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 88 to 100% by mass with respect to the total solid content of the film. According to this aspect, it is easy to obtain a temporary adhesion laminate having excellent adhesion and peelability. The polymer component may contain a plurality of the types listed above.
Further, the polymer component preferably contains 50 to 100% by mass of a styrene elastomer, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and only the styrene elastomer. It is particularly preferable that it is configured. According to this aspect, it is easy to obtain a temporary adhesion laminate having excellent adhesion and peelability.
＜＜＜酸化防止剤＞＞＞
　接着フィルムは、加熱時の酸化によるポリマー成分の低分子化やゲル化を防止する観点から、酸化防止剤を含有してもよい。酸化防止剤としては、フェノール系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤、キノン系酸化防止剤、アミン系酸化防止剤などが使用できる。
　フェノール系酸化防止剤としては例えば、ｐ－メトキシフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、ＢＡＳＦ（株）製「Ｉｒｇａｎｏｘ（登録商標）１０１０」、「Ｉｒｇａｎｏｘ（登録商標）１３３０」、「Ｉｒｇａｎｏｘ（登録商標）３１１４」、「Ｉｒｇａｎｏｘ（登録商標）１０３５」、住友化学（株）製「Ｓｕｍｉｌｉｚｅｒ（登録商標）　ＭＤＰ－Ｓ」、「Ｓｕｍｉｌｉｚｅｒ（登録商標）　ＧＡ－８０」などが挙げられる。
　硫黄系酸化防止剤としては例えば、３，３’－チオジプロピオネートジステアリル、住友化学（株）製「Ｓｕｍｉｌｉｚｅｒ（登録商標）　ＴＰＭ」、「Ｓｕｍｉｌｉｚｅｒ（登録商標）　ＴＰＳ」、「Ｓｕｍｉｌｉｚｅｒ（登録商標）　ＴＰ－Ｄ」などが挙げられる。
　リン系酸化防止剤としては例えば、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスフィト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスフィト、ポリ（ジプロピレングリコール）フェニルホスフィト、ジフェニルイソデシルホスフィト、２－エチルヘキシルジフェニルホスフィト、トリフェニルホスフィト、ＢＡＳＦ（株）製「Ｉｒｇａｆｏｓ（登録商標）１６８」、「Ｉｒｇａｆｏｓ（登録商標）３８」などが挙げられる。
　キノン系酸化防止剤としては例えば、ｐ－ベンゾキノン、２－ｔｅｒｔ－ブチル－１，４－ベンゾキノンなどが挙げられる。
　アミン系酸化防止剤としては例えば、ジメチルアニリンやフェノチアジンなどが挙げられる。
　酸化防止剤は、Ｉｒｇａｎｏｘ（登録商標）１０１０、Ｉｒｇａｎｏｘ（登録商標）１３３０、３，３’－チオジプロピオネートジステアリル、Ｓｕｍｉｌｉｚｅｒ（登録商標）　ＴＰ－Ｄが好ましく、Ｉｒｇａｎｏｘ（登録商標）１０１０、Ｉｒｇａｎｏｘ（登録商標）１３３０がより好ましく、Ｉｒｇａｎｏｘ（登録商標）１０１０が特に好ましい。
　また、上記酸化防止剤のうち、フェノール系酸化防止剤と、硫黄系酸化防止剤またはリン系酸化防止剤とを併用することが好ましく、フェノール系酸化防止剤と硫黄系酸化防止剤とを併用することが最も好ましい。特に、エラストマーとして、ポリスチレン系エラストマーを使用した場合において、フェノール系酸化防止剤と硫黄系酸化防止剤とを併用することが好ましい。このような組み合わせにすることにより、酸化反応によるエラストマーの劣化を、効率よく抑制できる効果が期待できる。フェノール系酸化防止剤と硫黄系酸化防止剤とを併用する場合、フェノール系酸化防止剤と硫黄系酸化防止剤との質量比は、フェノール系酸化防止剤：硫黄系酸化防止剤＝９５：５～５：９５が好ましく、２５：７５～７５：２５がより好ましい。
　酸化防止剤の組み合わせとしては、Ｉｒｇａｎｏｘ（登録商標）１０１０とＳｕｍｉｌｉｚｅｒ（登録商標）　ＴＰ－Ｄ、Ｉｒｇａｎｏｘ（登録商標）１３３０とＳｕｍｉｌｉｚｅｒ（登録商標）　ＴＰ－Ｄ、および、Ｓｕｍｉｌｉｚｅｒ（登録商標）　ＧＡ－８０とＳｕｍｉｌｉｚｅｒ（登録商標）　ＴＰ－Ｄが好ましく、Ｉｒｇａｎｏｘ（登録商標）１０１０とＳｕｍｉｌｉｚｅｒ（登録商標）　ＴＰ－Ｄ、Ｉｒｇａｎｏｘ（登録商標）１３３０とＳｕｍｉｌｉｚｅｒ（登録商標）　ＴＰ－Ｄがより好ましく、Ｉｒｇａｎｏｘ（登録商標）１０１０とＳｕｍｉｌｉｚｅｒ（登録商標）　ＴＰ－Ｄが特に好ましい。 <<< Antioxidant >>>
The adhesive film may contain an antioxidant from the viewpoint of preventing the polymer component from being lowered in molecular weight or gelled due to oxidation during heating. As the 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.
Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, “Irganox (registered trademark) 1010” and “Irganox (registered trademark) 1330 manufactured by BASF Corporation. "Irganox (registered trademark) 3114", "Irganox (registered trademark) 1035", "Sumilizer (registered trademark) MDP-S" manufactured by Sumitomo Chemical Co., Ltd., "Sumilizer (registered trademark) GA-80", and the like. It is done.
Examples of the sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, “Sumilizer (registered trademark) TPM”, “Sumilizer (registered trademark) TPS”, and “Sumilizer (registered trademark)” manufactured by Sumitomo Chemical Co., Ltd. TP-D ”and the like.
Examples of 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 (registered trademark) 168” manufactured by BASF Corporation, and “Irgafos (registered trademark) 38”.
Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
The antioxidant is preferably Irganox® 1010, Irganox® 1330, 3,3′-thiodipropionate distearyl, Sumilizer® TP-D, Irganox® 1010, Irganox (Registered trademark) 1330 is more preferable, and Irganox (registered trademark) 1010 is particularly preferable.
Of the above antioxidants, it is preferable to use 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. Most preferred. In particular, when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. By using such a combination, it can be expected that the deterioration of the elastomer due to the oxidation reaction can be efficiently suppressed. When a phenolic antioxidant and a sulfurous antioxidant are used in combination, the mass ratio of the phenolic antioxidant to the sulfurous antioxidant is: phenolic antioxidant: sulfurous antioxidant = 95: 5 to 5:95 is preferable, and 25:75 to 75:25 is more preferable.
The combination of antioxidants includes Irganox® 1010 and Sumilizer® TP-D, Irganox® 1330 and Sumilizer® TP-D, and Sumilizer® GA-80. And Sumilizer (R) TP-D are preferred, Irganox (R) 1010, Sumilizer (R) TP-D, Irganox (R) 1330 and Sumilizer (R) TP-D are more preferred, and Irganox (R) Trademark) 1010 and Sumilizer® TP-D are particularly preferred.
　酸化防止剤の分子量は加熱中の昇華防止の観点から、４００以上が好ましく、６００以上がさらに好ましく、７５０以上が特に好ましい。 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.
　接着フィルムが酸化防止剤を有する場合、酸化防止剤の含有量は、接着フィルムの全固形分に対して、０．００１～２０．０質量％が好ましく、０．００５～１０．０質量％がより好ましい。
　酸化防止剤は１種類のみでもよいし、２種類以上であってもよい。酸化防止剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive film has an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass, and 0.005 to 10.0% by mass with respect to the total solid content of the adhesive film. More preferred.
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.
＜＜＜高分子化合物＞＞＞
　接着フィルムは、必要に応じて上述したポリマー成分以外の高分子化合物を有していてもよい。
　本発明においては、高分子化合物は任意のものを使用できる。高分子化合物は、重量平均分子量が２０００以上の化合物であり、通常は、重合性基を含まない化合物である。高分子化合物の重量平均分子量は、１０，０００～１，０００，０００であることが好ましく、５０，０００～５００，０００であることが好ましく、１００，０００～３００，０００であることがより好ましい。
　高分子化合物の具体例としては、例えば、炭化水素樹脂、ノボラック樹脂、フェノール樹脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂、アルキド樹脂、ポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、テフロン（登録商標）、ポリアミド樹脂、ポリアセタール樹脂、ポリカーボネート樹脂、ポリブチレンテラフタレート樹脂、ポリエチレンテレフタラート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリアリレート樹脂などの合成樹脂や、天然ゴムなどの天然樹脂が挙げられる。中でも、炭化水素樹脂、ノボラック樹脂、が好ましく、炭化水素樹脂がよりさらに好ましい。高分子化合物は必要に応じて２種以上を組み合わせて使用しても良い。 <<< polymer compound >>>
The adhesive film may have a polymer compound other than the above-described polymer component as necessary.
In the present invention, any polymer compound can be used. The polymer compound is a compound having a weight average molecular weight of 2000 or more and is usually a compound not containing a polymerizable group. The weight average molecular weight of the polymer compound is preferably 10,000 to 1,000,000, preferably 50,000 to 500,000, and more preferably 100,000 to 300,000. .
Specific examples of the polymer compound include, for example, hydrocarbon resins, novolak resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyvinyl chloride resins, polyvinyl acetate resins, Teflon ( Registered resins), polyamide resins, polyacetal resins, polycarbonate resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polysulfone resins, polyethersulfone resins, polyarylate resins, and natural resins such as natural rubber. . Among these, hydrocarbon resins and novolac 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.
　炭化水素樹脂として任意のものを使用できる。
　炭化水素樹脂は、基本的には炭素原子と水素原子のみからなる樹脂を意味するが、基本となる骨格が炭化水素樹脂であれば、側鎖としてその他の原子を含んでいても良い。すなわち、炭素原子と水素原子のみからなる炭化水素樹脂に、アクリル樹脂、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルピロリドン樹脂のように、主鎖に炭化水素基以外の官能基が直接結合する場合も本発明における炭化水素樹脂に包含されるものであり、この場合、主鎖に炭化水素基が直接結合されてなる繰り返し単位の含有量が、樹脂の全繰り返し単位に対して３０モル％以上であることが好ましい。
　上記条件に合致する炭化水素樹脂としては例えば、テルペン樹脂、テルペンフェノール樹脂、変性テルペン樹脂、水添テルペン樹脂、水添テルペンフェノール樹脂、ロジン、ロジンエステル、水添ロジン、水添ロジンエステル、重合ロジン、重合ロジンエステル、変性ロジン、ロジン変性フェノール樹脂、アルキルフェノール樹脂、脂肪族石油樹脂、芳香族石油樹脂、水添石油樹脂、変性石油樹脂、脂環族石油樹脂、クマロン石油樹脂、インデン石油樹脂、ポリスチレン－ポリオレフィン共重合体、オレフィンポリマー（例えば、メチルペンテン共重合体）、および、シクロオレフィンポリマー（例えば、ノルボルネン共重合体、ジシクロペンタジエン共重合体、テトラシクロドデセン共重合体）などが挙げられる。
　炭化水素樹脂は、中でも、テルペン樹脂、ロジン、石油樹脂、水素化ロジン、重合ロジン、オレフィンポリマー、または、シクロオレフィンポリマーであることが好ましく、テルペン樹脂、ロジン、オレフィンポリマー、または、シクロオレフィンポリマーであることがより好ましく、テルペン樹脂、ロジン、オレフィンポリマー、または、シクロオレフィンポリマーであることがより好ましく、テルペン樹脂、ロジン、シクロオレフィンポリマー、または、オレフィンポリマーであることが更に好ましく、シクロオレフィンポリマーであることが特に好ましい。 Any hydrocarbon resin can be used.
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. It is included in the hydrocarbon resin in the invention, and in this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is 30 mol% or more based on the total repeating unit of the resin. Is preferred.
Examples of 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, polystyrene -Polyolefin copolymers, olefin polymers (eg methylpentene copolymer), and cycloolefin polymers (eg norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer), etc. .
The hydrocarbon resin is preferably a terpene resin, rosin, petroleum resin, hydrogenated rosin, polymerized rosin, olefin polymer, or cycloolefin polymer, and is preferably a terpene resin, rosin, olefin polymer, or cycloolefin polymer. More preferably, it is a terpene resin, rosin, olefin polymer or cycloolefin polymer, more preferably a terpene resin, rosin, cycloolefin polymer or olefin polymer, and a cycloolefin polymer. It is particularly preferred.
　シクロオレフィンポリマーとしては、ノルボルネン系重合体、単環の環状オレフィンの重合体、環状共役ジエンの重合体、ビニル脂環式炭化水素重合体、およびこれら重合体の水素化物などが挙げられる。シクロオレフィンポリマーの好ましい例としては、下記一般式（ＩＩ）で表される繰り返し単位を少なくとも１種以上含む付加（共）重合体、および、一般式（Ｉ）で表される繰り返し単位の少なくとも１種以上をさらに含んでなる付加（共）重合体が挙げられる。また、シクロオレフィンポリマーの他の好ましい例としては、一般式（ＩＩＩ）で表される環状繰り返し単位を少なくとも１種含む開環（共）重合体が挙げられる。 Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferred examples of the cycloolefin polymer include addition (co) polymers containing at least one repeating unit represented by the following general formula (II), and at least one repeating unit represented by the general formula (I). An addition (co) polymer further comprising a species or more is mentioned. Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式中、ｍは０～４の整数を表す。Ｒ1～Ｒ6は、それぞれ、水素原子または炭素数１～１０の炭化水素基を表し、Ｘ1～Ｘ3、および、Ｙ1～Ｙ3は、それぞれ、水素原子、炭素数１～１０の炭化水素基、ハロゲン原子、ハロゲン原子で置換された炭素数１～１０の炭化水素基、－（ＣＨ2）ｎＣＯＯＲ11、－（ＣＨ2）ｎＯＣＯＲ12、－（ＣＨ2）ｎＮＣＯ、－（ＣＨ2）ｎＮＯ2、－（ＣＨ2）ｎＣＮ、－（ＣＨ2）ｎＣＯＮＲ13Ｒ14、－（ＣＨ2）ｎＮＲ15Ｒ16、－（ＣＨ2）ｎＯＺ、－（ＣＨ2）ｎＷ、または、Ｘ1とＹ1、Ｘ2とＹ2、若しくはＸ3とＹ3から構成された（－ＣＯ）2Ｏ、（－ＣＯ）2ＮＲ17を表す。Ｒ11、Ｒ12、Ｒ13、Ｒ14、Ｒ15、Ｒ16およびＲ17は、それぞれ、水素原子、または、炭化水素基（好ましくは炭素数１～２０の炭化水素基）、Ｚは、炭化水素基、または、ハロゲンで置換された炭化水素基を表し、Ｗは、ＳｉＲ18 pＤ3-p（Ｒ18は炭素数１～１０の炭化水素基を表し、Ｄはハロゲン原子を表し、－ＯＣＯＲ18または－ＯＲ18を表し、ｐは０～３の整数を示す）を表す。ｎは０～１０の整数を表す。 In the formula, m represents an integer of 0 to 4. R 1 to R 6 each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X 1 to X 3 and Y 1 to Y 3 are each a hydrogen atom, or a carbon group having 1 to 10 carbon atoms. A hydrocarbon group, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted by a halogen atom, — (CH 2 ) nCOOR 11 , — (CH 2 ) nOCOR 12 , — (CH 2 ) nNCO, — (CH 2 ) NNO 2 , — (CH 2 ) nCN, — (CH 2 ) nCONR 13 R 14 , — (CH 2 ) nNR 15 R 16 , — (CH 2 ) nOZ, — (CH 2 ) nW, or X 1 It represents (—CO) 2 O, (—CO) 2 NR 17 composed of Y 1 , X 2 and Y 2 , or X 3 and Y 3 . R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), and Z is a carbon atom Represents a hydrogen group or a hydrocarbon group substituted with halogen, W represents SiR 18 p D 3-p (R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, Represents OCOR 18 or —OR 18 , and p represents an integer of 0 to 3. n represents an integer of 0 to 10.
　ノルボルネン系重合体は、特開平１０－７７３２号公報、特表２００２－５０４１８４号公報、ＵＳ２００４／２２９１５７Ａ１号公報あるいはＷＯ２００４／０７０４６３Ａ１号公報等に開示されている。ノルボルネン系重合体は、ノルボルネン系多環状不飽和化合物同士を付加重合することによって得ることができる。また、必要に応じ、ノルボルネン系多環状不飽和化合物と、エチレン、プロピレン、ブテン；ブタジエン、イソプレンのような共役ジエン；エチリデンノルボルネンのような非共役ジエンとを付加重合することもできる。このノルボルネン系重合体は、三井化学（株）よりアペルの商品名で発売されており、ガラス転移温度（Ｔｇ）の異なる例えばＡＰＬ８００８Ｔ（Ｔｇ７０℃）、ＡＰＬ６０１３Ｔ（Ｔｇ１２５℃）あるいはＡＰＬ６０１５Ｔ（Ｔｇ１４５℃）などのグレードがある。ポリプラスチック（株）よりＴＯＰＡＳ８００７、同５０１３、同６０１３、同６０１５などのペレットが発売されている。さらに、Ｆｅｒｒａｎｉａ社よりＡｐｐｅａｒ３０００が発売されている。 Norbornene polymers are disclosed in JP-A-10-7732, JP-T 2002-504184, US2004 / 229157A1, WO2004 / 070463A1, and the like. The norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, a norbornene-based polycyclic unsaturated compound and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene can also be subjected to addition polymerization. This norbornene-based polymer is marketed by Mitsui Chemicals, Inc. under the name of Apel, and has different glass transition temperatures (Tg), such as APL8008T (Tg70 ° C), APL6013T (Tg125 ° C), APL6015T (Tg145 ° C), etc. There are grades. Pellets such as TOPAS 8007, 5013, 6013, 6015, etc. are available from Polyplastics. Further, Appear 3000 is sold by Ferrania.
　ノルボルネン系重合体の水素化物は、特開平１－２４０５１７号公報、特開平７－１９６７３６号公報、特開昭６０－２６０２４号公報、特開昭６２－１９８０１号公報、特開２００３－１１５９７６７号公報あるいは特開２００４－３０９９７９号公報等に開示されているように、多環状不飽和化合物を付加重合あるいはメタセシス開環重合した後、水素添加することにより製造できる。
　一般式（ＩＩＩ）中、Ｒ5およびＲ6は、水素原子またはメチル基であることが好ましく、Ｘ3およびＹ3は水素原子であることが好ましく、その他の基は適宜選択される。このノルボルネン系重合体は、ＪＳＲ（株）からアートン（Ａｒｔｏｎ）ＧあるいはアートンＦという商品名で発売されており、また日本ゼオン（株）からゼオノア（Ｚｅｏｎｏｒ）ＺＦ１４、ＺＦ１６、ゼオネックス（Ｚｅｏｎｅｘ）２５０、同２８０、同４８０Ｒという商品名で市販されており、これらを使用することができる。 The hydrides of norbornene polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, and JP-A-2003-1159767. Alternatively, as disclosed in JP-A-2004-309979, etc., it can be produced by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization and then hydrogenation.
In general formula (III), R 5 and R 6 are preferably hydrogen atoms or methyl groups, X 3 and Y 3 are preferably hydrogen atoms, and other groups are appropriately selected. This norbornene polymer is sold under the trade name Arton G or Arton F by JSR Co., Ltd., and Zeonor ZF14, ZF16, Zeonex 250, Nippon Zeon Co., Ltd., These are commercially available under the trade names 280 and 480R, and these can be used.
　接着フィルムが、高分子化合物を有する場合、高分子化合物の含有量は、接着フィルムの全固形分に対して、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、２０質量％以上であることがさらに好ましい。また、高分子化合物の含有量の上限は、仮止め接着剤の全固形分に対して、７０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下がさらに好ましく、４０質量％以下が特に好ましい。
　接着フィルムは、ポリマー成分以外の高分子化合物を実質的に含有しない構成とすることもできる。「高分子化合物を実質的に含有しない」とは、例えば、接着フィルムの全固形部に対し、高分子化合物の含有量が１質量％以下が好ましく、０．１質量％以下がより好ましく、含有しないことが一層好ましい。 When the adhesive film has a polymer compound, the content of the polymer compound is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the adhesive film, More preferably, it is 20 mass% or more. Further, 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. The following are particularly preferred:
An adhesive film can also be set as the structure which does not contain polymer compounds other than a polymer component substantially. “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 adhesive film. More preferably not.
＜＜＜界面活性剤＞＞＞
　接着フィルムは、界面活性剤を含有してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用でき、フッ素系界面活性剤が好ましい。界面活性剤を含有させることで、液特性（特に、流動性）が向上し、接着フィルムを塗布形成する場合において、塗布厚の均一性や省液性をより改善することができる。 <<< surfactant >>>
The adhesive film may contain a surfactant. As the surfactant, various surfactants such as a fluorosurfactant, nonionic surfactant, cationic surfactant, anionic surfactant, and silicone surfactant can be used. Is preferred. By containing the surfactant, the liquid properties (particularly fluidity) are improved, and in the case of coating and forming an adhesive film, the uniformity of coating thickness and the liquid-saving property can be further improved.
　フッ素系界面活性剤は、フッ素含有率が３～４０質量％であることが好ましく、５～３０質量％がより好ましく、７～２５質量％が更に好ましい。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的である。さらには、溶解性も良好である。 The fluorine-containing surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties. Furthermore, the solubility is also good.
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、同Ｆ７８１（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレートおよびプロポキシレート（例えば、グリセロールプロポキシレート、グリセリンエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル（ＢＡＳＦ社製のプルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１、ソルスパース２００００（日本ルーブリゾール（株）製）等が挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2 manufactured by BASF) 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Spa Scan 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
　カチオン系界面活性剤としては、フタロシアニン誘導体（商品名：ＥＦＫＡ－７４５、森下産業（株）製）、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等が挙げられる。 Examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) heavy. Combined polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
　アニオン系界面活性剤としては、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）社製）等が挙げられる。 Examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and the like.
　シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング（株）製「トーレシリコーンＤＣ３ＰＡ」、「トーレシリコーンＳＨ７ＰＡ」、「トーレシリコーンＤＣ１１ＰＡ」、「トーレシリコーンＳＨ２１ＰＡ」、「トーレシリコーンＳＨ２８ＰＡ」、「トーレシリコーンＳＨ２９ＰＡ」、「トーレシリコーンＳＨ３０ＰＡ」、「トーレシリコーンＳＨ８４００」、モメンティブ・パフォーマンス・マテリアルズ社製「ＴＳＦ－４４４０」、「ＴＳＦ－４３００」、「ＴＳＦ－４４４５」、「ＴＳＦ－４４６０」、「ＴＳＦ－４４５２」、信越シリコーン株式会社製「ＫＰ３４１」、「ＫＦ６００１」、「ＫＦ６００２」、ビックケミー社製「ＢＹＫ３０７」、「ＢＹＫ３２３」、「ＢＹＫ３３０」等が挙げられる。 Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
　接着フィルムが界面活性剤を有する場合、界面活性剤の含有量は、接着フィルムの全固形分に対して、０．００１～２．０質量％が好ましく、０．００５～１．０質量％がより好ましい。
　界面活性剤は１種類のみでもよいし、２種類以上であってもよい。界面活性剤が２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesive film has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, and 0.005 to 1.0% by mass with respect to the total solid content of the adhesive film. More preferred.
Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
＜＜その他の添加剤＞＞
　接着フィルムは、本発明の効果を損なわない範囲で、必要に応じて、各種添加物、例えば、硬化剤、硬化触媒、充填剤、密着促進剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は接着フィルムの全固形分の３質量％以下が好ましい。 << Other additives >>
The adhesive film may contain various additives such as a curing agent, a curing catalyst, a filler, an adhesion promoter, an ultraviolet absorber, an anti-aggregation agent, etc. Can do. When these additives are blended, the total blending amount is preferably 3% by mass or less based on the total solid content of the adhesive film.
＜＜離型層＞＞
　本発明の仮接着用積層体は、接着フィルムの片方の表面（片面）または両方の表面（両面）に、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を有する。
　離型層の膜厚は、薄膜であっても効果が得られるので、特に限定はない。例えば、０．００１～１μｍが好ましく、０．０１～０．５μｍがより好ましい。上記範囲であれば、仮接着用積層体が適度な接着力を有し、デバイスウエハや支持体との接着性が良好であるとともに、仮接着用積層体を基材や支持体から容易に剥離することができる。
　本発明において、離型層の平均厚みは、離型層の一方向に沿った断面において、一方の端面から他方の端面に向かって、等間隔で５か所の場所における厚みを、エリプソメトリーにより測定した値の平均値と定義する。「離型層の一方向に沿った断面」は、上述した「接着フィルムの一方向に沿った断面」と同義である。
　離型層のフッ素含有率は、５～９０質量％が好ましく、２０～８０質量％がより好ましく、５０～７５質量％が特に好ましい。フッ素含有率は、「｛（１分子中のフッ素原子数×フッ素原子の質量）／１分子中の全原子の質量｝×１００」で定義される。
　離型層は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を、離型層の全固形分に対して、５～１００質量％含有することが好ましく、５０～１００質量％がより好ましく、９０～１００質量％が更に好ましい。離型層は複数の種類の離型剤を有していてもよい。 << Release layer >>
The laminate for temporary bonding according to the present invention comprises a release layer containing a release agent containing at least one selected from fluorine atoms and silicon atoms on one surface (one surface) or both surfaces (both surfaces) of an adhesive film. Have.
The film thickness of the release layer is not particularly limited because an effect can be obtained even if it is a thin film. For example, 0.001 to 1 μm is preferable, and 0.01 to 0.5 μm is more preferable. If it is the said range, while the laminated body for temporary adhesion has moderate adhesive force, while adhering with a device wafer or a support body is favorable, the laminated body for temporary adhesion is easily peeled from a base material or a support body. can do.
In the present invention, the average thickness of the release layer is determined by ellipsometry in five sections at equal intervals from one end face to the other end face in a cross section along one direction of the release layer. Defined as the average of the measured values. The “cross section along one direction of the release layer” is synonymous with the above-described “cross section along one direction of the adhesive film”.
The fluorine content of the release layer is preferably 5 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 50 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 5 to 100% by weight, preferably 50 to 100% by weight, of a release agent containing at least one selected from fluorine atoms and silicon atoms, based on the total solid content of the release layer. Is more preferable, and 90 to 100% by mass is even more preferable. The release layer may have a plurality of types of release agents.
＜＜＜離型剤＞＞＞
　離型剤は、フッ素原子を少なくとも含む化合物が好ましく、フッ素原子とケイ素原子を含む化合物がより好ましい。
　また、離型剤は、シランカップリング剤が好ましく、フッ素原子を少なくとも含むシランカップリング剤がさらに好ましい。
　フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤は、熱硬化性の化合物であっても非熱硬化性の化合物であってもよい。熱硬化性の化合物としては、例えば、シランカップリング剤などが挙げられる。このような化合物としては、フッ素原子が一分子中に２個以上含まれる、一般的にパーフルオロ基と呼ばれる基を有している化合物であることが好ましい。なお、離型剤がモノマー成分を含む場合においては、モノマー成分の少なくとも一部は、重合してポリマーとして存在している。 <<< release agent >>>
The release agent is preferably a compound containing at least a fluorine atom, and more preferably a compound containing a fluorine atom and a silicon atom.
The release agent is preferably a silane coupling agent, and more preferably a silane coupling agent containing at least a fluorine atom.
The release agent containing at least one selected from a fluorine atom and a silicon atom may be a thermosetting compound or a non-thermosetting compound. Examples of the thermosetting compound include a silane coupling agent. Such a compound is preferably a compound having a group generally called a perfluoro group containing two or more fluorine atoms in one molecule. When the release agent contains a monomer component, at least a part of the monomer component is polymerized and exists as a polymer.
＜＜＜＜熱硬化性の化合物＞＞＞＞
　熱硬化性の化合物としては、フッ素原子および架橋性基を有する化合物を好ましく使用できる。架橋性基としては例えば、水酸基又は加水分解可能な基を有するシリル基（例えばアルコキシシリル基、アシルオキシシリル基等）、反応性不飽和二重結合を有する基（（メタ）アクリロイル基、アリル基、ビニルオキシ基等）、開環重合反応性基（エポキシ基、オキセタニル基、オキサゾリル基等）、活性水素原子を有する基（たとえば水酸基、カルボキシル基、アミノ基、カルバモイル基、メルカプト基、β－ケトエステル基、ヒドロシリル基、シラノール基等）、酸無水物、求核剤によって置換され得る基（活性ハロゲン原子、スルホン酸エステル等）等が挙げられる。
　これらの中でも、架橋性基として、水酸基又は加水分解可能な基を有するシリル基（例えばアルコキシシリル基、アシルオキシシリル基等）、または反応性不飽和二重結合を有する基（（メタ）アクリロイル基、アリル基、ビニルオキシ基等）を有する化合物が好ましい。 <<<<< thermosetting compound >>>>
As the thermosetting compound, a compound having a fluorine atom and a crosslinkable group can be preferably used. Examples of the crosslinkable group include a silyl group having a hydroxyl group or a hydrolyzable group (eg, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) acryloyl group, allyl group, Vinyloxy groups, etc.), ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, mercapto groups, β-ketoester groups, Hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like.
Among these, as the crosslinkable group, a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), or a group having a reactive unsaturated double bond ((meth) acryloyl group, Compounds having an allyl group, a vinyloxy group, etc.) are preferred.
　水酸基又は加水分解可能な基を有するシリル基を有する化合物としては、具体的には、フッ素原子を少なくとも一つ有する基と、シリル基を少なくとも一つ有する化合物が挙げられる。フッ素原子を少なくとも一つ有する基としては、フッ素原子が一分子中に２個以上含まれる、一般的にパーフルオロアルキル基またはパーフルオロエーテル基と呼ばれる基を有している化合物であることが好ましい。フッ素原子を有する基は置換基を有していてもよい。置換基としては、反応性や熱安定性の観点から任意に選択することができ、例えば、塩素原子、臭素原子及びヨウ素原子等のハロゲン原子；メトキシ基、エトキシ基及びｔｅｒｔ－ブトキシ基等のアルコキシ基；フェノキシ基及びｐ－トリルオキシ基等のアリールオキシ基；メトキシカルボニル基、ブトキシカルボニル基及びフェノキシカルボニル基等のアルコキシカルボニル基；アセトキシ基、プロピオニルオキシ基及びベンゾイルオキシ基等のアシルオキシ基；アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基及びメトキサリル基等のアシル基；メチルスルファニル基及びｔｅｒｔ－ブチルスルファニル基等のアルキルスルファニル基；フェニルスルファニル基及びｐ－トリルスルファニル基等のアリールスルファニル基；メチル基、エチル基、ｔｅｒｔ－ブチル基及びドデシル基等のアルキル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基、アダマンチル基等のシクロアルキル基；フェニル基、ｐ－トリル基、キシリル基、クメニル基、ナフチル基、アンスリル基及びフェナントリル基等のアリール基；ヒドロキシ基；カルボキシ基；ホルミル基；スルホニル基；シアノ基；アルキルアミノカルボニル基；アリールアミノカルボニル基；スルホンアミド基；シリル基；アミノ基；モノアルキルアミノ基；ジアルキルアミノ基；アリールアミノ基；及びジアリールアミノ基チオキシ基；又はこれらの組み合わせが挙げられる。 Specific examples of the compound having a silyl group having a hydroxyl group or a hydrolyzable group include a group having at least one fluorine atom and a compound having at least one silyl group. The group having at least one fluorine atom is preferably a compound having a group generally called a perfluoroalkyl group or a perfluoroether group in which two or more fluorine atoms are contained in one molecule. . The group having a fluorine atom may have a substituent. The substituent can be arbitrarily selected from the viewpoints of reactivity and thermal stability. For example, halogen atoms such as chlorine, bromine and iodine atoms; alkoxy such as methoxy, ethoxy and tert-butoxy An aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group and a benzoyloxy group; an acetyl group; Acyl groups such as benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; aryls such as phenylsulfanyl group and p-tolylsulfanyl group Sulfanyl group; alkyl group such as methyl group, ethyl group, tert-butyl group and dodecyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group; phenyl group, p-tolyl group, xylyl group, Aryl groups such as cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxy group; carboxy group; formyl group; sulfonyl group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; A monoalkylamino group; a dialkylamino group; an arylamino group; and a diarylamino group thioxy group; or a combination thereof.
　シリル基としては、シラノール基または加水分解性シリル基を有することが好ましい。加水分解性シリル基とは、加水分解性を有するシリル基のことであり、加水分解性基としては、アルコキシ基、メルカプト基、ハロゲン原子、アミド基、アセトキシ基、アミノ基、イソプロペノキシ基等を挙げることができる。シリル基は加水分解してシラノール基となり、シラノール基は脱水縮合してシロキサン結合が生成する。このような加水分解性シリル基又はシラノール基は下記式（Ｂ－１）で表されるものが好ましい。 The silyl group preferably has a silanol group or a hydrolyzable silyl group. The hydrolyzable silyl group is a hydrolyzable silyl group. Examples of the hydrolyzable group include an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. be able to. The silyl group is hydrolyzed to become a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond. Such a hydrolyzable silyl group or silanol group is preferably one represented by the following formula (B-1).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（Ｂ－１）中、Ｒh1～Ｒh3の少なくともいずれか１つは、アルコキシ基、メルカプト基、ハロゲン原子、アミド基、アセトキシ基、アミノ基、及び、イソプロペノキシ基よりなる群から選択される加水分解性基、又は、ヒドロキシ基を表す。残りのＲh1～Ｒh3はそれぞれ独立に水素原子、ハロゲン原子、又は、１価の有機置換基（例えば、アルキル基、アリール基、アルケニル基、アルキニル基、アラルキル基を挙げることができる。）を表す。
　式（Ｂ－１）中、ケイ素原子に結合する加水分解性基としては、特にアルコキシ基、ハロゲン原子が好ましく、アルコキシ基がより好ましい。
　アルコキシ基としては、剥離性の観点から、炭素数１～３０のアルコキシ基が好ましい。より好ましくは炭素数１～１５のアルコキシ基、更に好ましくは炭素数１～５のアルコキシ基、特に好ましくは炭素数１～３のアルコキシ基、最も好ましくはメトキシ基又はエトキシ基である。
　ハロゲン原子としては、Ｆ原子、Ｃｌ原子、Ｂｒ原子、Ｉ原子が挙げられ、合成のしやすさ及び安定性の観点で、好ましくはＣｌ原子及びＢｒ原子であり、より好ましくはＣｌ原子である。 In the formula (B-1), at least one of R h1 to R h3 is selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. Represents a hydrolyzable group or a hydroxy group. The remaining R h1 to R h3 are each independently a hydrogen atom, a halogen atom, or a monovalent organic substituent (for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group). To express.
In formula (B-1), the hydrolyzable group bonded to the silicon atom is particularly preferably an alkoxy group or a halogen atom, and more preferably an alkoxy group.
The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms from the viewpoint of peelability. More preferably, it is an alkoxy group having 1 to 15 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, particularly preferably an alkoxy group having 1 to 3 carbon atoms, most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom include an F atom, a Cl atom, a Br atom, and an I atom. From the viewpoint of ease of synthesis and stability, a Cl atom and a Br atom are preferable, and a Cl atom is more preferable.
　加水分解性シリル基及びシラノール基の少なくとも１種を有する化合物は、上記式（Ｂ－１）で表される基を１つ以上有する化合物であることが好ましく、２つ以上有する化合物も使用することができる。 The compound having at least one of a hydrolyzable silyl group and a silanol group is preferably a compound having one or more groups represented by the above formula (B-1), and a compound having two or more is also used. Can do.
　加水分解性基は１個のケイ素原子に１～４個の範囲で結合することができ、式（Ｂ－１）中における加水分解性基の総個数は２又は３の範囲であることが好ましい。特に３つの加水分解性基がケイ素原子に結合していることが好ましい。加水分解性基がケイ素原子に２個以上結合するときは、それらは互いに同一であっても、異なっていてもよい。
　好ましいアルコキシ基として、具体的には、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、ｔｅｒｔ－ブトキシ基、フェノキシ基、ベンジルオキシ基などを挙げることができる。これらの各アルコキシ基を複数個組み合わせて用いてもよいし、異なるアルコキシ基を複数個組み合わせて用いてもよい。
　アルコキシ基の結合したアルコキシシリル基としては、例えば、トリメトキシシリル基、トリエトキシシリル基、トリイソプロポキシシリル基、トリフェノキシシリル基などのトリアルコキシシリル基；ジメトキシメチルシリル基、ジエトキシメチルシリル基などのジアルコキシモノアルキルシリル基；メトキシジメチルシリル基、エトキシジメチルシリル基などのモノアルコキシジアルキルシリル基を挙げることができる。 The hydrolyzable group can be bonded to one silicon atom in the range of 1 to 4, and the total number of hydrolyzable groups in the formula (B-1) is preferably in the range of 2 or 3. . In particular, it is preferable that three hydrolyzable groups are bonded to a silicon atom. When two or more hydrolyzable groups are bonded to a silicon atom, they may be the same as or different from each other.
Specific examples of preferred alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, phenoxy, and benzyloxy groups. A plurality of these alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.
Examples of the alkoxysilyl group to which the alkoxy group is bonded include, for example, a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group; a dimethoxymethylsilyl group, a diethoxymethylsilyl group And dialkoxymonoalkylsilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group.
　フッ素原子およびシリル基を有する化合物としては、具体的には、トリクロロ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－ヘプタデカフルオロデシル）シラン、トリメトキシ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－ヘプタデカフルオロデシル）シラン、メチルジクロロ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－ヘプタデカフルオロデシル）シラン、（３－ヘプタフルオロイソプロポキシ）プロピルトリクロロシラン、トリクロロ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－ｎ－オクチル）シラン、トリエトキシ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－ｎ－オクチル）シラン、トリメトキシ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－ｎ－オクチル）シラン、ジメチルクロロ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－ｎ－オクチル）シラン、メチルジクロロ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－ｎ－オクチル）シラン、オプツールＤＳＸ（ダイキン（株）製）、エフトップＤＢ２－ＥＯＳ（三菱マテリアル電子化成（株））が挙げられる。 Specific examples of the compound having a fluorine atom and a silyl group include trichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, Methyldichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, (3-heptafluoroisopropoxy) propyltrichlorosilane, trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, Triethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, dimethylchloro (1H, 1H, 2H, 2H -Tridecafluoro-n-octyl) silane, methyldichloro IH, IH, 2H, 2H-tridecafluoro -n- octyl) silane, manufactured OPTOOL DSX (Daikin Co.), EFTOP DB2-EOS (Mitsubishi Materials Electronic Chemicals Co.) and the like.
　フッ素原子を有する基および反応性不飽和二重結合を有する化合物としては、フッ素原子を有するラジカル重合性モノマーが挙げられ、以下の一般式（１）で表すことができる化合物が好ましい。
一般式（Ｉ）：Ｒｆ｛－Ｌ－Ｙ｝ｎ
（式中、Ｒｆは少なくとも炭素原子及びフッ素原子を含み、酸素原子及び水素原子のうちいずれかを含んでも良い、鎖状又は環状のｎ価の基を表し、ｎは２以上の整数を表す。Ｌは単結合又は二価の連結基を表す。Ｙは重合性基を表す。） Examples of the compound having a fluorine atom-containing group and a reactive unsaturated double bond include a radical polymerizable monomer having a fluorine atom, and a compound that can be represented by the following general formula (1) is preferable.
Formula (I): Rf {-LY} n
(In the formula, Rf represents a chain or cyclic n-valent group containing at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom, and n represents an integer of 2 or more. L represents a single bond or a divalent linking group, and Y represents a polymerizable group.)
　上記一般式（Ｉ）において、Ｙは重合性基であり、例えば、水酸基又は加水分解可能な基を有するシリル基（例えば、アルコキシシリル基、アシルオキシシリル基等）、反応性不飽和二重結合を有する基（（メタ）アクリロイル基、アリル基、ビニルオキシ基等）、開環重合反応性基（エポキシ基、オキセタニル基、オキサゾリル基等）、活性水素原子を有する基（たとえば水酸基、カルボキシル基、アミノ基、カルバモイル基、メルカプト基、β－ケトエステル基、ヒドロシリル基、シラノール基等）、酸無水物、求核剤によって置換され得る基（活性ハロゲン原子、スルホン酸エステル等）等が好ましい。
　より好ましくは、Ｙは、ラジカル重合性基を表し、反応性不飽和二重結合を有する基が更に好ましい。具体的には、Ｔは下記一般式（９）で表されるラジカル重合性官能基を表すことが好ましい。 In the above general formula (I), Y is a polymerizable group, for example, a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), a reactive unsaturated double bond. Groups having (meth) acryloyl groups, allyl groups, vinyloxy groups, etc., ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups) Carbamoyl group, mercapto group, β-ketoester group, hydrosilyl group, silanol group, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like are preferable.
More preferably, Y represents a radical polymerizable group, and more preferably a group having a reactive unsaturated double bond. Specifically, T preferably represents a radical polymerizable functional group represented by the following general formula (9).
Figure JPOXMLDOC01-appb-C000006
 （一般式（９）中、Ｒ901～Ｒ903は、それぞれ独立して、水素原子、アルキル基又はアリール基を表す。点線は、Ｌへ連結する基への結合を表す。）
Figure JPOXMLDOC01-appb-C000006
 (In general formula (9), R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group. The dotted line represents a bond to a group linked to L.)
　アルキル基の例は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。Ｒ901～Ｒ903はとしては、なかでも、水素原子またはメチル基が好ましい。
　Ｌは単結合又は二価の連結基を表す。二価の連結基としては、２価の脂肪族基、２価の芳香族基、－Ｏ－、－Ｓ－、－ＣＯ－、－Ｎ（Ｒ）－、及びこれらを２種以上組み合わせて得られる２価の連結基を表す。ただし、Ｒは水素原子又は炭素数１～５のアルキル基を表す。
Ｌがアルキレン基又はアリーレン基を有する場合、アルキレン基及びアリーレン基はハロゲン原子で置換されていることが好ましく、フッ素原子で置換されていることがより好ましい。
　Ｒｆは、少なくとも炭素原子及びフッ素原子を含み、酸素原子及び水素原子のうちいずれかを含んでも良い、鎖状又は環状のｎ価の基を表す。Ｒｆは、フッ素原子を有する繰り返し単位を有する線状または分岐状の高分子構造であってもよい。 Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples thereof include 2-methylhexyl group and cyclopentyl group. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
L represents a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group, a divalent aromatic group, —O—, —S—, —CO—, —N (R) —, and a combination of two or more thereof are obtained. Represents a divalent linking group. R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
When L has an alkylene group or an arylene group, the alkylene group and the arylene group are preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.
Rf 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.
　このようなフッ素原子を有するモノマーとしては、特開２０１１－４８３５８号公報の段落番号００１９～００３３に記載の化合物も好ましく使用でき、これらの内容は本願明細書に組み込まれる。 As such a monomer having a fluorine atom, the compounds described in paragraph numbers 0019 to 0033 of JP2011-48358A can also be preferably used, and the contents thereof are incorporated in the present specification.
　また、フッ素原子を有するラジカル重合性モノマーは、下記構造式（１）、（２）、（３）、（４）及び（５）で表される化合物から選択される少なくとも１種であることも好ましい。 The radically polymerizable monomer having a fluorine atom may be at least one selected from compounds represented by the following structural formulas (1), (2), (3), (4) and (5). preferable.
　ＣＨ2＝ＣＲ1ＣＯＯＲ2Ｒf　・・・構造式（１）
（構造式（１）中、Ｒ1は、水素原子、またはメチル基を表す。Ｒ2は、－ＣpＨ2p－、－Ｃ（ＣpＨ2p+1）Ｈ－、－ＣＨ2Ｃ（ＣpＨ2p+1）Ｈ－、または－ＣＨ2ＣＨ2Ｏ－を表す。Ｒfは、－ＣnＦ2n+1、－（ＣＦ2）nＨ、－ＣnＦ2n+1－ＣＦ3、－（ＣＦ2）pＯＣnＨ2nＣiＦ2i+1、－（ＣＦ2）pＯＣmＨ2mＣiＦ2iＨ、－Ｎ（ＣpＨ2p+1）ＣＯＣnＦ2n+1、または、－Ｎ（ＣpＨ2p+1）ＳＯ2ＣnＦ2n+1を表す。ただし、ｐは１～１０の整数、ｎは１～１６の整数、ｍは０～１０の整数、ｉは０～１６の整数をそれぞれ表す。） CH 2 = CR 1 COOR 2 R f ··· structural formula (1)
(In the structural formula (1), R 1 represents a hydrogen atom or a methyl group. R 2 represents —C p H 2p —, —C (C p H 2p + 1 ) H—, —CH 2 C ( C p H 2p + 1 ) H— or —CH 2 CH 2 O—, where R f is —C n F 2n + 1 , — (CF 2 ) n H, —C n F 2n + 1 —CF 3, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, or, -N (C p H 2p + 1) represents the SO 2 C n F 2n + 1 . Here, p is an integer of 1 ~ 10, n is an integer of 1 ~ 16, m is 0 to 10 integer I represents an integer of 0 to 16, respectively.)
　ＣＦ2＝ＣＦＯＲg・・・構造式（２）
（構造式（２）中、Ｒgは、炭素数１～２０のフルオロアルキル基を表す。） CF 2 = CFOR g. Structural formula (2)
(In the structural formula (2), R g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
　ＣＨ2＝ＣＨＲg・・・構造式（３）
（構造式（３）中、Ｒgは、炭素数１～２０のフルオロアルキル基を表す。） CH 2 = CHR g ... Structural formula (3)
(In the structural formula (3), R g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
　ＣＨ2＝ＣＲ3ＣＯＯＲ5ＲjＲ6ＯＣＯＣＲ4＝ＣＨ2・・・構造式（４）
（構造式（４）中、Ｒ3およびＲ4は、水素原子、またはメチル基を表す。Ｒ5およびＲ6は、－ＣqＨ2q－、－Ｃ（ＣqＨ2q+1）Ｈ－、－ＣＨ2Ｃ（ＣqＨ2q+1）Ｈ－または－ＣＨ2ＣＨ2Ｏ－、Ｒjは－ＣtＦ2tを表す。ｑは１～１０の整数であり、ｔは１～１６の整数である。） CH 2 = CR 3 COOR 5 R j R 6 OCOCR 4 = CH 2 ··· structural formula (4)
(In the structural formula (4), R 3 and R 4 represent a hydrogen atom or a methyl group. R 5 and R 6 represent —C q H 2q —, —C (C q H 2q + 1 ) H— , —CH 2 C (C q H 2q + 1 ) H— or —CH 2 CH 2 O—, R j represents —C t F 2t , q is an integer of 1 to 10, and t is 1 to 16 Is an integer.)
　ＣＨ2＝ＣＨＲ7ＣＯＯＣＨ2（ＣＨ2Ｒk）ＣＨＯＣＯＣＲ8＝ＣＨ2・・・構造式（５）
（構造式（５）中、Ｒ7およびＲ8は、水素原子、またはメチル基を表す。Ｒkは－ＣｙＦ2y+1である。ｙは１～１６の整数である。） CH 2 = CHR 7 COOCH 2 (CH 2 R k ) CHOCOCR 8 = CH 2. Structural formula (5)
(In the structural formula (5), R 7 and R 8 are, .R k representing a hydrogen atom or a methyl group, is .y is -CyF 2y + 1 is an integer of 1 to 16.)
　構造式（１）で表されるモノマーとしては、例えば、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＦ3ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＦ3（ＣＦ2）4ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、Ｃ7Ｆ15ＣＯＮ（Ｃ2Ｈ5）ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）7ＳＯ2Ｎ（ＣＨ2）ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＦ2（ＣＦ2）7ＳＯ2Ｎ（Ｃ3Ｈ7）ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｃ2Ｆ5ＳＯ2Ｎ（Ｃ3Ｈ7）ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、（ＣＦ3）2ＣＦ（ＣＦ2）6（ＣＨ2）3ＯＣＯＣＨ＝ＣＨ2、（ＣＦ3）2ＣＦ（ＣＦ2）10（ＣＨ2）3ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）4ＣＨ（ＣＨ3）ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3ＣＨ2ＯＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｃ2Ｆ5（ＣＨ2ＣＨ2Ｏ）2ＣＨ2ＯＣＯＣＨ＝ＣＨ2、（ＣＦ3）2ＣＦＯ（ＣＨ2）5ＯＣＯＣＨ＝ＣＨ2、ＣＦ3（ＣＦ2）4ＯＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、Ｃ2Ｆ5ＣＯＮ（Ｃ2Ｈ5）ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＦ3（ＣＦ2）2ＣＯＮ（ＣＨ3）ＣＨ（ＣＨ3）ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｈ（ＣＦ2）6Ｃ（Ｃ2Ｈ5）ＯＣＯＣ（ＣＨ3）＝ＣＨ2、Ｈ（ＣＦ2）8ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｈ（ＣＦ2）4ＣＨ2ＯＣＯＣＨ＝ＣＨ2、Ｈ（ＣＦ2）ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）7ＳＯ2Ｎ（ＣＨ3）ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）7ＳＯ2Ｎ（ＣＨ3）（ＣＨ2）10ＯＣＯＣＨ＝ＣＨ2、Ｃ2Ｆ5ＳＯ2Ｎ（Ｃ2Ｈ5）ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2、ＣＦ3（ＣＦ2）7ＳＯ2Ｎ（ＣＨ3）（ＣＨ2）4ＯＣＯＣＨ＝ＣＨ2、Ｃ2Ｆ5ＳＯ2Ｎ（Ｃ2Ｈ5）Ｃ（Ｃ2Ｈ5）ＨＣＨ2ＯＣＯＣＨ＝ＣＨ2、等が挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。 Examples of the monomer represented by the structural formula (1) include CF 3 (CF 2 ) 5 CH 2 CH 2 OCOCH═CH 2 , CF 3 CH 2 OCOCH═CH 2 , CF 3 (CF 2 ) 4 CH 2 CH 2 OCOC (CH 3) = CH 2, C 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 2) CH 2 CH 2 OCOCH═CH 2 , CF 2 (CF 2 ) 7 SO 2 N (C 3 H 7 ) CH 2 CH 2 OCOCH═CH 2 , C 2 F 5 SO 2 N (C 3 H 7 ) CH 2 CH 2 OCOC (CH 3) = CH 2, (CF 3) 2 CF (CF 2) 6 (CH 2) 3 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 10 (CH 2) 3 OCOC (CH 3) = CH 2, CF 3 (CF 2) 4 CH (CH 3) OCOC (CH 3) = CH 2, CF 3 CH 2 OCH 2 C 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH = CH 2, (CF 3) 2 CFO (CH 2) 5 OCOCH = CH 2, CF 3 (CF 2) 4 OCH 2 CH 2 OCOC (CH 3) = CH 2, C 2 F 5 CON (C 2 H 5) CH 2 OCOCH = CH 2, CF 3 (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, H (CF 2) 6 C (C 2 H 5) OCOC (CH 3) = CH 2, H (CF 2) 8 CH 2 OCOCH = CH 2, H (CF 2) 4 CH 2 OCOCH = CH 2 H (CF 2 ) CH 2 OCOC (CH 3 ) ═CH 2 , CF 3 (CF 2 ) 7 SO 2 N (CH 3 ) CH 2 CH 2 OCOC (CH 3 ) ═CH 2 , CF 3 (CF 2 ) 7 SO 2 N (CH 3) (CH 2) 10 OCOCH = CH 2, C 2 F 5 SO 2 N (C 2 H 5 CH 2 CH 2 OCOC (CH 3 ) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 4 OCOCH = CH 2, C 2 F 5 SO 2 N (C 2 H 5) C (C 2 H 5) HCH 2 OCOCH = CH 2, and the like. These may be used individually by 1 type and may use 2 or more types together.
　構造式（２）または（３）で表されるフルオロアルキル化オレフィンとしては、例えば、Ｃ3Ｆ7ＣＨ＝ＣＨ2、Ｃ4Ｆ9ＣＨ＝ＣＨ2、Ｃ10Ｆ21ＣＨ＝ＣＨ2、Ｃ3Ｆ7ＯＣＦ＝ＣＦ2、Ｃ7Ｆ15ＯＣＦ＝ＣＦ2、Ｃ8Ｆ17ＯＣＦ＝ＣＦ2、などが挙げられる。 Examples of the fluoroalkylated olefin represented by the structural formula (2) or (3) include C 3 F 7 CH═CH 2 , C 4 F 9 CH═CH 2 , C 10 F 21 CH═CH 2 , C 3 F 7 OCF = CF 2, C 7 F 15 OCF = CF 2, C 8 F 17 OCF = CF 2, and the like.
　構造式（４）または（５）で表されるモノマーとしては、例えば、ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）3ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）6ＣＨ2ＯＣＯＣＨ＝ＣＨ2、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ（ＣＨ2Ｃ8Ｆ17）ＯＣＯＣＨ＝ＣＨ2、などが挙げられる。 Examples of the monomer represented by the structural formula (4) or (5), for example, CH 2 = CHCOOCH 2 (CF 2) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 (CF 2) 6 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 CH (CH 2 C 8 F 17) OCOCH = CH 2, and the like.
　フッ素原子を有するラジカル重合性モノマーまたはオリゴマーとして、フッ素原子を有する繰り返し単位と、ラジカル重合性官能基を有する繰り返し単位とを有するオリゴマーも好ましく使用できる。
　フッ素原子を有する繰り返し単位としては、下記式（６）、（７）および（１０）で表される繰り返し単位の少なくとも１種から選択されることが好ましい。 As the 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).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（６）中、Ｒ1、Ｒ2、Ｒ3、およびＲ4は、それぞれ独立して水素原子、ハロゲン原子、水酸基、又は１価の有機基を表し、Ｒ1、Ｒ2、Ｒ3、及び、Ｒ4の内の少なくとも一つは、フッ素原子、又は、フッ素原子を有する１価の有機基である。
　式（７）中、Ｒ5、Ｒ6、Ｒ7は、それぞれ独立して水素原子、ハロゲン原子、水酸基、又は１価の有機基を表し、Ｙ1は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｒｆは、フッ素原子、又は、フッ素原子を有する１価の有機基を表す。
　式（１０）中、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12、Ｒ13は、それぞれ独立して水素原子、ハロゲン原子、水酸基、又は１価の有機基を表し、Ｙ2およびＹ3は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｒｆは、フッ素原子を有する２価の有機基を表す。 In formula (6), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, and R 1 , R 2 , R 3 , At least one of R 4 is a fluorine atom or a monovalent organic group having a fluorine atom.
In formula (7), R 5 , R 6 and R 7 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and Y 1 represents a single bond 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. Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.
In the formula (10), R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, Y 2 and Y 3 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. . Rf represents a divalent organic group having a fluorine atom.
　式（６）及び式（７）中のフッ素原子を有する１価の有機基としては、特に限定はないが、炭素数１～３０の含フッ素アルキル基が好ましく、炭素数１～２０がより好ましく、炭素数１～１５の含フッ素アルキル基が特に好ましい。この含フッ素アルキル基は、直鎖（例えば－ＣＦ2ＣＦ3、－ＣＨ2（ＣＦ2）4Ｈ、－ＣＨ2（ＣＦ2）8ＣＦ3、－ＣＨ2ＣＨ2（ＣＦ2）4Ｈ等）であっても、分岐構造（例えば－ＣＨ（ＣＦ3）2、－ＣＨ2ＣＦ（ＣＦ3）2、－ＣＨ（ＣＨ3）ＣＦ2ＣＦ3、－ＣＨ（ＣＨ3）（ＣＦ2）5ＣＦ2Ｈ等）を有していてもよく、また脂環式構造（好ましくは５員環又は６員環、例えばペルフルオロシクロへキシル基、ペルフルオロシクロペンチル基又はこれらで置換されたアルキル基等）を有していてもよく、エーテル結合（例えば、－ＣＨ2ＯＣＨ2ＣＦ2ＣＦ3、－ＣＨ2ＣＨ2ＯＣＨ2Ｃ4Ｆ8Ｈ、－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2Ｃ8Ｆ17、－ＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2Ｈ等）を有していてもよい。また、ペルフルオロアルキル基であってもよい。 The monovalent organic group having a fluorine atom in formula (6) and formula (7) is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. A fluorine-containing alkyl group having 1 to 15 carbon atoms is particularly preferred. This fluorine-containing alkyl group is a straight chain (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc. ) Even in branched structures (for example, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like, and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these). An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , — CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
　式（１０）中のフッ素原子を有する２価の有機基としては、特に限定はないが、炭素数１～３０の含フッ素アルキレン基が好ましく、炭素数１～２０がより好ましく、炭素数１～１５の含フッ素アルキレン基が特に好ましい。この含フッ素アルキレン基は、直鎖（例えば－ＣＦ2ＣＦ2－、－ＣＨ2（ＣＦ2）4－、－ＣＨ2（ＣＦ2）8ＣＦ2－、－ＣＨ2ＣＨ2（ＣＦ2）4－等）であっても、分岐構造（例えば－ＣＨ（ＣＦ3）ＣＦ2－、－ＣＨ2ＣＦ（ＣＦ3）ＣＦ2－、－ＣＨ（ＣＨ3）ＣＦ2ＣＦ2－、－ＣＨ（ＣＨ3）（ＣＦ2）5ＣＦ2－等）を有していてもよく、また脂環式構造（好ましくは５員環又は６員環、例えばペルフルオロシクロへキシル基、ペルフルオロシクロペンチル基又はこれらで置換されたアルキル基等）を有する連結基でもよく、エーテル結合（例えば－ＣＨ2ＯＣＨ2ＣＦ2ＣＦ2－、－ＣＨ2ＣＨ2ＯＣＨ2Ｃ4Ｆ8－、－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2Ｃ8Ｆ16－、－ＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2－、－ＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2－、ポリパーフルオロアルキレンエーテル鎖等）を有していてもよい。また、ペルフルオロアルキレン基であってもよい。 The divalent organic group having a fluorine atom in the formula (10) is not particularly limited, but is preferably a fluorine-containing alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Fifteen fluorine-containing alkylene groups are particularly preferred. This fluorine-containing alkylene group is a straight chain (for example, —CF 2 CF 2 —, —CH 2 (CF 2 ) 4 —, —CH 2 (CF 2 ) 8 CF 2 —, —CH 2 CH 2 (CF 2 ) 4 -, Etc.), branched structures (eg, —CH (CF 3 ) CF 2 —, —CH 2 CF (CF 3 ) CF 2 —, —CH (CH 3 ) CF 2 CF 2 —, —CH (CH 3 ) (CF 2 ) 5 CF 2- and the like) and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl, perfluorocyclopentyl, or substituted therewith A linking group having an alkyl group, etc.) or an ether bond (for example, —CH 2 OCH 2 CF 2 CF 2 —, —CH 2 CH 2 OCH 2 C 4 F 8 —, —CH 2 CH 2 OCH 2 CH 2 C 8 F 16 —, —CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 —, —C H 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 —, polyperfluoroalkylene ether chain, etc.). Further, it may be a perfluoroalkylene group.
　式（６）、（７）、（１０）中の１価の有機基は、３～１０価の非金属原子から構成される有機基であることが好ましく、例えば、１から６０個までの炭素原子、０個から１０個までの窒素原子、０個から５０個までの酸素原子、１個から１００個までの水素原子、及び０個から２０個までの硫黄原子から選ばれる少なくとも１種以上の元素から構成される有機基が挙げられる。
　より具体的な例としては、下記の構造が単独又は複数組み合わさって構成される有機基を挙げることができる。
　１価の有機基は、更に置換基を有してもよく、導入可能な置換基としては、例えば、ハロゲン原子、ヒドロキシ基、カルボキシ基、スルホナト基、ニトロ基、シアノ基、アミド基、アミノ基、アルキル基、アルケニル基、アルキニル基、アリール基、置換オキシ基、置換スルホニル基、置換カルボニル基、置換スルフィニル基、スルホ基、ホスホノ基、ホスホナト基、シリル基、複素環基、等が挙げられる。また有機基は、エーテル結合、エステル結合、ウレイド結合を含んでいてもよい。 The monovalent organic group in the formulas (6), (7), and (10) is preferably an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms. At least one or more selected from atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms Examples include organic groups composed of elements.
More specific examples include organic groups composed of the following structures singly or in combination.
The monovalent organic group may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group. , Alkyl group, alkenyl group, alkynyl group, aryl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonato group, silyl group, heterocyclic group, and the like. The organic group may contain an ether bond, an ester bond, or a ureido bond.
　１価の有機基は、アルキル基、アルケニル基、アルキニル基、アリール基が好ましい。アルキル基は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アルケニル基、炭素数２～２０のアルケニル基であることが好ましく、例えば、ビニル基、アリル基、プレニル基、ゲラニル基、オレイル基等が挙げられる。アルキニル基は、炭素数３～１０のアルキニル基であることが好ましく、エチニル基、プロパルギル基、トリメチルシリルエチニル基等が挙げられる。アリール基は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。更に、ヘテロ環基は、炭素数２～１０のヘテロ環基であることが好ましく、フラニル基、チオフェニル基、ピリジニル基などが挙げられる。 The monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-ethylhexyl group, A methylhexyl group, a cyclopentyl group, etc. are mentioned. An alkenyl group and an alkenyl group having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group. The alkynyl group is preferably an alkynyl group having 3 to 10 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethylsilylethynyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Furthermore, the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.
　式（６）中のＲ1、Ｒ2、Ｒ3、およびＲ4、式（７）中、Ｒ5、Ｒ6、Ｒ7、式（１０）中、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12、Ｒ13はで表される１価の有機基としては、アルキル基又はアリール基が好ましくい。
　アルキル基の例は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。Ｒ901～Ｒ903はとしては、なかでも、水素原子またはメチル基が好ましい。 R 1 , R 2 , R 3 and R 4 in formula (6), R 5 , R 6 , R 7 in formula ( 7 ), R 8 , R 9 , R 10 , R in formula (10) As the monovalent organic group represented by 11 , R 12 and R 13 , an alkyl group or an aryl group is preferable.
Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples thereof include 2-methylhexyl group and cyclopentyl group. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
　式（７）中のＹ1および、式（１０）中のＹ2およびＹ3で表される－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基の具体例を以下に挙げる。なお、下記例において左側が主鎖に結合し、右側がＲｆに結合する。 -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group represented by Y 1 in formula (7) and Y 2 and Y 3 in formula (10) Specific examples of the divalent linking group selected from the group consisting of these and combinations thereof are given below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to Rf.
Ｌ１：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ２：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ３：－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ５：－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ６：－ＣＯ－ＮＨ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ７：－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ８：－２価の芳香族基－Ｏ－ＣＯ－
Ｌ９：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１０：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１１：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１２：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１３：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１５：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１６：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１７：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１８：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１９：－２価の芳香族基－２価の脂肪族基
Ｌ２０：－２価の芳香族基－２価の脂肪族基－Ｏ－２価の脂肪族基－
Ｌ２１：－２価の芳香族基－２価の脂肪族基－Ｏ－２価の脂肪族基－Ｏ－
Ｌ２２：－ＣＯ－Ｏ－２価の脂肪族基－
Ｌ２３：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ L1: -CO-NH-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
L2: —CO—NH-divalent aliphatic group —O—CO—
L3: —CO-2 valent aliphatic group —O—CO—
L4: —CO—O-2 valent aliphatic group —O—CO—
L5: -valent aliphatic group -O-CO-
L6: —CO—NH-divalent aromatic group —O—CO—
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 divalent aromatic group -O-CO-NH-2 divalent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
L19: -2-valent aromatic group -2-valent aliphatic group L20: -2-valent aromatic group -2-valent aliphatic group -O-2-valent aliphatic group-
L21: a bivalent aromatic group, a bivalent aliphatic group, an O-2 valent aliphatic group, and -O-
L22: -CO-O-2 valent aliphatic group-
L23: —CO—O-2 valent aliphatic group —O—
　ここで２価の脂肪族基とは、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基またはポリアルキレンオキシ基を意味する。なかでもアルキレン基、置換アルキレン基、アルケニレン基、および置換アルケニレン基が好ましく、アルキレン基および置換アルキレン基がさらに好ましい。
　２価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。２価の脂肪族基の炭素原子数は、１～２０であることが好ましく、１～１５であることがより好ましく、１～１２であることがさらに好ましく、１～１０であることがさらにまた好ましく、１～８であることがよりさらに好ましく、１～４であることが特に好ましい。
　２価の脂肪族基の置換基の例としては、ハロゲン原子（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、アリールアミノ基およびジアリールアミノ基等が挙げられる。 Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
　２価の芳香族基の例としては、フェニレン基、置換フェニレン基、ナフタレン基および置換ナフタレン基が挙げられ、フェニレン基が好ましい。２価の芳香族基の置換基の例としては、上記２価の脂肪族基の置換基の例に加えて、アルキル基が挙げられる。 Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
　フッ素原子を有する繰り返し単位の含有量は、フッ素原子を有するラジカル重合性オリゴマーの全繰り返し単位に対して、２モル％～９８モル％であることが好ましく、１０モル％～９０モル％であることがより好ましい。 The content of the repeating unit having a fluorine atom is preferably 2 mol% to 98 mol%, preferably 10 mol% to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. Is more preferable.
　ラジカル重合性官能基を有する繰り返し単位としては、下記式（８）で表される繰り返し単位が好ましい。 As the repeating unit having a radical polymerizable functional group, a repeating unit represented by the following formula (8) is preferable.
Figure JPOXMLDOC01-appb-C000008
 （一般式（８）において、Ｒ801～Ｒ803は、それぞれ独立して、水素原子、アルキル基、又はハロゲン原子を表す。Ｙ8は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｔはラジカル重合性官能基を有する構造を表す。）
Figure JPOXMLDOC01-appb-C000008
 (In the general formula (8), R 801 to R 803 each independently represents a hydrogen atom, an alkyl group, or a halogen atom. Y 8 represents a single bond, or —CO—, —O—, — NH— represents a divalent linking group selected from the group consisting of a divalent aliphatic group, a divalent aromatic group, and combinations thereof, and T represents a structure having a radical polymerizable functional group.
　Ｒ801～Ｒ803としてのアルキル基は、炭素数１～６のアルキル基であることが好ましい。
　Ｔは一般式（９）で表されるラジカル重合性官能基を表すことが好ましい。 The alkyl group as R 801 to R 803 is preferably an alkyl group having 1 to 6 carbon atoms.
T preferably represents a radical polymerizable functional group represented by the general formula (9).
Figure JPOXMLDOC01-appb-C000009
 （一般式（９）中、Ｒ901～Ｒ903は、それぞれ独立して、水素原子、アルキル基又はアリール基を表す。点線は、Ｙ8へ連結する基への結合を表す。）
Figure JPOXMLDOC01-appb-C000009
 (In the general formula (9), R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group. The dotted line represents a bond to a group linked to Y 8. )
　アルキル基の例は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。Ｒ901～Ｒ903はとしては、なかでも、水素原子またはメチル基が好ましい。
　Ｙ8は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。組み合わせからなるＹ8の具体例を以下に挙げる。なお、下記例において左側が主鎖に結合し、右側が式（９）に結合する。 Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples thereof include 2-methylhexyl group and cyclopentyl group. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
Y 8 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. To express. Specific examples of comprising the combination Y 8 below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the formula (9).
Ｌ１：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ２：－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ３：－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ５：－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ６：－ＣＯ－ＮＨ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ７：－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ８：－２価の芳香族基－Ｏ－ＣＯ－
Ｌ９：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１０：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１１：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１２：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１３：－ＣＯ－Ｏ－２価の脂肪族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１４：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１５：－ＣＯ－Ｏ－２価の芳香族基－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１６：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－２価の芳香族基－Ｏ－ＣＯ－
Ｌ１７：－ＣＯ－Ｏ－２価の芳香族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－
Ｌ１８：－ＣＯ－Ｏ－２価の脂肪族基－Ｏ－ＣＯ－ＮＨ－２価の脂肪族基－Ｏ－ＣＯ－ L1: -CO-NH-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
L2: —CO—NH-divalent aliphatic group —O—CO—
L3: —CO-2 valent aliphatic group —O—CO—
L4: —CO—O-2 valent aliphatic group —O—CO—
L5: -valent aliphatic group -O-CO-
L6: —CO—NH-divalent aromatic group —O—CO—
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 divalent aromatic group -O-CO-NH-2 divalent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
　ここで２価の脂肪族基とは、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基またはポリアルキレンオキシ基を意味する。なかでもアルキレン基、置換アルキレン基、アルケニレン基、および置換アルケニレン基が好ましく、アルキレン基および置換アルキレン基がさらに好ましい。
　２価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。２価の脂肪族基の炭素原子数は、１～２０であることが好ましく、１～１５であることがより好ましく、１～１２であることがさらに好ましく、１～１０であることがさらにまた好ましく、１～８であることがよりさらに好ましく、１～４であることが特に好ましい。
　２価の脂肪族基の置換基の例としては、ハロゲン原子（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、アリールアミノ基およびジアリールアミノ基等が挙げられる。 Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
　２価の芳香族基の例としては、フェニレン基、置換フェニレン基、ナフタレン基および置換ナフタレン基が挙げられ、フェニレン基が好ましい。２価の芳香族基の置換基の例としては、上記２価の脂肪族基の置換基の例に加えて、アルキル基が挙げられる。 Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
　ラジカル重合性官能基を有する繰り返し単位の含有量は、フッ素原子を有するラジカル重合性オリゴマーの全繰り返し単位に対して、２モル％～９８モル％であることが好ましく、１０モル％～９０モル％であることがより好ましい。 The content of the repeating unit having a radical polymerizable functional group is preferably 2 mol% to 98 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom, and is preferably 10 mol% to 90 mol%. It is more preferable that
　フッ素原子を有するラジカル重合性オリゴマーのゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によるポリスチレン換算の重量平均分子量は、２０００～２００００であることが好ましく、２０００～１５０００がより好ましく、２０００～１００００であることが最も好ましい。 The weight average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a fluorine atom as measured by gel permeation chromatography (GPC) is preferably 2000 to 20000, more preferably 2000 to 15000, and more preferably 2000 to 10,000. Most preferred.
　ケイ素原子を有するラジカル重合性モノマーまたはオリゴマーは、シリコーンモノマーまたはシリコーンオリゴマーであることが好ましく、例えば、ポリジメチルシロキサン結合の少なくとも片末端が（メタ）アクリロイル基およびスチリル基等のエチレン性不飽和基となっている化合物が挙げられ、（メタ）アクリロイル基を有する化合物が好ましい。 The radical polymerizable monomer or oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer. For example, at least one terminal of a polydimethylsiloxane bond is an ethylenically unsaturated group such as a (meth) acryloyl group and a styryl group. And a compound having a (meth) acryloyl group is preferable.
　ケイ素原子を有するラジカル重合性オリゴマーのゲルパーミエーションクロマトグラフィー法によるポリスチレン換算の数平均分子量は、１，０００～１０，０００であることが好ましい。 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.
　ケイ素原子を有するラジカル重合性モノマーとしては、一般式（１１）または（１２）で示される化合物が好ましい。 As the radical polymerizable monomer having a silicon atom, a compound represented by the general formula (11) or (12) is preferable.
Figure JPOXMLDOC01-appb-C000010
 （一般式（１１）及び（１２）中、Ｒ11～Ｒ19は、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、又はアリール基を表す。Ｚ11、Ｚ12、及びＺ13は、それぞれ独立に、ラジカル重合性基を表す。Ｌ11、Ｌ12、及び、Ｌ13はそれぞれ独立に、単結合又は二価の連結基を表す。ｎ及びｍは、それぞれ独立に０以上の整数を表す。）
Figure JPOXMLDOC01-appb-C000010
 (In the general formulas (11) and (12), R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group. Z 11 , Z 12 , and Z 13 each independently represents a radically polymerizable group, L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group, and n and m each independently represents 0 or more. Represents an integer.)
　一般式（１１）および（１２）中、Ｒ11～Ｒ19は、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、または、アリール基を表す。 In general formulas (11) and (12), R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group.
　アルキル基は、直鎖状であっても、分枝鎖状であっても良く、炭素数１～５のアルキル基であることが好ましく、具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等が挙げられる。アルコキシ基は、－ＯＲ20を意味するもので、Ｒ20はアルキル基（好ましくは炭素数１～５のアルキル基）を表し、具体的には、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等が挙げられる。アルコキシカルボニル基は、－Ｃ（＝Ｏ）Ｒ21を意味するもので、Ｒ21はアルコキシ基（好ましくは炭素数１～５のアルコキシ基）を表し、具体的には、メトキシカルボニル、エトキシカルボニル、プロポキシカルボニル等が挙げられる。アリール基は、フェニル基、トリル基、ナフチル基などが挙げられ、それらは置換基を有していても良く、フェニルメチル（ベンジル）基、フェニルエチル基、フェニルプロピル基、フェニルブチル基、ナフチルメチル基等が挙げられる。 The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, n-propyl group. Group, isopropyl group and the like. An alkoxy group means —OR 20 , wherein R 20 represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group And a butoxy group. An alkoxycarbonyl group means —C (═O) R 21 , where R 21 represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specifically includes methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group, which may have a substituent, such as phenylmethyl (benzyl) group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl. Groups and the like.
　Ｌ11、Ｌ12、および、Ｌ13はそれぞれ独立に、単結合または二価の連結基を表す。二価の連結基としては、－ＣＯ－、－Ｏ－、－ＮＨ－、二価の脂肪族基、二価の芳香族基およびそれらの組み合わせからなる群より選ばれる二価の連結基を表す。 L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group. The divalent linking group represents a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. .
　ｎおよびｍは、それぞれ独立に０以上の整数を表し、０～１００の整数が好ましく、０～５０の整数がより好ましい。 N and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, and more preferably an integer of 0 to 50.
　Ｚ11、Ｚ12、およびＺ13は、それぞれ独立に、ラジカル重合性基を表し、下記一般式（ｉ）～（ｉｉｉ）のいずれかで表される官能基が特に好ましい。 Z 11 , Z 12 , and Z 13 each independently represent a radical polymerizable group, and a functional group represented by any one of the following general formulas (i) to (iii) is particularly preferable.
Figure JPOXMLDOC01-appb-C000011
 （一般式（ｉ）中、Ｒ101～Ｒ103はそれぞれ独立に、水素原子又は１価の有機基を表す。Ｘ101は、酸素原子、硫黄原子、又は－Ｎ（Ｒ104）－を表し、Ｒ104は、水素原子又は１価の有機基を表す。）
Figure JPOXMLDOC01-appb-C000011
 (In the general formula (i), R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group. X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —, R 104 represents a hydrogen atom or a monovalent organic group.)
　一般式（ｉ）において、Ｒ101～Ｒ103はそれぞれ独立に、水素原子または１価の有機基を表す。Ｒ101は、好ましくは、水素原子または置換基を有してもよいアルキル基などが挙げられ、なかでも、水素原子およびメチル基は、ラジカル反応性が高いことから好ましい。また、Ｒ102およびＲ103は、それぞれ独立に、好ましくは、水素原子、ハロゲン原子、アミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、または、置換基を有してもよいアリールスルホニル基を表し、なかでも、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基がラジカル反応性が高いことから好ましい。 In the general formula (i), R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group. R 101 preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity. R 102 and R 103 are each independently preferably a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, or optionally substituted alkyl. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent Represents an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, among which a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.
　Ｘ101は、酸素原子、硫黄原子、または－Ｎ（Ｒ104）－を表し、Ｒ104は、水素原子または１価の有機基を表す。１価の有機基としては、置換基を有してもよいアルキル基などが挙げられる。Ｒ104が、水素原子、メチル基、エチル基、または、イソプロピル基であることが、ラジカル反応性が高いことから好ましい。 X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —, and R 104 represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group which may have a substituent. R 104 is preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.
　導入し得る置換基としては、アルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、ハロゲン原子、アミノ基、アルキルアミノ基、アリールアミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、アミド基、アルキルスルホニル基、アリールスルホニル基などが挙げられる。 Examples of substituents that can be introduced include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, A nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.
Figure JPOXMLDOC01-appb-C000012
 （一般式（ｉｉ）中、Ｒ201～Ｒ205は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｙ201は、酸素原子、硫黄原子、又は－Ｎ（Ｒ206）－を表す。Ｒ206は、水素原子又は１価の有機基を表す。）
Figure JPOXMLDOC01-appb-C000012
 (In general formula (ii), R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group. Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —. R 206 represents a hydrogen atom or a monovalent organic group.)
　一般式（ｉｉ）において、Ｒ201～Ｒ205は、それぞれ独立に、水素原子または１価の有機基を表す。Ｒ201～Ｒ205は、それぞれ独立に、水素原子、ハロゲン原子、アミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、または、置換基を有してもよいアリールスルホニル基であることが好ましく、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、または、置換基を有してもよいアリール基であることがより好ましい。 In the general formula (ii), R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group. R 201 to R 205 each independently represents a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent. An aryl group that may have, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent It is preferably a good arylamino group, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group, having a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent. It is more preferably an alkyl group which may be substituted or an aryl group which may have a substituent.
　導入し得る置換基としては、一般式（ｉ）で記載した置換基と同様のものが挙げられる。
　Ｙ201は、酸素原子、硫黄原子、または－Ｎ（Ｒ206）－を表す。Ｒ206は、一般式（ｉ）のＲ104と同義であり、好ましい例も同様である。 Examples of the substituent that can be introduced include the same substituents as those described in formula (i).
Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —. R 206 has the same meaning as R 104 in formula (i), and preferred examples thereof are also the same.
Figure JPOXMLDOC01-appb-C000013
 （一般式（ｉｉｉ）中、Ｒ301～Ｒ303は、それぞれ独立に水素原子又は１価の有機基を表す。Ｚ301は、酸素原子、硫黄原子、－Ｎ（Ｒ304）－又は置換基を有してもよいフェニレン基を表す。Ｒ304は、一般式（ｉ）のＲ104と同義である。）
Figure JPOXMLDOC01-appb-C000013
 (In the general formula (iii), R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group. Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or a substituent. Represents a phenylene group which may have R. R 304 has the same meaning as R 104 in formula (i).
　一般式（ｉｉｉ）において、Ｒ301～Ｒ303は、それぞれ独立に水素原子または１価の有機基を表す。Ｒ301は、水素原子、または、置換基を有してもよいアルキル基であることが好ましく、なかでも、水素原子、または、メチル基であることが、ラジカル反応性が高いことからより好ましい。Ｒ302、および、Ｒ303は、それぞれ独立に、水素原子、ハロゲン原子、アミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいアルキルスルホニル基、または、置換基を有してもよいアリールスルホニル基であることが好ましく、水素原子、カルボキシル基、アルコキシカルボニル基、置換基を有してもよいアルキル基、または、置換基を有してもよいアリール基であることが、ラジカル反応性が高いことからより好ましい。 In general formula (iii), R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group. R 301 is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group because of high radical reactivity. R 302 and R 303 are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent. An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent. An alkyl group that may have a substituent or an aryl group that may have a substituent is more preferable because of high radical reactivity.
　導入し得る置換基としては、一般式（ｉ）で記載した置換基と同様のものが挙げられる。Ｚ301は、酸素原子、硫黄原子、－Ｎ（Ｒ304）－または置換基を有してもよいフェニレン基を表す。Ｒ304は、一般式（ｉ）のＲ104と同義であり、１価の有機基としては、置換基を有してもよいアルキル基などが挙げられ、なかでも、メチル基、エチル基、および、イソプロピル基がラジカル反応性が高いことから好ましい。 Examples of the substituent that can be introduced include the same substituents as those described in formula (i). Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or an optionally substituted phenylene group. R 304 has the same meaning as R 104 in the general formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and An isopropyl group is preferable because of high radical reactivity.
　離型剤がケイ素原子を有するラジカル重合性モノマーまたはオリゴマーを有する場合、ケイ素原子を有するラジカル重合性モノマーまたはオリゴマーの含有量は、離型剤の全固形分に対して、０．０１～１５質量％が好ましい。０．０１質量％以上であれば、十分な剥離性が得られる。１５質量％以下であれば、十分な接着力が得られる。ケイ素原子を有するラジカル重合性モノマー又はオリゴマーは１種類のみでもよいし、２種類以上であってもよい。ケイ素原子を有するラジカル重合性モノマー又はオリゴマーが２種類以上の場合は、その合計が上記範囲であることが好ましい。 When the release agent has a radical polymerizable monomer or oligomer having a silicon atom, the content of the radical polymerizable monomer or oligomer having a silicon atom is 0.01 to 15 mass based on the total solid content of the release agent. % Is preferred. 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.
　フッ素原子又はシリコン原子を有するラジカル重合性モノマーとしては、例えば、ＤＩＣ株式会社製のＲＳ－７５、ＲＳ－７２－Ｋ、ＲＳ－７６－Ｅ、ＲＳ－７２－Ｋ、ダイキン工業株式会社製のオプツールＤＡＣ－ＨＰ（フッ素系シランカップリング剤）、信越化学工業株式会社製のＸ－２２－１６４、Ｘ－２２－１６４ＡＳ、Ｘ－２２－１６４Ａ、Ｘ－２２－１６４Ｂ、Ｘ－２２－１６４Ｃ、Ｘ－２２－１６４Ｅ、ダイセル・サイテック株式会社製のＥＢＥＣＲＹＬ３５０、ＥＢＥＣＲＹＬ１３６０、デグサ社製のＴＥＧＯＲａｄ２７００、ＵＶ－３５００Ｂ（ＢＹＫ社製）なども例示される。 Examples of the radical polymerizable monomer having a fluorine atom or a silicon atom 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), X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X, manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include -22-164E, EBECRYL350, EBECRYL1360 manufactured by Daicel-Cytec, TEGORad2700 manufactured by Degussa, and UV-3500B (manufactured by BYK).
　フッ素原子又はシリコン原子を有する材料としては、上述の他、ヘプタデカフルオロ－１，１，２－テトラヒドラデシル）トリクロロシラン、（フルオロ）アルキルホスナート、フッ化パリレン、シリコンアクリレートコポリマー、テトラフルオロエチレンおよび２，２－ビス－トリフルオロメチル－４，５－ジフルオロ－１，３－ジオキソールのコポリマー類、ペンダントペルフルオロアルコキシ基を持つポリマー、フッ化エチレン－プロピレンコポリマーなどが挙げられる。 In addition to the above-mentioned materials having fluorine atoms or silicon atoms, heptadecafluoro-1,1,2-tetrahydradecyl) trichlorosilane, (fluoro) alkyl phosphate, parylene fluoride, silicon acrylate copolymer, tetrafluoroethylene And copolymers of 2,2-bis-trifluoromethyl-4,5-difluoro-1,3-dioxole, polymers having pendant perfluoroalkoxy groups, fluorinated ethylene-propylene copolymers, and the like.
＜＜＜＜非熱硬化性の化合物＞＞＞＞
　非熱硬化性の化合物としては、非重合性のフッ素原子を有する高分子化合物が好ましい。非重合性のフッ素原子を有する高分子化合物としては、１種または２種以上の含フッ素単官能モノマーからなる重合体を好ましく使用できる。より具体的には、テトラフルオロエチレン、ヘキサフルオロプロペン、テトラフルオロエチレンオキシド、ヘキサフルオロプロペンオキシド、パーフルオロアルキルビニルエーテル、クロロトリフルオロエチレン、ビニリデンフルオライド、パーフルオロアルキル基含有（メタ）アクリル酸エステルから選ばれる１種又は２種以上の含フッ素単官能モノマーの単独重合体又はこれらモノマーの共重合体、含フッ素単官能モノマーの１種又は２種以上とエチレンとの共重合体、含フッ素単官能モノマーの１種又は２種以上とクロロトリフルオロエチレンとの共重合体から選ばれる少なくとも１種の含フッ素樹脂等を挙げることができる。 <<<<< Non-thermosetting Compound >>>>
As the non-thermosetting compound, a polymer compound having a non-polymerizable fluorine atom is preferable. As the polymer compound having a non-polymerizable fluorine atom, a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used. More specifically, it is selected from tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester. 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.
　非重合性のフッ素原子を有する高分子化合物としては、パーフルオロアルキル基含有（メタ）アクリル酸エステルから合成できるパーフルオロアルキル基含有の（メタ）アクリル樹脂であることが好ましい。 The polymer compound having a non-polymerizable fluorine atom is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic ester.
　パーフルオロアルキル基含有（メタ）アクリル酸エステルとしては、具体的には下記式（１０１）で表される化合物であることが好ましい。
　式（１０１）
Figure JPOXMLDOC01-appb-C000014
 Specifically, the perfluoroalkyl group-containing (meth) acrylic acid ester is preferably a compound represented by the following formula (101).
Formula (101)
Figure JPOXMLDOC01-appb-C000014
　一般式（１０１）中、Ｒ101、Ｒ102、Ｒ103はそれぞれ独立に、水素原子、アルキル基、又はハロゲン原子を表す。Ｙ101は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表す。Ｒｆはフッ素原子またはフッ素原子を少なくとも一つ有する一価の有機基である。 In General Formula (101), R 101 , R 102 , and R 103 each independently represent a hydrogen atom, an alkyl group, or a halogen atom. Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. To express. Rf is a fluorine atom or a monovalent organic group having at least one fluorine atom.
　一般式（１０１）中、Ｒ101、Ｒ102、Ｒ103で表されるアルキル基の例は、炭素数１～８のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、ｔｅｒｔ－ブチル基、イソペンチル基、２－エチルヘキシル基、２－メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数６～１２のアリール基であることが好ましく、フェニル基、１－ナフチル基、２－ナフチル基などが挙げられる。Ｒ101～Ｒ103はとしては、なかでも、水素原子またはメチル基が好ましい。 In the general formula (101), examples of the alkyl group represented by R 101 , R 102 , R 103 are preferably alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Examples include octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 101 to R 103 are preferably a hydrogen atom or a methyl group.
　Ｙ101は、単結合、または、－ＣＯ－、－Ｏ－、－ＮＨ－、２価の脂肪族基、２価の芳香族基およびそれらの組み合わせからなる群より選ばれる２価の連結基を表し、２価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。２価の脂肪族基の炭素原子数は、１～２０であることが好ましく、１～１５であることがより好ましく、１～１２であることがさらに好ましく、１～１０であることがさらにまた好ましく、１～８であることがよりさらに好ましく、１～４であることが特に好ましい。
　２価の芳香族基の例としては、フェニレン基、置換フェニレン基、ナフタレン基および置換ナフタレン基が挙げられ、フェニレン基が好ましい。
　Ｙ101としては、２価の直鎖状構造の脂肪族基であることが好ましい。 Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. The divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
Y 101 is preferably an aliphatic group having a divalent linear structure.
　Ｒｆで表される、フッ素原子を有する一価の有機基としては、特に限定はないが、炭素数１～３０の含フッ素アルキル基が好ましく、炭素数１～２０がより好ましく、炭素数１～１５の含フッ素アルキル基が特に好ましい。この含フッ素アルキル基は、直鎖｛例えば－ＣＦ2ＣＦ3、－ＣＨ2（ＣＦ2）4Ｈ、－ＣＨ2（ＣＦ2）8ＣＦ3、－ＣＨ2ＣＨ2（ＣＦ2）4Ｈ等｝であっても、分岐構造｛例えば－ＣＨ（ＣＦ3）2、－ＣＨ2ＣＦ（ＣＦ3）2、－ＣＨ（ＣＨ3）ＣＦ2ＣＦ3、－ＣＨ（ＣＨ3）（ＣＦ2）5ＣＦ2Ｈ等｝を有していてもよく、また脂環式構造（好ましくは５員環又は６員環、例えばペルフルオロシクロへキシル基、ペルフルオロシクロペンチル基又はこれらで置換されたアルキル基等）を有していてもよく、エーテル結合（例えば－ＣＨ2ＯＣＨ2ＣＦ2ＣＦ3、－ＣＨ2ＣＨ2ＯＣＨ2Ｃ4Ｆ8Ｈ、－ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2Ｃ8Ｆ17、－ＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2Ｈ等）を有していてもよい。また、ペルフルオロアルキル基であってもよい。 The monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to Fifteen fluorine-containing alkyl groups are particularly preferred. This fluorine-containing alkyl group is a straight chain {for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc. }, A branched structure {eg, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like} and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these). An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , —CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
　パーフルオロアルキル基含有（メタ）アクリル樹脂は、下記式（１０２）で表される繰り返し単位を有することが好ましい。
　式（１０２）
Figure JPOXMLDOC01-appb-C000015
 The perfluoroalkyl group-containing (meth) acrylic resin preferably has a repeating unit represented by the following formula (102).
Formula (102)
Figure JPOXMLDOC01-appb-C000015
　一般式（１０２）中、Ｒ101、Ｒ102、Ｒ103、Ｙ101、Ｒｆはそれぞれ、一般式（１０１）と同義であり、好ましい態様も同義である。 In General Formula (102), R 101 , R 102 , R 103 , Y 101 , and Rf are each synonymous with General Formula (101), and preferred embodiments are also synonymous.
　パーフルオロアルキル基含有（メタ）アクリル樹脂は、剥離性の観点から任意にパーフルオロアルキル基含有（メタ）アクリル酸エステルに加えて、共重合成分を選択することができる。共重合成分を形成し得るラジカル重合性化合物としては、例えば、アクリル酸エステル類、メタクリル酸エステル類、Ｎ，Ｎ－２置換アクリルアミド類、Ｎ，Ｎ－２置換メタクリルアミド類、スチレン類、アクリロニトリル類、メタクリロニトリル類などから選ばれるラジカル重合性化合物が挙げられる。 In the perfluoroalkyl group-containing (meth) acrylic resin, a copolymer component can be selected in addition to the perfluoroalkyl group-containing (meth) acrylic acid ester from the viewpoint of peelability. Examples of the radical polymerizable compound capable of forming a copolymer component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, and acrylonitriles. And radical polymerizable compounds selected from methacrylonitriles and the like.
　より具体的には、例えば、アルキルアクリレート（アルキル基の炭素原子数は１～２０のものが好ましい）等のアクリル酸エステル類、（例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸アミル、アクリル酸エチルヘキシル、アクリル酸オクチル、アクリル酸－ｔ－オクチル、クロルエチルアクリレート、２，２－ジメチルヒドロキシプロピルアクリレート、５－ヒドロキシペンチルアクリレート、トリメチロールプロパンモノアクリレート、ペンタエリヌリトールモノアクリレート、グリシジルアクリレート、ベンジルアクリレート、メトキシベンジルアクリレート、フルフリルアクリレート、テトラヒドロフルフリルアクリレートなど）、アリールアクリレート（例えば、フェニルアクリレートなど）、アルキルメタクリレート（アルキル基の炭素原子は１～２０のものが好ましい）等のメタクリル酸エステル類（例えば、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、アミルメタクリレート、ヘキシルメタクリレート、シクロヘキシルメタクリレート、ベンジルメタクリレート、クロルベンジルメタクリレート、オクチルメタクリレート、４－ヒドロキシブチルメタクゾレート、５－ヒドロキシペンチルメタクリレート、２，２－ジメチル－３－ヒドロキシプロピルメタクリレート、トリメチロールプロパンモノメタクリレート、ペンタエリスリトールモノメタクリレート、グリシジルメタクリレート、フルフリルメタクリレート、テトラヒドロフルフリルメタクリレートなど）、アリールメタクリレート（例えば、フェニルメタクリレート、クレジルメタクリレート、ナフチルメタクリレートなど）、スチレン、アルキルスチレン等のスチレン（例えば、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、イソプロピルスチレン、ブチルスチレン、ヘキシルスチレン、シクロヘキシルスチレン、デシルスチレン、ベンジルスチレン、クロルメチルスチレン、トリフルオルメチルスチレン、エトキシメチルスチレン、アセトキシメチルスチレンなど）、アルコキシスチレン（例えば、メトキシスチレン、４－メトキシ－３－メチルスチレン、ジメトキシスチレンなど）、ハロゲンスチレン（例えば、クロルスチレン、ジクロルスチレン、トリクロルスチレン、テトラクロルスチレン、ペンタクロルスチレン、プロムスチレン、ジブロムスチレン、ヨードスチレン、フルオルスチレン、トリフルオルスチレン、２－ブロム－４－トリフルオルメチルスチレン、４－フルオル－３－トリフルオルメチルスチレンなど）、アクリロニトリル、メタクリロニトリルアクリル酸、カルボン酸を含有するラジカル重合性化合物（アクリル酸、メタクリル酸、イタコン酸、クロトン酸、インクロトン酸、マレイン酸、ｐ－カルボキシルスチレン、及びこれらの酸基の金属塩、アンモニウム塩化合物等）が挙げられる。剥離性の観点から特に、炭素数１～２４の炭化水素基を有する（メタ）アクリル酸エステルが好ましく、例えば（メタ）アクリル酸のメチル、ブチル、２－エチルヘキシル、ラウリル、ステアリル、グリシジルエステル等が挙げられ、２－エチルヘキシル、ラウリル、ステアリル等の高級アルコールの（メタ）アクリレート、特にアクリレートが好ましい。 More specifically, for example, 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 methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate). , Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl Methacrylate, furfuryl methacrylate, tetrahydrofurfurylme Acrylate, etc.), aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), styrene such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl) Styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4-methoxy-3-methyl styrene, Dimethoxystyrene), halogen styrene (eg, chlorostyrene, dichlorostyrene, trichlorostyrene) , Tetrachlorostyrene, pentachlorostyrene, prom styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc. ), Radically polymerizable compounds containing acrylonitrile, methacrylonitrile acrylic acid, carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxylstyrene, and the acid groups thereof. Metal salts, ammonium salt compounds, etc.). From the viewpoint of releasability, (meth) acrylic acid esters having a hydrocarbon group having 1 to 24 carbon atoms are particularly preferred, such as methyl, butyl, 2-ethylhexyl, lauryl, stearyl, and glycidyl esters of (meth) acrylic acid. (Meth) acrylates of higher alcohols such as 2-ethylhexyl, lauryl and stearyl, particularly acrylates are preferred.
　非重合性のフッ素原子を有する高分子化合物として、市販されているものとしては、テフロン（登録商標）（デュポン社）、テフゼル（デュポン社）、フルオン（旭硝子社）、ヘイラー（ＳｏｌｖａｙＳｏｌｅｘｉｓ社）、ハイラー（ＳｏｌｖａｙＳｏｌｅｘｉｓ社）、ルミフロン（旭硝子社）、アフラス（旭硝子社）、セフラルソフト（セントラル硝子社）、セフラルコート（セントラル硝子社）、等のフッ素樹脂、ヴァイトン（デュポン社）、カルレッツ（デュポン社）、ＳＩＦＥＬ（信越化学工業社）等の商標名のフッ素ゴム、クライトックス（デュポン社）、フォンブリン（ダイトクテック社）、デムナム(ダイキン工業社)等のパーフルオロポリエーテルオイルをはじめとする各種のフッ素オイルや、ダイフリーＦＢ９６２等のダイフリーＦＢシリーズ（ダイキン工業社）、メガファックシリーズ（ＤＩＣ社）等の商標名のフッ素含有離型剤などが挙げられるが、これらに限定されるものではなく、非重合性のフッ素原子を有する高分子化合物であればいかなるものでも好適に使用できる。
　特に、ＤＩＣ社製メガファックシリーズのＦ－２５１、Ｆ－２８１、Ｆ－４７７、Ｆ－５５３、Ｆ－５５４、Ｆ－５５５、Ｆ－５５６、Ｆ－５５７、Ｆ－５５８、Ｆ－５５９、Ｆ－５６０、Ｆ－５６１、Ｆ－５６３、Ｆ－５６５、Ｆ－５６７、Ｆ－５６８、Ｆ－５７１、Ｒ－４０、Ｒ－４１、Ｒ－４３、Ｒ－９４や、ネオス社製フタージェントシリーズの７１０Ｆ、７１０ＦＭ、７１０ＦＳ、７３０ＦＬ、７３０ＬＭが好ましく使用できる。 Examples of commercially available polymer compounds having non-polymerizable fluorine atoms include Teflon (registered trademark) (DuPont), Tefzel (DuPont), Fullon (Asahi Glass Co.), Halar (Solvay Solexis), Heiler. (Solvay Solexis), Lumiflon (Asahi Glass Co., Ltd.), Afras (Asahi Glass Co., Ltd.), Cefral Soft (Central Glass Co., Ltd.), etc. Various fluoro oils such as perfluoropolyether oils such as fluoroelastomers with trade names such as Shin-Etsu Chemical Co., Ltd. Dies such as die-free FB962 Examples include fluorine-containing mold release agents such as Lee FB series (Daikin Industries Co., Ltd.) and Megafax series (DIC Co.), but are not limited to these. Any molecular compound can be suitably used.
Especially, F-251, F-281, F-477, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F -560, F-561, F-563, F-565, F-567, F-568, F-571, R-40, R-41, R-43, R-94 710F, 710FM, 710FS, 730FL, and 730LM can be preferably used.
　非重合性のフッ素原子を有する高分子化合物の重量平均分子量は、２０００～１０００００が好ましく、２０００～５００００がより好ましく、２０００～１００００が最も好ましい。 The weight average molecular weight of the polymer compound having a non-polymerizable fluorine atom is preferably 2000 to 100,000, more preferably 2000 to 50000, and most preferably 2000 to 10,000.
＜＜＜他の成分＞＞＞
　離型層は、離型剤に加えて、さらに本発明の効果を損なわない範囲において、目的に応じて種々の化合物を含むことができる。例えば、熱重合開始剤、増感色素、連鎖移動剤、酸化防止剤、界面活性剤を好ましく使用することができる。これらは、上述した接着フィルムで説明したものを用いることができる。 <<< other ingredients >>>
In addition to the release agent, the release layer can contain various compounds depending on the purpose within a range not impairing the effects of the present invention. For example, a thermal polymerization initiator, a sensitizing dye, a chain transfer agent, an antioxidant, and a surfactant can be preferably used. These can use what was demonstrated with the adhesive film mentioned above.
＜仮接着用積層体の製造方法＞
　次に、本発明の仮接着用積層体の製造方法について説明する。
　本発明の仮接着用積層体の製造方法は、上述した接着フィルムの表面に、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を形成する工程を含む。 <Method for producing temporary adhesive laminate>
Next, the manufacturing method of the laminated body for temporary adhesion of this invention is demonstrated.
The manufacturing method of the laminated body for temporary adhesion of this invention includes the process of forming the mold release layer containing the mold release agent containing at least 1 type chosen from a fluorine atom and a silicon atom on the surface of the adhesive film mentioned above.
＜＜接着フィルムの製造方法＞＞
　接着フィルムは、従来公知の方法により製造できる。例えば、溶融製膜法、溶液製膜法などにより製造できる。好ましくは溶融製膜法である。溶融製膜法であれば、平坦性を維持しながら厚膜化が可能である。更には、溶剤に溶解しにくいポリマー成分やその他添加剤を使用することもでき、材料選択の自由度が高い。特に、溶剤に溶解しにくい傾向がある、高耐熱性添加剤を用いることが可能であり、耐熱性に優れた接着フィルムが得られやすい。 << Method for producing adhesive film >>
The adhesive film can be produced by a conventionally known method. For example, it can be produced by a melt film forming method, a solution film forming method or the like. A melt film forming method is preferred. With the melt film forming method, it is possible to increase the thickness while maintaining flatness. Furthermore, polymer components and other additives that are difficult to dissolve in the solvent can be used, and the degree of freedom in material selection is high. In particular, it is possible to use a highly heat-resistant additive that tends to hardly dissolve in a solvent, and an adhesive film excellent in heat resistance can be easily obtained.
　溶融製膜法は、原料組成物を過熱して溶融することで流動性を実現し、この融液を押出成型装置や射出成型装置を使用してシート状にし、冷却することでフィルム（シート）を得る方法である。押出成型法では、平坦性のよい長尺フィルムを得ることができる。長尺フィルムの長さは、特に限定はないが、下限は、例えば５０００ｍｍ以上が好ましく、１０００ｍｍ以上がより好ましい。上限は、例えば５０００００ｍｍ以下が好ましく、２０００００ｍｍ以下がより好ましい。射出成型法では長尺フィルムを得ることは難しいが高い膜厚精度を得られる。他の添加剤も混合溶融撹拌することで添加することができる。フィルムの片面または両面に離型フィルムを貼合して、「離型フィルム付き接着フィルム」としても良い。 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. In the extrusion method, a long film with good flatness can be obtained. The length of the long film is not particularly limited, but the lower limit is preferably, for example, 5000 mm or more, and more preferably 1000 mm or more. For example, the upper limit is preferably 500000 mm or less, and more preferably 200000 mm or less. Although it is difficult to obtain a long film by the injection molding method, 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 or both sides of the film to form an “adhesive film with a release film”.
　溶液製膜法は、原料組成物を溶剤で溶解することで流動性を実現し、この溶液をフィルムやドラムやバンドなどの支持体に塗工してシート状にし、乾燥することでフィルム（シート）を得る方法である。
　溶剤としては、溶剤は、公知のものを制限なく使用でき、有機溶剤が好ましい。
　有機溶剤としては、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、オキシ酢酸アルキル（例：オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－オキシプロピオン酸アルキルエステル類（例：３－オキシプロピオン酸メチル、３－オキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－オキシプロピオン酸アルキルエステル類（例：２－オキシプロピオン酸メチル、２－オキシプロピオン酸エチル、２－オキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－オキシ－２－メチルプロピオン酸メチルおよび２－オキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル、１－メトキシ－２－プロピルアセテート等のエステル類；
　ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等のエーテル類；
メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン、γブチロラクトン等のケトン類；
トルエン、キシレン、アニソール、メシチレン等の芳香族炭化水素類；
リモネン、ｐ－メンタン等の炭化水素類などが好適に挙げられる。
　これらの溶剤は、塗布面状の改良などの観点から、２種以上を混合する形態も好ましい。この場合、特に好ましくは、メシチレン、ｐ－メンタン、γブチロラクトン、アニソール、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートから選択される２種以上で構成される混合溶液である。
　溶液の塗工方法としては、スリット状の開口から溶液を圧力で押し出して塗工する方法、グラビアやアロニクスローラーで溶液を転写して塗工する方法、スプレーやディスペンサーから溶液を吐出しながら走査して塗工する方法、溶液をタンクに溜めてその中にフィルムやドラムやバンドを通過させることでディップ塗工する方法、ワイヤバーで溶液を押流しながらかきとることで塗工する方法などが挙げられる。
　支持体に溶液を塗工した後に、乾燥して固体化したシートになった後、シートを支持体から機械的に引き剥がすことにより、単体のフィルム（シート）を得ることができる。引き剥がしやすいように、予め支持体上に剥離性を付与する処理として、離型層の塗布、浸漬処理、ガス処理、電磁波照射処理、プラズマ照射処理などを行っても良い。あるいは、フィルムを支持体から引き剥がさずにそのまま残して、フィルム支持体上にシートが接着した状態のまま、「離型フィルム付き接着フィルム」としても良い。これらの処理を連続的に行うことで、ロール状の長尺フィルムを得ることができる。また、接着フィルムの両面に、離形フィルムを貼合して、「両面離型フィルム付き接着フィルム」としても良い。 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) ).
As the solvent, known solvents can be used without limitation, and organic solvents are preferred.
Examples of organic solvents 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. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), 2-oxy Alkyl propionate Stealth (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate) Ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1-methoxy- Esters such as 2-propyl acetate
Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethers such as monoethyl ether acetate and propylene glycol monopropyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone;
Aromatic hydrocarbons such as toluene, xylene, anisole, mesitylene;
Preferred examples include hydrocarbons such as limonene and p-menthane.
These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface. In this case, particularly preferred are mesitylene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid. It is a mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
The solution coating method includes a method in which the solution is extruded by applying pressure from a slit-shaped opening, a method in which the solution is transferred by gravure or an aronics roller, and a scan is performed while discharging the solution from a spray or dispenser. Coating method, dip coating by storing the solution in a tank and letting it pass through a film, drum or band, and coating by swirling the solution with a wire bar It is done.
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. As a process for imparting peelability to the support in advance so as to be easily peeled off, a release layer coating, dipping process, gas process, electromagnetic wave irradiation process, plasma irradiation process, or the like may be performed. 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 | seat adhere | attached on the film support body. By performing these treatments continuously, a roll-like long film can be obtained. Alternatively, a release film may be bonded to both surfaces of the adhesive film to form an “adhesive film with a double-sided release film”.
＜＜離型層の形成方法＞＞ << Method for Forming Release Layer >>
　接着フィルムの表面に離型層を形成させる方法としては、ラミネート法、塗工法、共押出法が挙げられる。 Examples of a method for forming a release layer on the surface of the adhesive film include a laminating method, a coating method, and a co-extrusion method.
　ラミネート法は、離型フィルムに、上記離型剤を少なくとも含む組成物を塗工して、フィルム状の離型層（離型層フィルム）を形成し、接着フィルムの離型フィルムの無い面と、離型層フィルムの離型フィルムの無い面とを接触させて、ラミネートする方法である。
　ラミネートは、ローララミネート（加熱、加圧してもよい）、真空ラミネート（加熱してもよい）など、公知の装置を使用可能である。接着フィルムの両面に離型層フィルムをラミネートすることで、接着フィルムの両面に離型層を設けることができる。 In the laminating method, the release film is coated with a composition containing at least the release agent to form a film-like release layer (release layer film), and the surface of the adhesive film having no release film is used. In this method, the release layer film is laminated by bringing it into contact with the surface without the release film.
For the lamination, a known apparatus such as roller lamination (which may be heated or pressurized) or vacuum lamination (which may be heated) can be used. By laminating release layer films on both sides of the adhesive film, release layers can be provided on both sides of the adhesive film.
　塗工法は、接着フィルムの離型フィルムの無い面に、離型層形成用溶液を塗布後、乾燥して形成する方法である。離型層形成用組成物は、上述した離型剤と溶剤とを含む溶液を用いることが好ましい。溶剤としては、離型剤を溶解可能なものであれば、何れも好ましく用いることができる。例えば、フロリナートＦＣ４０（３Ｍ社製）などが挙げられる。
　接着フィルムを溶液製膜法で作成する場合は、インラインで、接着フィルム形成用溶液を塗布、乾燥後、巻き取らずに、離型層形成用溶液を塗布、乾燥しても良い。
　また、接着フィルム形成用溶液と、離型層形成用溶液とが相溶性がないように溶液の物性を設計した場合には、同時に塗布し、同時に乾燥しても良い。
　また、接着フィルム形成用溶液を塗布後、乾燥せずに、離型層形成用溶液を塗布し、両者を同時に乾燥しても良い。
　また、接着フィルム形成用溶液と離型層形成用溶液が一旦は相溶するが、乾燥して濃度が高くなると相分離するような物性に設計した場合には、混合溶液を塗布し、乾燥中に接着フィルムと離型層に分離するようにしても良い。
　また、接着フィルムの両面に離型層形成用溶液を塗工することで、接着フィルムの両面に離型層を設けることができる。 The coating method is a method in which a release layer forming solution is applied to the surface of the adhesive film without the release film and then dried. As the release layer forming composition, it is preferable to use a solution containing the release agent and the solvent described above. Any solvent can be preferably used as long as it can dissolve the release agent. For example, Fluorinert FC40 (manufactured by 3M Corporation) can be used.
When the adhesive film is prepared by a solution casting method, the release layer forming solution may be applied and dried in-line, after applying and drying the adhesive film forming solution, without winding.
In addition, when the physical properties of the solution are designed so that the adhesive film forming solution and the release layer forming solution are not compatible, they may be applied simultaneously and dried simultaneously.
Alternatively, after the adhesive film forming solution is applied, the release layer forming solution may be applied without drying, and both may be dried simultaneously.
Also, if the adhesive film forming solution and release layer forming solution are compatible with each other but are designed to have physical properties that cause phase separation when the concentration increases after drying, the mixed solution is applied and dried. Further, it may be separated into an adhesive film and a release layer.
Moreover, a release layer can be provided on both surfaces of an adhesive film by coating the release layer forming solution on both surfaces of the adhesive film.
　共押出法は、接着フィルム形成用の材料と、離型層形成用の材料をそれぞれ熱溶融し、同時に押出成型しながら一体化することによって、接着フィルムと離型層が一体になったシートを得る方法である。接着フィルム形成用の材料の両面に離型層形成用の材料を押出すことで、接着フィルムの両面に離型層を設けることができる。 In the coextrusion method, the material for forming the adhesive film and the material for forming the release layer are respectively melted by heat and integrated while extruding at the same time. How to get. A release layer can be provided on both sides of the adhesive film by extruding the release layer forming material on both sides of the adhesive film forming material.
　本発明の仮接着用積層体は、溶剤含有率が、１質量％以下が好ましく、０．１質量％以下がより好ましく、含有しないことが特に好ましい。 In the laminate for temporary bonding of the present invention, the solvent content is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably not contained.
　本発明の仮接着用積層体は、仮接着用積層体の片面または両面に、離型フィルムを貼合して「離型フィルム付き仮接着用積層体」としてもよい、この態様によれば、長尺状の仮接着用積層体をロール状に巻き取る際に、仮接着用積層体の表面に傷がついたり、保管中に貼りついたりするトラブルを防止することができる。
　離型フィルムは、使用する際に剥離除去することができる。例えば、両面に離型フィルムが貼合されている場合においては、片面の離型フィルムを剥がし、接着面をデバイスウエハや支持体などにラミネートした後で、残った離型フィルムを剥がすことで、シート面の清浄をできるだけ保つことができる。 According to this aspect, the temporary adhesive laminate of the present invention may be a temporary adhesive laminate with a release film by pasting a release film on one or both sides of the temporary adhesive laminate. When winding the long temporary laminate for temporary bonding into a roll, it is possible to prevent troubles that the surface of the temporary adhesive laminate is scratched or stuck during storage.
The release film can be peeled off when used. For example, in the case where a release film is bonded to both sides, by peeling off the release film on one side, laminating the adhesive surface on a device wafer or support, and then peeling off the remaining release film, The sheet surface can be kept as clean as possible.
＜接着性支持体＞
　次に、本発明の仮接着用積層体を用いた接着性支持体について説明する。
　接着性支持体は、支持体の表面に、上述した仮接着用積層体を有する。
　仮接着用積層体は、支持体上に、上述した本発明の仮接着用積層体をラミネートして形成することができる。例えば、仮接着用積層体を真空ラミネーターにセットし、本装置にて仮接着用積層体を支持体上に位置させ、真空下で、仮接着用積層体と支持体とを接触させ、ローラなどで圧着して仮接着用積層体を支持体に固定（積層）する方法などが挙げられる。また、支持体に固定された仮接着用積層体は、例えば円形状など、所望の形状にカットしてもよい。 <Adhesive support>
Next, an adhesive support using the temporary adhesive laminate of the present invention will be described.
An adhesive support body has the laminated body for temporary adhesion mentioned above on the surface of a support body.
The temporary bonding laminate can be formed by laminating the above-described temporary bonding laminate of the present invention on a support. For example, the temporary bonding laminate is set on a vacuum laminator, the temporary bonding laminate is positioned on the support with this apparatus, the temporary adhesion laminate and the support are brought into contact with each other under vacuum, a roller, etc. And a method of fixing (laminating) the temporary bonding laminate to the support by pressing. Moreover, you may cut the laminated body for temporary attachment fixed to the support body in desired shapes, such as circular shape, for example.
　接着性支持体において、仮接着用積層体は、接着フィルムの片面のみに離型層が形成されてなるものであってもよいし、両面に離型層が形成されてなるものであってもよい。また、片面のみに離型層が形成されている場合は、支持体側に離型層が配置されていてもよいし、支持体とは反対側の面に離型層が配置されていてもよい。 In the adhesive support, the temporary adhesive laminate may be one in which a release layer is formed only on one side of the adhesive film, or may be one in which a release layer is formed on both sides. Good. When the release layer is formed only on one side, the release layer may be disposed on the support side, or the release layer may be disposed on the surface opposite to the support side. .
　接着性支持体において、支持体（キャリア支持体ともいう）は特に限定されないが、例えば、シリコン基板、ガラス基板、金属基板、化合物半導体基板などが挙げられる。なかでも、半導体装置の基板として代表的に用いられるシリコン基板を汚染しにくい点や、半導体装置の製造工程において汎用されている静電チャックを使用できる点などを鑑みると、シリコン基板であることが好ましい。
　支持体の厚みは、特に限定されるものではないが、例えば、３００μｍ～１００ｍｍが好ましく、３００μｍ～１０ｍｍがより好ましい。
　支持体の表面には、離型層が設けられていてもよい。すなわち、支持体は、離型層付き支持体であってもよい。
　離型層としては、フッ素原子および／またはケイ素原子を含む低表面エネルギー層が好ましく、フッ素原子および／またはケイ素原子を含む材料を有することが好ましい。離型層のフッ素含有率は、３０～８０質量％が好ましく、４０～７６質量％がより好ましく、６０～７５質量％が特に好ましい。
　離型層の材料としては、上述した仮接着用積層体の離型層で説明したものと同様のものを用いることができる。 In the adhesive support, the support (also referred to as carrier support) is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. In particular, 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. preferable.
The thickness of the support is not particularly limited, but is preferably 300 μm to 100 mm, and more preferably 300 μm to 10 mm.
A release layer may be provided on the surface of the support. That is, the support may be a support with a release layer.
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.
As the material for the release layer, the same materials as those described for the release layer of the temporary bonding laminate described above can be used.
＜デバイスウエハ付き積層体＞
　次に、本発明のデバイスウエハ付き積層体について説明する。
　本発明のデバイスウエハ付き積層体は、デバイスウエハと支持体との間に、上述した本発明の仮接着用積層体を有し、仮接着用積層体がデバイスウエハおよび支持体に接してなるものである。すなわち、仮接着用積層体の一方の表面がデバイスウエハのデバイス面に接し、他方の表面が支持体の表面に接している。
　なお、仮接着用積層体が、接着フィルムの両面に離型層を有する場合は、一方の面の離型層は、デバイスウエハと接しており、他方の面の離型層は、支持体と接している。また、仮接着用積層体が、接着フィルムの片面のみに離型層を有する場合は、離型層は、デバイスウエハまたは支持体のいずれか一方のみと接している。 <Laminated body with device wafer>
Next, the laminated body with a device wafer of this invention is demonstrated.
The laminate with a device wafer of the present invention has the above-mentioned temporary adhesion laminate of the present invention between the device wafer and the support, and the temporary adhesion laminate is in contact with the device wafer and the support. It is. That is, one surface of the temporary bonding laminate is in contact with the device surface of the device wafer, and the other surface is in contact with the surface of the support.
In addition, when the laminated body for temporary adhesion has a release layer on both surfaces of the adhesive film, the release layer on one surface is in contact with the device wafer, and the release layer on the other surface is the support and It touches. Moreover, when the laminated body for temporary adhesion has a release layer only on the single side | surface of an adhesive film, the release layer is in contact with either one of a device wafer or a support body.
　デバイスウエハは、公知のものを制限なく使用することができ、例えば、シリコン基板、化合物半導体基板などが挙げられる。化合物半導体基板の具体例としては、ＳｉＣ基板、ＳｉＧｅ基板、ＺｎＳ基板、ＺｎＳｅ基板、ＧａＡｓ基板、ＩｎＰ基板、ＧａＮ基板などが挙げられる。
　デバイスウエハの表面には、機械構造や回路が形成されていてもよい。機械構造や回路が形成されたデバイスウエハとしては、例えば、ＭＥＭＳ（Ｍｉｃｒｏ　Ｅｌｅｃｔｒｏ　Ｍｅｃｈａｎｉｃａｌ　Ｓｙｓｔｅｍｓ）、パワーデバイス、イメージセンサー、マイクロセンサー、ＬＥＤ、光学デバイス、インターポーザー、埋め込み型デバイス、マイクロデバイスなどが挙げられる。
　デバイスウエハは、金属バンク等の構造を有していることが好ましい。本発明によれば、表面に構造を有しているデバイスウエハに対しても、安定して仮接着できるとともに、デバイスウエハに対する仮接着を容易に解除できる。構造の高さは、特に限定はないが、例えば、１～１５０μｍが好ましく、５～１００μｍがより好ましい。
　機械的または化学的な処理を施す前のデバイスウエハの膜厚は、５００μｍ以上が好ましく、６００μｍ以上がより好ましく、７００μｍ以上が更に好ましい。上限は、例えば、２０００μｍ以下が好ましく、１５００μｍ以下がより好ましい。
　機械的または化学的な処理を施して薄膜化した後のデバイスウエハの膜厚は、例えば、５００μｍ未満が好ましく、４００μｍ以下がより好ましく、３００μｍ以下が更に好ましい。下限は、例えば、１μｍ以上が好ましく、５μｍ以上がより好ましい。 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, LEDs, optical devices, interposers, embedded devices, and micro devices. .
The device wafer preferably has a structure such as a metal bank. According to the present invention, it is possible to stably temporarily bond a device wafer having a structure on the surface, and to easily release the temporary adhesion to the device wafer. The height of the structure is not particularly limited, but is preferably 1 to 150 μm, for example, and more preferably 5 to 100 μm.
The film thickness of the device wafer before the mechanical or chemical treatment is preferably 500 μm or more, more preferably 600 μm or more, and still more preferably 700 μm or more. For example, the upper limit is preferably 2000 μm or less, and more preferably 1500 μm or less.
For example, the film thickness of the device wafer after thinning by mechanical or chemical treatment is preferably less than 500 μm, more preferably 400 μm or less, and even more preferably 300 μm or less. For example, the lower limit is preferably 1 μm or more, and more preferably 5 μm or more.
　本発明のデバイスウエハ付き積層体において、支持体（キャリア支持体）としては、上述した接着性支持体で説明した支持体と同義であり、好ましい範囲も同様である。 In the laminate with a device wafer of the present invention, the support (carrier support) has the same meaning as the support described in the adhesive support described above, and the preferred range is also the same.
　本発明のデバイスウエハ付き積層体は、上述した接着性支持体の、仮接着用積層体が形成された側の面と、デバイスウエハとを加熱圧着することにより製造できる。加圧接着条件は、例えば、温度１００～２００℃、圧力０．０１～１ＭＰａ、時間１～１５分が好ましい。
　また、支持体とデバイスウエハとの間に、上述した本発明の仮接着用積層体を配置し、加熱圧着して製造することもできる。 The laminated body with a device wafer of the present invention can be produced by thermocompression bonding the surface of the adhesive support described above on which the temporary bonding laminated body is formed and the device wafer. 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.
Moreover, it can also be manufactured by disposing the above-mentioned temporary bonding laminate of the present invention between a support and a device wafer and thermocompression bonding.
＜半導体装置の製造方法＞
　以下、デバイスウエハ付き積層体を製造する工程を経た半導体装置の製造方法の一実施形態について、図１を合わせて参照しながら説明する。なお、本発明は、以下の実施形態に限定されるものではない。
　図１（Ａ）～（Ｅ）は、それぞれ、支持体とデバイスウエハとの仮接着を説明する概略断面図（図１（Ａ）、（Ｂ））、支持体に仮接着されたデバイスウエハが薄型化された状態（図１（Ｃ））、支持体とデバイスウエハを剥離した状態（図１（Ｄ））、デバイスウエハから接着層を除去後の状態（図１（Ｅ））を示す概略断面図である。 <Method for Manufacturing Semiconductor Device>
Hereinafter, an embodiment of a method of manufacturing a semiconductor device that has undergone a process of manufacturing a laminated body with a device wafer will be described with reference to FIG. In addition, this invention is not limited to the following embodiment.
1A to 1E are schematic cross-sectional views (FIGS. 1A and 1B) illustrating temporary bonding between a support and a device wafer, respectively, and a device wafer temporarily bonded to the support. Schematic showing a thinned state (FIG. 1C), a state where the support and the device wafer are peeled off (FIG. 1D), and a state after removing the adhesive layer from the device wafer (FIG. 1E). It is sectional drawing.
　この実施形態では、図１（Ａ）に示すように、先ず、支持体１２に仮接着用積層体１１が設けられてなる接着性支持体１００が準備される。接着性支持体１００は、上述した方法で製造できる。接着性支持体１００は、実質的に溶剤を含まない態様であることが好ましい。
　デバイスウエハ６０は、シリコン基板６１の表面６１ａに複数のデバイスチップ６２が設けられてなる。
　シリコン基板６１の厚さは、例えば、２００～１２００μｍが好ましい。デバイスチップ６２は例えば金属構造体であることが好ましく、高さは１０～１００μｍが好ましい。 In this embodiment, as shown in FIG. 1 (A), first, an adhesive support 100 is prepared in which a temporary adhesive laminate 11 is provided on a support 12. The adhesive support 100 can be manufactured by the method described above. The adhesive support 100 is preferably in an embodiment that does not substantially contain a solvent.
The device wafer 60 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 μm, for example. The device chip 62 is preferably a metal structure, for example, and the height is preferably 10 to 100 μm.
　次いで、図１（Ｂ）に示す通り、接着性支持体１００とデバイスウエハ６０とを圧着させ、支持体１２とデバイスウエハ６０とを仮接着させる。
　仮接着用積層体１１は、デバイスチップ６２を完全に覆っていることが好ましく、デバイスチップの高さがＸμｍ、仮接着用積層体の厚みをＹμｍの場合、「Ｘ＋１００≧Ｙ＞Ｘ」の関係を満たすことが好ましい。
　仮接着用積層体１１がデバイスチップ６２を完全に被覆していることは、薄型デバイスウエハのＴＴＶ（Ｔｏｔａｌ　Ｔｈｉｃｋｎｅｓｓ　Ｖａｒｉａｔｉｏｎ）をより低下したい場合（すなわち、薄型デバイスウエハの平坦性をより向上させたい場合）に有効である。
　すなわち、デバイスウエハを薄型化する際において、複数のデバイスチップ６２を仮接着用積層体１１によって保護することにより、支持体１２との接触面において、凹凸形状をほとんど無くすことが可能である。よって、このようなに支持した状態で薄型化しても、複数のデバイスチップ６２に由来する形状が、薄型デバイスウエハの裏面６１ｂ１に転写されるおそれは低減され、その結果、最終的に得られる薄型デバイスウエハのＴＴＶをより低下することができる。 Next, as shown in FIG. 1B, the adhesive support 100 and the device wafer 60 are pressure-bonded, and the support 12 and the device wafer 60 are temporarily bonded.
The temporary bonding laminate 11 preferably completely covers the device chip 62. When the height of the device chip is X μm and the thickness of the temporary bonding laminate is Y μm, the relationship of “X + 100 ≧ Y> X” is satisfied. It is preferable to satisfy.
The case where the laminated body 11 for temporary adhesion completely covers the device chip 62 is intended to further reduce the TTV (Total Thickness Variation) of the thin device wafer (that is, to improve the flatness of the thin device wafer). ) Is effective.
That is, when the device wafer is thinned, the plurality of device chips 62 are protected by the temporary bonding laminate 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.
　次いで、図１（Ｃ）に示すように、シリコン基板６１の裏面６１ｂに対して、機械的または化学的な処理（特に限定されないが、例えば、グライディングや化学機械研磨（ＣＭＰ）等の薄膜化処理、化学気相成長（ＣＶＤ）や物理気相成長（ＰＶＤ）などの高温・真空下での処理、有機溶剤、酸性処理液や塩基性処理液などの薬品を用いた処理、めっき処理、活性光線の照射、加熱・冷却処理など）を施して、図１（Ｃ）に示すように、シリコン基板６１の厚さを薄くし（例えば、平均厚さ５００μｍ未満であることが好ましく、１～２００μｍであることがより好ましい）、薄型デバイスウエハ６０ａを得る。
　また、機械的または化学的な処理として、薄膜化処理の後に、薄型デバイスウエハ６０ａの裏面６１ｂ１からシリコン基板を貫通する貫通孔（図示せず）を形成し、この貫通孔内にシリコン貫通電極（図示せず）を形成する処理を行ってもよい。具体的には、加熱処理における最高到達温度は１３０℃～４００℃が好ましく、１８０℃～３５０℃がより好ましい。加熱処理における最高到達温度は、接着フィルムの軟化点よりも低い温度とすることが好ましい。加熱処理は、最高到達温度での３０秒～３０分の加熱であることが好ましく、最高到達温度での１分～１０分の加熱であることがより好ましい。 Next, as shown in FIG. 1C, 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 1) to reduce the thickness of the silicon substrate 61 (for example, the average thickness is preferably less than 500 μm, preferably 1 to 200 μm). More preferably, a thin device wafer 60a is obtained.
Further, as a mechanical or chemical treatment, 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. Specifically, the highest temperature achieved in the heat treatment is preferably 130 ° C. to 400 ° C., more preferably 180 ° C. to 350 ° C. The highest temperature achieved in the heat treatment is preferably a temperature lower than the softening point of the adhesive film. 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.
　次いで、図１（Ｄ）に示すように、支持体１２を、薄型デバイスウエハ６０ａから脱離させる。脱離の方法は特に限定されるものではないが、何ら処理することなく薄型デバイスウエハ６０ａの端部から薄型デバイスウエハ６０ａに対して垂直方向に引き上げて剥離することが好ましい。このとき、剥離界面は、支持体１２と仮接着用積層体１１の界面で剥離されることが好ましい。この場合、支持体１２と仮接着用積層体１１の界面の剥離強度をＡ、デバイスウエハ表面６１ａと仮接着用積層体１１の剥離強度Ｂとすると、以下の式を満たすことが好ましい。
　Ａ＜Ｂ　　　・・・・式（１） Next, as shown in FIG. 1D, 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. At this time, the peeling interface is preferably peeled off at the interface between the support 12 and the temporary bonding laminate 11. In this case, if the peel strength at the interface between the support 12 and the temporary bonding laminate 11 is A, and the peel strength B between the device wafer surface 61a and the temporary bonding laminate 11 is, it is preferable to satisfy the following formula.
A <B Formula (1)
　また、仮接着用積層体１１に後述する剥離液に接触させ、その後、必要に応じて、支持体１２に対して薄型デバイスウエハ６０ａを摺動させた後に、薄型デバイスウエハ６０ａの端部からデバイスウエハに対して垂直方向に引き上げて剥離することもできる。 Moreover, after making the laminated body 11 for temporary adhesion contact the peeling liquid mentioned later, and sliding the thin device wafer 60a with respect to the support body 12 as needed after that, it is a device from the edge part of the thin device wafer 60a. It can also be peeled off by pulling up in the direction perpendicular to the wafer.
＜剥離液＞
　以下、剥離液について詳細に説明する。
　剥離液としては、水および、溶剤（有機溶剤）を使用することができる。
　また、剥離液としては、接着層１１を溶解する有機溶剤が好ましい。有機溶剤としては、例えば、脂肪族炭化水素類（ヘキサン、ヘプタン、アイソパーＥ、Ｈ、Ｇ（エッソ化学（株）製）等）、芳香族炭化水素類（トルエン、キシレン等）、ハロゲン化炭化水素（メチレンジクロライド、エチレンジクロライド、トリクレン、モノクロルベンゼン等）、極性溶剤が挙げられる。極性溶剤としては、アルコール類（メタノール、エタノール、プロパノール、イソプロパノール、１－ブタノール、１－ペンタノール、１－ヘキサノール、１－ヘプタノール、１－オクタノール、２－オクタノール、２－エチル－１－ヘキサノール、１－ノナノール、１－デカノール、ベンジルアルコール、エチレングリコールモノメチルエーテル、２－エトキシエタノール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノヘキシルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、ポリエチレングリコールモノメチルエーテル、ポリプロピレングリコール、テトラエチレングリコール、エチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル、メチルフェニルカルビノール、ｎ－アミルアルコール、メチルアミルアルコール等）、ケトン類（アセトン、メチルエチルケトン、エチルブチルケトン、メチルイソブチルケトン、シクロヘキサノン等）、エステル類（酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸アミル、酢酸ベンジル、乳酸メチル、乳酸ブチル、エチレングリコールモノブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールアセテート、ジエチルフタレート、レブリン酸ブチル等）、その他（トリエチルフォスフェート、トリクレジルフォスフェート、Ｎ－フェニルエタノールアミン、Ｎ－フェニルジエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、４－（２－ヒドロキシエチル）モルホリン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン等）等が挙げられる。 <Release solution>
Hereinafter, the stripping solution will be described in detail.
As the stripping solution, water and a solvent (organic solvent) can be used.
Moreover, as a peeling liquid, the organic solvent which melt | dissolves the contact bonding layer 11 is preferable. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons. (Methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents. Polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone) , Cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate Etc.), others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine) , N- phenyldiethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N- dimethylacetamide, N- methylpyrrolidone and the like) and the like.
　さらに、剥離性の観点から、剥離液は、アルカリ、酸、および界面活性剤を含んでいても良い。これらの成分を配合する場合、配合量は、それぞれ、剥離液の０．１～５．０質量％であることが好ましい。
　さらに剥離性の観点から、２種以上の有機溶剤および水、２種以上のアルカリ、酸および界面活性剤を混合する形態も好ましい。 Furthermore, from the viewpoint of peelability, the stripping solution may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amount is preferably 0.1 to 5.0% by mass of the stripping solution.
Further, from the viewpoint of peelability, a form in which two or more organic solvents and water, two or more alkalis, an acid, and a surfactant are mixed is also preferable.
　アルカリとしては、例えば、第三リン酸ナトリウム、第三リン酸カリウム、第三リン酸アンモニウム、第二リン酸ナトリウム、第二リン酸カリウム、第二リン酸アンモニウム、炭酸ナトリウム、炭酸カリウム、炭酸アンモニウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素アンモニウム、ホウ酸ナトリウム、ホウ酸カリウム、ホウ酸アンモニウム、水酸化ナトリウム、水酸化アンモニウム、水酸化カリウムおよび水酸化リチウムなどの無機アルカリ剤や、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、ｎ－ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、エチレンイミン、エチレンジアミン、ピリジン、テトラメチルアンモニウムヒドロキシドなどの有機アルカリ剤を使用することができる。これらのアルカリ剤は、単独若しくは２種以上を組み合わせて用いることができる。 Examples of the alkali include tribasic sodium phosphate, tribasic potassium phosphate, tribasic ammonium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, and ammonium carbonate. , Inorganic alkali agents such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, monomethylamine, Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanol Min, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, may be used an organic alkali agent such as tetramethylammonium hydroxide. These alkali agents can be used alone or in combination of two or more.
　酸としては、ハロゲン化水素、硫酸、硝酸、リン酸、ホウ酸などの無機酸や、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸、トリフルオロメタンスルホン酸、酢酸、クエン酸、ギ酸、グルコン酸、乳酸、シュウ酸、酒石酸などの有機酸を使用することができる。 Acids include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid, boric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid Organic acids such as formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid can be used.
　界面活性剤としては、アニオン系、カチオン系、ノニオン系、両性イオン系の界面活性剤を使用することができる。この場合、界面活性剤の含有量は、アルカリ水溶液の全量に対して１～２０質量％であることが好ましく、１～１０質量％であることがより好ましい。
　界面活性剤の含有量を上記した範囲内とすることにより、接着層１１と薄型デバイスウエハ６０ａとの剥離性をより向上できる傾向となる。 As the surfactant, an anionic, cationic, nonionic or zwitterionic surfactant can be used. In this case, the content of the surfactant is preferably 1 to 20% by mass and more preferably 1 to 10% by mass with respect to the total amount of the alkaline aqueous solution.
By making the content of the surfactant within the above-described range, the peelability between the adhesive layer 11 and the thin device wafer 60a tends to be further improved.
　アニオン系界面活性剤としては、特に限定されないが、脂肪酸塩類、アビエチン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホコハク酸塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルジフェニルエーテル（ジ）スルホン酸塩類、アルキルフェノキシポリオキシエチレンアルキルスルホン酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、Ｎ－アルキル－Ｎ－オレイルタウリンナトリウム類、Ｎ－アルキルスルホコハク酸モノアミド二ナトリウム塩類、石油スルホン酸塩類、硫酸化ヒマシ油、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸エステル塩類、スチレン－無水マレイン酸共重合物の部分けん化物類、オレフィン－無水マレイン酸共重合物の部分けん化物類、ナフタレンスルホン酸塩ホルマリン縮合物類等が挙げられる。この中で、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルジフェニルエーテル（ジ）スルホン酸塩類が特に好ましく用いられる。 Examples of the anionic surfactant include, but are not limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid salts, Alkylnaphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid Monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate esters, polio Siethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxy Examples thereof include ethylene alkylphenyl ether phosphoric acid ester salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, and naphthalene sulfonate formalin condensates. Of these, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates are particularly preferably used.
　カチオン系界面活性剤としては、特に限定されないが、従来公知のものを用いることができる。例えば、アルキルアミン塩類、第四級アンモニウム塩類、アルキルイミダゾリニウム塩、ポリオキシエチレンアルキルアミン塩類、ポリエチレンポリアミン誘導体が挙げられる。 The cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkyl imidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
　ノニオン系界面活性剤としては、特に限定されないが、ポリエチレングリコール型の高級アルコールエチレンオキサイド付加物、アルキルフェノールエチレンオキサイド付加物、アルキルナフトールエチレンオキサイド付加物、フェノールエチレンオキサイド付加物、ナフトールエチレンオキサイド付加物、脂肪酸エチレンオキサイド付加物、多価アルコール脂肪酸エステルエチレンオキサイド付加物、高級アルキルアミンエチレンオキサイド付加物、脂肪酸アミドエチレンオキサイド付加物、油脂のエチレンオキサイド付加物、ポリプロピレングリコールエチレンオキサイド付加物、ジメチルシロキサン－エチレンオキサイドブロックコポリマー、ジメチルシロキサン－（プロピレンオキサイド－エチレンオキサイド）ブロックコポリマー、多価アルコール型のグリセロールの脂肪酸エステル、ペンタエリスリトールの脂肪酸エステル、ソルビトールおよびソルビタンの脂肪酸エステル、ショ糖の脂肪酸エステル、多価アルコールのアルキルエーテル、アルカノールアミン類の脂肪酸アミド等が挙げられる。この中で、芳香環とエチレンオキサイド鎖を有するものが好ましく、アルキル置換または無置換のフェノールエチレンオキサイド付加物またはアルキル置換または無置換のナフトールエチレンオキサイド付加物がより好ましい。 The nonionic surfactant is not particularly limited, but is a polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid. Ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block Copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer , Fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines. Among these, those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol ethylene oxide adduct is more preferable.
　両性イオン系界面活性剤としては、特に限定されないが、アルキルジメチルアミンオキシドなどのアミンオキシド系、アルキルベタインなどのベタイン系、アルキルアミノ脂肪酸ナトリウムなどのアミノ酸系が挙げられる。特に、置換基を有してもよいアルキルジメチルアミンオキシド、置換基を有してもよいアルキルカルボキシベタイン、置換基を有してもよいアルキルスルホベタインが好ましく用いられる。具体的には、特開２００８－２０３３５９号公報の段落番号〔０２５６〕の式（２）で示される化合物、特開２００８－２７６１６６号公報の段落番号〔００２８〕の式（Ｉ）、式（ＩＩ）、式（ＶＩ）で示される化合物、特開２００９－４７９２７号公報の段落番号〔００２２〕～〔００２９〕で示される化合物を用いることができる。 Zwitterionic surfactants include, but are not limited to, amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaines, and amino acids such as sodium alkylamino fatty acids. In particular, alkyldimethylamine oxide which may have a substituent, alkylcarboxybetaine which may have a substituent, and alkylsulfobetaine which may have a substituent are preferably used. Specifically, the compound represented by the formula (2) in paragraph [0256] of JP-A-2008-203359, the formula (I) and the formula (II) in paragraph [0028] of JP-A-2008-276166 are disclosed. ), A compound represented by the formula (VI), and compounds represented by paragraph numbers [0022] to [0029] of JP-A-2009-47927 can be used.
　さらに必要に応じ、消泡剤および硬水軟化剤のような添加剤を含有することもできる。 Furthermore, additives such as an antifoaming agent and a water softening agent can be contained as required.
　そして、図１（Ｅ）に示すように、薄型デバイスウエハ６０ａから仮接着用積層体１１を除去することにより、薄型デバイスウエハを得ることができる。
　仮接着用積層体１１の除去方法は、例えば、仮接着用積層体をフィルム状のまま剥離除去（機械剥離）する方法、仮接着用積層体を剥離液で膨潤させた後に剥離除去する方法、仮接着用積層体に剥離液を噴射して破壊除去する方法、仮接着用積層体を剥離液に溶解させて溶解除去する方法、仮接着用積層体を活性光線、放射線または熱の照射により分解、気化して除去する方法などが挙げられる。仮接着用積層体をフィルム状のまま剥離除去する方法、仮接着用積層体を水溶液または有機溶剤に溶解させて溶解除去する方法が好ましく使用できる。溶剤の使用量削減の観点から、フィルム状のまま除去することが好ましく、フィルム状のまま除去するためには、デバイスウエハ表面６１aと仮接着用積層体１１の剥離強度Ｂが以下の式（２）を満たすことが好ましい。
　Ｂ≦４Ｎ／ｃｍ　　　・・・・式（２） Then, as shown in FIG. 1E, the thin device wafer can be obtained by removing the temporary bonding laminate 11 from the thin device wafer 60a.
The removal method of the temporary bonding laminate 11 includes, for example, a method of peeling and removing the temporary bonding laminate in a film state (mechanical peeling), a method of peeling and removing the temporary bonding laminate after swelling with a peeling solution, A method of spraying a release liquid onto a temporary adhesive laminate to remove it by destruction, a method of dissolving and removing a temporary adhesive laminate in a release liquid, and decomposing the temporary adhesive laminate by irradiation with actinic rays, radiation or heat And a method of removing by vaporization. A method of peeling and removing the temporarily adhering laminate in the form of a film and a method of dissolving and removing the temporarily adhering laminate in an aqueous solution or an organic solvent can be preferably used. From the viewpoint of reducing the amount of solvent used, it is preferable to remove the film as it is. In order to remove the film as it is, the peel strength B between the device wafer surface 61a and the temporary bonding laminate 11 is expressed by the following formula (2 ) Is preferably satisfied.
B ≦ 4N / cm ・ ・ ・ ・ Formula (2)
　本発明では、支持体１２を薄型デバイスウエハ６０ａから剥離する際に、何ら処理することなく薄型デバイスウエハ６０ａの端部からデバイスウエハに対して垂直方向に引き上げて剥離することが好ましく、デバイスウエハ表面６１ａ上の仮接着用積層体１１を除去する方法としては、フィルム状のまま除去することが好ましい。
　支持体１２と仮接着用積層体１１の界面の剥離強度をＡ、デバイスウエハ表面６１ａと接着層１１の剥離強度Ｂとすると、上述した式（１）および（２）をともに満たすことにより、支持体１２、仮接着用積層体１１を、上述した態様で、デバイスウエハから除去することができる。
　なお、デバイスウエハから支持体を剥離する際、デバイスウエハと仮接着用積層体との界面で剥離する場合（すなわち、デバイスウエハ側に仮接着用積層体が残らない場合）は、図１（Ｅ）の工程は省略することもできる。 In the present invention, when the support 12 is peeled from the thin device wafer 60a, it is preferable that the support 12 is lifted from the end of the thin device wafer 60a in the direction perpendicular to the device wafer without any treatment. As a method for removing the temporary adhering laminate 11 on 61a, it is preferable to remove the laminated body 11 in the form of a film.
When the peel strength at the interface between the support 12 and the temporary bonding laminate 11 is A, and the peel strength B between the device wafer surface 61a and the adhesive layer 11, the support is satisfied by satisfying both the above-described formulas (1) and (2). The body 12 and the temporary bonding laminate 11 can be removed from the device wafer in the above-described manner.
When the support is peeled from the device wafer, if the peel is made at the interface between the device wafer and the temporary bonding laminate (that is, the temporary bonding laminate does not remain on the device wafer side), FIG. ) Can be omitted.
　支持体１２を薄型デバイスウエハ６０ａから脱離した後、必要に応じて、薄型デバイスウエハ６０ａに対して、種々の公知の処理を施し、薄型デバイスウエハ６０ａを有する半導体装置を製造する。 After the support 12 is detached from the thin device wafer 60a, various known processes are performed on the thin device wafer 60a as necessary to manufacture a semiconductor device having the thin device wafer 60a.
　また、支持体に仮接着用積層体が付着している場合は、仮接着用積層体を除去することにより、支持体を再生することができる。仮接着用積層体を除去する方法としては、フィルム状のままと、ブラシ、超音波、氷粒子、エアロゾルの吹付けにより物理的に除去する方法、水溶液または有機溶剤に溶解させて溶解除去する方法、活性光線、放射線、熱の照射により分解、気化させる方法などの化学的に除去する方法が挙げられるが、支持体に応じて、従来既知の洗浄方法を利用することができる。
　例えば、支持体としてシリコン基板を使用した場合、従来既知のシリコンウエハの洗浄方法を使用することができ、例えば化学的に除去する場合に使用できる水溶液または有機溶剤としては、強酸、強塩基、強酸化剤、またはそれらの混合物が上げられ、具体的には、硫酸、塩酸、フッ酸、硝酸、有機酸などの酸類、テトラメチルアンモニウム、アンモニア、有機塩基などの塩基類、過酸化水素などの酸化剤、またはアンモニアと過酸化水素の混合物、塩酸と過酸化水素水の混合物、硫酸と過酸化水素水の混合物、フッ酸と過酸化水素水の混合物、フッ酸とフッ化アンモニウムとの混合物などが挙げられる。 Moreover, when the laminated body for temporary adhesion has adhered to the support body, a support body can be reproduced | regenerated by removing the laminated body for temporary adhesion. As a method for removing the temporary adhesive laminate, a method of physically removing the laminated body as a film, by spraying a brush, ultrasonic waves, ice particles or aerosol, a method of dissolving and removing by dissolving in an aqueous solution or an organic solvent In addition, a chemical removal method such as a method of decomposing and vaporizing by irradiation with actinic rays, radiation, and heat can be used, and conventionally known cleaning methods can be used depending on the support.
For example, when a silicon substrate is used as the support, a conventionally known silicon wafer cleaning method can be used. For example, 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. Specifically, 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.
　再生した支持体を使った場合の接着性の観点から、支持体洗浄液を用いることが好ましい。
　支持体洗浄液は、ｐＫａが０未満の酸（強酸）と過酸化水素を含んでいることが好ましい。ｐＫａが０未満の酸としては、ヨウ化水素、過塩素酸、臭化水素、塩化水素、硝酸、硫酸などの無機酸、又はアルキルスルホン酸、アリールスルホン酸などの有機酸から選択される。支持体上の接着層の洗浄性の観点から無機酸であることが好ましく、硫酸が最も好ましい。 From the viewpoint of adhesiveness when the regenerated support is used, it is preferable to use a support cleaning liquid.
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. From the viewpoint of detergency of the adhesive layer on the support, an inorganic acid is preferable, and sulfuric acid is most preferable.
　過酸化水素としては、３０質量％過酸化水素水が好ましく使用でき、上記強酸と３０質量％過酸化水素水との混合比は、質量比で０．１：１～１００：１が好ましく、１：１～１０：１がより好ましく、３：１～５：１が最も好ましい。 As the hydrogen peroxide, 30% 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.
＜＜従来の実施形態＞＞
　次いで、従来の実施形態について説明する。
　図２は、従来の接着性支持体とデバイスウエハとの仮接着状態の解除を説明する概略断面図である。
　従来の実施形態においては、図２に示すように、接着性支持体として、支持体１２の上に、従来の仮接着剤により形成された接着層１１ｂが設けられてなる接着性支持体１００ａを使用し、それ以外は、図１を参照して説明した手順と同様に、接着性支持体１００ａとデバイスウエハとを仮接着し、デバイスウエハにおけるシリコン基板の薄膜化処理を行い、次いで、上記した手順と同様に、接着性支持体１００ａから薄型デバイスウエハ６０ａを剥離する。 << Conventional Embodiment >>
Next, a conventional embodiment will be described.
FIG. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the conventional adhesive support and the device wafer.
In the conventional embodiment, as shown in FIG. 2, an adhesive support 100a in which an adhesive layer 11b formed of a conventional temporary adhesive is provided on a support 12 as an adhesive support. Otherwise, the adhesive support 100a and the device wafer are temporarily bonded in the same manner as described with reference to FIG. 1, and the silicon wafer is thinned on the device wafer. Similar to the procedure, the thin device wafer 60a is peeled from the adhesive support 100a.
　しかしながら、従来の仮接着剤によれば、高い接着力により被処理部材を仮支持し、処理済部材に損傷を与えることなく、処理済部材に対する仮支持を容易に解除することが困難である。例えば、デバイスウエハと支持体との仮接着を充分にしようとするべく、従来の仮接着剤の内、接着性の高いものを採用すると、デバイスウエハと支持体との仮接着が強すぎる傾向となる。よって、この強すぎる仮接着を解除するべく、例えば、図３に示すように、薄型デバイスウエハ６０ａの裏面にテープ（例えば、ダイシングテープ）７０を貼り付け、接着性支持体１００ａから薄型デバイスウエハ６０ａを剥離する場合においては、構造体６３が設けられたデバイスチップ６２から、構造体６３が脱離するなどして、デバイスチップ６２を破損する不具合が生じやすい。
　一方、従来の仮接着剤の内、接着性が低いものを採用すると、処理済部材に対する仮支持を容易に解除することはできるが、そもそもデバイスウエハとキャリア基板との仮接着が弱すぎ、デバイスウエハをキャリア基板で確実に支持できないという不具合が生じやすい。 However, according to the conventional temporary adhesive, it is difficult to easily release the temporary support for the processed member without temporarily damaging the processed member with high adhesive force and damaging the processed member. For example, in order to ensure sufficient temporary bonding between the device wafer and the support, if a conventional temporary adhesive having high adhesiveness is adopted, the temporary bonding between the device wafer and the support tends to be too strong. Become. Therefore, in order to release the temporary bonding that is too strong, for example, as shown in FIG. 3, a tape (for example, a 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. In the case of peeling off, 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.
On the other hand, when a conventional temporary adhesive having low adhesiveness is adopted, temporary support to the processed member can be easily released, but the temporary adhesion between the device wafer and the carrier substrate is too weak in the first place. A problem that the wafer cannot be reliably supported by the carrier substrate is likely to occur.
　これに対し、本発明の仮接着用積層体は、充分な接着性を発現するとともに、デバイスウエハ６０と支持体１１との仮接着を容易に解除できる。すなわち、本発明の仮接着用積層体によれば、高い接着力によりデバイスウエハ６０を仮接着できるとともに、薄型デバイスウエハ６０ａに損傷を与えることなく、薄型デバイスウエハ６０ａに対する仮接着を容易に解除できる。 On the other hand, the temporary bonding laminate of the present invention exhibits sufficient adhesiveness and can easily release the temporary bonding between the device wafer 60 and the support 11. That is, according to the temporary bonding laminate 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. .
　本発明の半導体装置の製造方法は、上述した実施の形態に限定されるものではなく、適宜な変形、改良等が可能である。
　また、上述した実施形態においては、デバイスウエハとして、シリコン基板を挙げたが、これに限定されるものではなく、半導体装置の製造方法において、機械的または化学的な処理に供され得るいずれの被処理部材であっても良い。例えば、化合物半導体基板を挙げることもでき、化合物半導体基板の具体例としては、ＳｉＣ基板、ＳｉＧｅ基板、ＺｎＳ基板、ＺｎＳｅ基板、ＧａＡｓ基板、ＩｎＰ基板、および、ＧａＮ基板などが挙げられる。
　また、上述した実施形態においては、デバイスウエハ（シリコン基板）に対する機械的または化学的な処理として、デバイスウエハの薄膜化処理、および、シリコン貫通電極の形成処理を挙げたが、これらに限定されるものではなく、半導体装置の製造方法において必要ないずれの処理も挙げられる。
　その他、上述した実施形態において例示した、デバイスウエハにおけるデバイスチップの形状、寸法、数、配置箇所等は任意であり、限定されない。 The method for manufacturing a semiconductor device of the present invention is not limited to the above-described embodiment, and appropriate modifications and improvements can be made.
In the above-described embodiment, a silicon substrate is used as the device wafer. However, 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. For example, 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.
In the above-described embodiments, 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.
In addition, 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.
　以下、本発明を実施例によりさらに具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。尚、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, “part” and “%” are based on mass.
＜仮接着用積層体の作成方法＞
　下記記載のフィルム作成用組成物を、厚み７５μｍのポリエチレンテレフタレートフィルム（離型フィルム）上に、速度１ｍ／分の速度でワイヤバーによって塗工し、１４０℃で１０分間乾燥することによって、フィルム厚１００μｍの接着フィルムを作成した。
　また、以下の表１記載の仮接着用積層体１－４、１－５、１－１５、１－１６、１－１７、１－１８におけるフィルム作成用組成物は、３００℃５分間で溶融撹拌し、幅１００μｍのスリットから押し出すことで、フィルム厚１００μｍの押出成型シート（接着フィルム）を作成した。
　また、以下の表１記載の仮接着用積層体１－Ｒ２におけるフィルム作成用組成物は、市販のポリイミドフィルム（カプトン、東レデュポン製）を押し出し、フィルム厚１００μｍの押出成型シート（接着フィルム）として使用した。
　つづいて、接着フィルム上に、以下の離型層形成用塗布液を、バー塗布し、１２０℃で１分間、オーブン乾燥を行い、接着フィルムの両面に、厚さ６０ｎｍの離型層を有する仮接着用積層体を作成した。 <Method for creating temporary adhesive laminate>
The film forming composition described below is coated on a polyethylene terephthalate film (release film) having a thickness of 75 μm with a wire bar at a speed of 1 m / min, and dried at 140 ° C. for 10 minutes, whereby a film thickness of 100 μm is obtained. An adhesive film was prepared.
Also, the film-forming compositions in the temporary bonding laminates 1-4, 1-5, 1-15, 1-16, 1-17, and 1-18 shown in Table 1 below were melted at 300 ° C. for 5 minutes. By stirring and extruding from a slit having a width of 100 μm, an extruded sheet (adhesive film) having a film thickness of 100 μm was prepared.
In addition, the film-forming composition in the temporary adhering laminate 1-R2 shown in Table 1 below extrudes a commercially available polyimide film (Kapton, manufactured by Toray DuPont) as an extruded sheet (adhesive film) having a film thickness of 100 μm. used.
Subsequently, the following coating solution for forming a release layer is coated on the adhesive film with a bar, oven-dried at 120 ° C. for 1 minute, and a temporary release layer having a release layer having a thickness of 60 nm is formed on both surfaces of the adhesive film. An adhesive laminate was prepared.
［フィルム作成用組成物］
・表１記載のポリマー：表１に示す質量部
・Ｉｒｇａｎｏｘ（登録商標）１０１０（ＢＡＳＦ（株）製）：０．９質量部
・Ｓｕｍｉｌｉｚｅｒ（登録商標）ＴＰ－Ｄ（住友化学（株）製）：０．９質量部
・表１記載の溶剤：表１記載の質量部
［離型層形成用塗布液］
・表１記載の離型剤：表１記載の質量部
・表１記載の溶剤：表１記載の質量部 [Composition for film preparation]
-Polymers listed in Table 1: parts by mass shown in Table 1-Irganox (registered trademark) 1010 (manufactured by BASF): 0.9 parts by mass-Sumilizer (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.) : 0.9 parts by mass. Solvents listed in Table 1: parts by mass listed in Table 1 [Coating liquid for forming release layer]
-Release agent described in Table 1: parts by mass described in Table 1-Solvent described in Table 1: parts by mass described in Table 1
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
表１中に記載の化合物は以下の通りである。
＜ポリマー＞
（ａ－１）　セプトン２１０４（水添ポリスチレン系エラストマー、５％熱質量減少温度＝４００℃以上４５０℃未満、Ｍｗ＝５万以上１０万未満、クラレ（株）製）
（ａ－２）　タフテックＰ２０００（部分選択的水添ポリスチレン系エラストマー、５％熱質量減少温度＝４００℃以上４５０℃未満、Ｍｗ＝５万以上１０万未満、旭化成（株）製）
（ａ－３）　ＵｌｔｒａｓｏｎＥ６０２０（ポリエーテルスルホン、５％熱質量減少温度＝４５０℃以上、ＢＡＳＦ社製）
（ａ－４）　ハイトレル７２４７（ポリエステル系エラストマー、５％熱質量減少温度＝３５０℃以上４００℃未満、東レデュポン社製）
（ａ－５）　プリマロイＣＰ３００（ポリエステル系エラストマー、５％熱質量減少温度＝３５０℃以上４００℃未満、三菱化学社製）
（ａ－６）　ＳＩＳ－５２００Ｐ（非水添ポリスチレン系エラストマー、２５０℃以上３５０℃未満、Ｍｗ＝１０万以上２０万未満、ＪＳＲ（株）製）
（ａ－７）　サーモランＺ１０２Ｂ（ポリオレフィン系エラストマー、三菱化学（株）製）
（ａ－８）　ＰＡＮＤＥＸ　Ｔ－２１８５（ポリウレタン系エラストマー、ＤＩＣ（株）製）
（ａ－９）　ＵＢＥＳＴＡ　ＸＰＡ９０４０Ｆ１（ポリアミド系エラストマー、５％熱質量減少温度＝３５０℃以上４００℃未満、宇部興産（株）製）
（ａ－１０）ＸＹＲＯＮ　Ｓ２０１Ａ（ポリフェニレンエーテル、旭化成（株）製）
（Ｒａ－１）　カプトン（ポリイミド、５％熱質量減少温度＝４５０℃以上、東レデュポン製）
＜離型剤＞
（ｂ－１）　メガファックＦ－５５３（フッ素基・親水基・親油基含有オリゴマー、オイル、Ｍｗ＝０．２万以上２．０万未満、ＤＩＣ社製）
（ｂ－２）　メガファックＦ－５５７（フッ素基・親水基・親油基含有オリゴマー、オイル、Ｍｗ＝０．２万以上２．０万未満、ＤＩＣ社製）
（ｂ－３）　ダイフリーＦＢ９６２（フッ素系離型剤、Ｍｗ＝０．２万以上２．０万未満、ダイキン社製）
（ｂ－４）　メガファックＲＳ－７２－Ｋ（３０質量％溶液、反応性フッ素化合物、Ｍｗ＝０．２万以上２．０万未満、ＤＩＣ社製）
（ｂ－５）　オプツールＤＳＸ（２０質量％溶液、フッ素系シランカップリング剤、ダイキン社製）
（ｂ－６）　トリクロロ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－ｎ－オクチル）シラン　（フッ素系シランカップリング剤、東京化成工業製）
（ｂ－７）　トリメトキシ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－ヘプタデカフルオロデシル）シラン　（フッ素系シランカップリング剤、東京化成工業製）
（ｂ－８）　トリエトキシ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－ｎ－オクチル）シラン　（フッ素系シランカップリング剤、東京化成工業製）
（ｂ－９）　Ｘ－２２－１６４　（シリコン系２官能モノマー　信越化学工業製）
＜溶剤＞
フッ素溶媒１：フロリナートＦＣ４０（３Ｍ社製）
ＰＧＭＥＡ：プロピレングリコール－１－メチルエーテルアセテート The compounds described in Table 1 are as follows.
<Polymer>
(A-1) Septon 2104 (hydrogenated polystyrene elastomer, 5% thermal mass reduction temperature = 400 ° C. or higher and lower than 450 ° C., Mw = 50,000 or higher and lower than 100,000, manufactured by Kuraray Co., Ltd.)
(A-2) Tuftec P2000 (partially selective hydrogenated polystyrene elastomer, 5% thermal mass reduction temperature = 400 ° C. to less than 450 ° C., Mw = 50,000 to less than 100,000, manufactured by Asahi Kasei Corporation)
(A-3) Ultrason E6020 (polyethersulfone, 5% thermal mass reduction temperature = 450 ° C. or more, manufactured by BASF)
(A-4) Hytrel 7247 (polyester elastomer, 5% thermal mass loss temperature = 350 ° C. or higher and lower than 400 ° C., manufactured by Toray DuPont)
(A-5) Primalloy CP300 (polyester elastomer, 5% thermal mass reduction temperature = 350 ° C. or higher and lower than 400 ° C., manufactured by Mitsubishi Chemical Corporation)
(A-6) SIS-5200P (non-hydrogenated polystyrene elastomer, 250 ° C. or more and less than 350 ° C., Mw = 100,000 or more and less than 200,000, manufactured by JSR Corporation)
(A-7) Thermoran Z102B (polyolefin elastomer, manufactured by Mitsubishi Chemical Corporation)
(A-8) PANDEX T-2185 (polyurethane elastomer, manufactured by DIC Corporation)
(A-9) UBESTA XPA9040F1 (polyamide-based elastomer, 5% thermal mass reduction temperature = 350 ° C. or higher and lower than 400 ° C., manufactured by Ube Industries, Ltd.)
(A-10) XYRON S201A (polyphenylene ether, manufactured by Asahi Kasei Corporation)
(Ra-1) Kapton (Polyimide, 5% thermal mass loss temperature = 450 ° C or higher, manufactured by Toray DuPont)
<Release agent>
(B-1) MegaFuck F-553 (fluorine group / hydrophilic group / lipophilic group-containing oligomer, oil, Mw = 20,000 to less than 20,000, manufactured by DIC)
(B-2) MegaFuck F-557 (fluorine group / hydrophilic group / lipophilic group-containing oligomer, oil, Mw = 20,000 to less than 20,000, manufactured by DIC)
(B-3) Die-free FB962 (Fluorine-based mold release agent, Mw = 20,000 to less than 20,000, manufactured by Daikin)
(B-4) Megafuck RS-72-K (30% by mass solution, reactive fluorine compound, Mw = 20,000 to less than 20,000, manufactured by DIC)
(B-5) Optool DSX (20% by mass solution, fluorine-based silane coupling agent, manufactured by Daikin)
(B-6) Trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane (fluorine silane coupling agent, manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-7) Trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane (Fluorine silane coupling agent, manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-8) Triethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane (fluorine-based silane coupling agent, manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-9) X-22-164 (Silicon bifunctional monomer, manufactured by Shin-Etsu Chemical Co., Ltd.)
<Solvent>
Fluorine solvent 1: Fluorinert FC40 (manufactured by 3M)
PGMEA: Propylene glycol-1-methyl ether acetate
＜接着性支持体１の作成＞
　上記方法で作成した接着フィルムを、真空ラミネーターにセットした。そして、本装置にて、接着フィルムを１００ｍｍＳｉウエハ（支持体）上に位置させ、真空下でＳｉウエハと接着フィルムの離型層の反対側の面とを接触させ、ローラにて、接着フィルムとＳｉウエハとを固定し、接着性支持体１を作成した。 <Creation of adhesive support 1>
The adhesive film prepared by the above method was set in a vacuum laminator. Then, with this apparatus, the adhesive film is positioned on a 100 mm Si wafer (support), the Si wafer is brought into contact with the opposite surface of the release layer of the adhesive film under vacuum, and the adhesive film is The Si wafer was fixed and the adhesive support 1 was created.
＜試験片の作製＞
　接着性支持体１の接着フィルムが形成された側の面と、１００ｍｍＳｉウエハ（デバイスウエハ）のデバイス面とを、真空下、１９０℃、０．１１ＭＰａの圧力で３分間圧着を行い、試験片を作製した。 <Preparation of test piece>
The surface of the adhesive support 1 on which the adhesive film is formed and the device surface of a 100 mm Si wafer (device wafer) are pressure-bonded under a vacuum at 190 ° C. and a pressure of 0.11 MPa for 3 minutes, Produced.
＜仮接着用積層体（１－Ｒ３）および試験片の作成方法＞
　上記ポリマー（ａ－１）を２８．２質量部と、Ｉｒｇａｎｏｘ（登録商標）１０１０（ＢＡＳＦ（株）製）を０．９質量部と、Ｓｕｍｉｌｉｚｅｒ（登録商標）ＴＰ－Ｄ（住友化学（株）製）を０．９質量部と、メシチレン７０質量部とを含む組成物を、１００ｍｍＳｉウエハにスピンコーター塗布した後、１１０℃で１分ベークし、さらに１９０℃で４分ベークすることで厚さ１００μｍの接着層を形成した。
　次に、接着層の表面に、上記離型剤（ｂ－５）を０．５質量部と、上記フッ素溶媒１を９９．５質量部とを含む組成物をスピンコート塗布して１２０℃で３０秒ベークし、さらに、１９０℃で３分加熱して、厚さ６０ｎｍの離型層を形成し、仮接着用積層体を有する接着性支持体１を作製した。
　次に、接着性支持体１の仮接着用積層体が形成された側の面と、１００ｍｍＳｉウエハ（デバイスウエハ）のデバイス面とを、真空下、１９０℃、０．１１ＭＰａの圧力で３分間圧着を行い、試験片を作製した。 <Preparation Method of Temporary Bonding Laminate (1-R3) and Test Piece>
28.2 parts by mass of the polymer (a-1), 0.9 parts by mass of Irganox (registered trademark) 1010 (manufactured by BASF Corp.), Sumilizer (registered trademark) TP-D (Sumitomo Chemical Co., Ltd.) The composition containing 0.9 part by mass and 70 parts by mass of mesitylene is spin-coated on a 100 mm Si wafer, then baked at 110 ° C. for 1 minute, and further baked at 190 ° C. for 4 minutes. A 100 μm adhesive layer was formed.
Next, a composition containing 0.5 parts by mass of the release agent (b-5) and 99.5 parts by mass of the fluorine solvent 1 is spin-coated on the surface of the adhesive layer at 120 ° C. After baking for 30 seconds and further heating at 190 ° C. for 3 minutes, a release layer having a thickness of 60 nm was formed, and an adhesive support 1 having a laminate for temporary bonding was produced.
Next, the surface of the adhesive support 1 on which the laminated body for temporary bonding is formed and the device surface of a 100 mm Si wafer (device wafer) are pressure-bonded under vacuum at 190 ° C. and a pressure of 0.11 MPa for 3 minutes. A test piece was prepared.
＜平坦性＞
　仮接着用積層体の平均厚みを、接着性支持体の一方の端面から他方の端面に向かって、等間隔で５か所の場所における厚みを、エリプソメトリーにより測定した値の平均値（平均膜厚）と、最大厚みもしくは最小厚みとの差を測定し、以下の基準で評価した。
Ａ：｜平均膜厚－最大厚みもしくは最小厚み｜が、０μｍ以上５μｍ未満
Ｂ：｜平均膜厚－最大厚みもしくは最小厚み｜が、５μｍ以上２０μｍ未満
Ｃ：｜平均膜厚－最大厚みもしくは最小厚み｜が、２０μｍ以上 <Flatness>
The average thickness of the temporary adhesive laminate was measured by ellipsometry at five locations at equal intervals from one end face of the adhesive support to the other end face (average film) Thickness) and the maximum or minimum thickness were measured and evaluated according to the following criteria.
A: | average film thickness—maximum thickness or minimum thickness | is 0 μm to less than 5 μm B: | average film thickness—maximum thickness or minimum thickness | is 5 μm to less than 20 μm C: | average film thickness—maximum thickness or minimum thickness | Is over 20μm
＜接着性＞
　試験片のせん断接着力を、引っ張り試験機（(株)イマダ製デジタルフォースゲージ、型式：ＺＰ－５０Ｎ）を用いて、２５０ｍｍ／ｍｉｎの条件で接着層の面に沿った方向に引っ張り測定し、以下の基準で評価した。
Ａ：５０Ｎ以上の接着力
Ｂ：１０Ｎ以上５０Ｎ未満の接着力
Ｃ：１０Ｎ未満の接着力 <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.
A: Adhesive force of 50N or more B: Adhesive force of 10N or more and less than 50N C: Adhesive force of less than 10N
＜剥離性＞
　試験片を、ダイシングテープマウンターの中央にダイシングフレームとともにセットし、ダイシングテープを上方から位置した。ローラー（および真空）で試験片とダイシングテープを固定し、ダイシングフレーム上でダイシングテープをカットし、ダイシングテープ上に試験片をマウントした。
　試験片を５００ｍｍ／ｍｉｎの条件で接着層の垂直方向に引っ張り、剥離性を確認した。また、作製された試験片を２５０℃で３０分加熱した後に、同様に、２５０ｍｍ／ｍｉｎの条件で接着層の垂直方向に引っ張り、熱プロセス後の剥離性を確認し、以下の基準で評価した。なお、Ｓｉウエハの破損の有無は目視で確認した。
Ａ：最大の剥離力が６Ｎ未満で剥離できた。
Ｂ：最大の剥離力が６Ｎ以上１２Ｎ未満で剥離できた。
Ｃ：最大の剥離力が１２Ｎ以上２０Ｎ未満で剥離できた。
Ｄ：最大の剥離力が２０Ｎ以上で剥離できたか、Ｓｉウエハが破損してしまった。 <Peelability>
The 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 of the adhesive layer under the condition of 500 mm / min to confirm the peelability. In addition, after the prepared test piece was heated at 250 ° C. for 30 minutes, similarly, it was pulled in the vertical direction of the adhesive layer under the condition of 250 mm / min, and the peelability after the thermal process was confirmed, and evaluated according to the following criteria. . In addition, the presence or absence of the damage of Si wafer was confirmed visually.
A: The maximum peeling force was less than 6N, and peeling was possible.
B: Separation was possible when the maximum peeling force was 6N or more and less than 12N.
C: Separation was possible when the maximum peeling force was 12N or more and less than 20N.
D: The maximum peel force could be peeled off at 20 N or more, or the Si wafer was damaged.
＜除去性（溶解除去）＞
　剥離性試験終了後の接着フィルム付きＳｉウエハを、接着フィルムを上にしてスピンコーターにセットし、洗浄溶剤として下記表２に記載の溶剤を使用して、５分間噴霧した。更にスピン乾燥を行った。その後、外観を観察してＳｉウエハ上残存する接着フィルムの有無を目視でチェックし、以下の基準で評価した。
Ａ：接着フィルムの残存が認められない
Ｂ：接着フィルムの残存が認められた <Removability (dissolution removal)>
After completion of the peelability test, the Si wafer with the adhesive film was set on a spin coater with the adhesive film facing upward, and sprayed for 5 minutes using the solvents described in Table 2 below as the cleaning solvent. Further, spin drying was performed. Then, the external appearance was observed and the presence or absence of the adhesive film which remain | survived on Si wafer was checked visually, and the following references | standards evaluated.
A: No adhesive film remains B: Adhesive film remains
＜除去性（フィルム除去）＞
　剥離性試験終了後の接着フィルム付きＳｉウエハ上に剥離用テープ（リンテック株式会社製）を、Ｓｉウエハ外周部の一部に貼り付け、剥離用テープを垂直方向に引っ張り、Ｓｉウエハ上より接着フィルムを機械剥離した。その後、外観を観察して薄型デバイスウエハ上に残存する接着フィルムの剥離残渣の有無を目視でチェックし、以下の基準で評価した。
Ａ：破断することなく接着フィルムを除去でき、接着フィルムの剥離残渣が認められない。
Ｂ：剥離の途中で破断した。または、接着フィルムを除去できたが残渣が残った。 <Removability (film removal)>
A peeling tape (manufactured by LINTEC Co., Ltd.) is applied to a part of the outer periphery of the Si wafer on the Si wafer with an adhesive film after the peelability test is completed, and the peeling tape is pulled in the vertical direction, and the adhesive film is formed on the Si wafer. The machine was peeled off. Thereafter, the appearance was observed, and the presence or absence of a peeling residue of the adhesive film remaining on the thin device wafer was visually checked and evaluated according to the following criteria.
A: The adhesive film can be removed without breaking, and no peeling residue of the adhesive film is observed.
B: It broke in the middle of peeling. Alternatively, the adhesive film could be removed but the residue remained.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
　上記結果より、実施例１～１８は、平坦性、接着性および剥離性が良好であった。更には、接着層の除去性が、溶解除去、フィルム除去のいずれにおいても良好であった。
　一方、比較例１～３は、平坦性、接着性および剥離性のいずれかが劣るものであった。 From the above results, Examples 1 to 18 had good flatness, adhesiveness and peelability. Furthermore, the removability of the adhesive layer was good in both dissolution removal and film removal.
On the other hand, Comparative Examples 1 to 3 were inferior in any of flatness, adhesiveness and peelability.
１１、１１ａ：接着層
１２：支持体
６０：デバイスウエハ
６０ａ：薄型デバイスウエハ
６１：シリコン基板
６１ａ：表面
６１ｂ：、６１ｂ１：裏面
６２：デバイスチップ
６３：構造体
１００：接着性支持体 DESCRIPTION OF SYMBOLS 11, 11a: Adhesion layer 12: Support body 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 body

Claims (13)

  1. 　デバイスウエハのデバイス面と支持体とを、剥離可能に仮接着するために用いる仮接着用積層体であって、
    　ポリスチレン系エラストマー、ポリエステル系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマー、ポリアクリル系エラストマー、シリコーン系エラストマー、ポリイミド系エラストマー、ポリエーテルエーテルケトン、ポリフェニレンスルファイド、ポリフェニレンエーテルおよびポリエーテルスルホンから選ばれる少なくとも１種を含むフィルムと、
    　前記フィルムの少なくとも一方の表面に、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を有する、仮接着用積層体。     A temporary bonding laminate used for temporarily bonding the device surface of the device wafer and the support so as to be peelable,
    Polystyrene elastomer, polyester elastomer, polyolefin elastomer, polyurethane elastomer, polyamide elastomer, polyacryl elastomer, silicone elastomer, polyimide elastomer, polyether ether ketone, polyphenylene sulfide, polyphenylene ether, and polyether sulfone A film comprising at least one selected from
    A laminate for temporary adhesion, which has a release layer containing a release agent containing at least one selected from fluorine atoms and silicon atoms on at least one surface of the film.
  2. 　前記フィルムが、ポリスチレン系エラストマーおよびポリエーテルスルホンから選ばれる少なくとも１種を含む請求項１記載の仮接着用積層体。 The laminate for temporary adhesion according to claim 1, wherein the film contains at least one selected from polystyrene-based elastomer and polyethersulfone.
  3. 　前記フィルムが、ポリスチレン系エラストマーを含む請求項１に記載の仮接着用積層体。 The laminate for temporary bonding according to claim 1, wherein the film contains a polystyrene-based elastomer.
  4. 　前記ポリスチレン系エラストマーが、水添物である請求項１～３のいずれか１項に記載の仮接着用積層体。 The laminate for temporary bonding according to any one of claims 1 to 3, wherein the polystyrene-based elastomer is a hydrogenated product.
  5. 　前記ポリスチレン系エラストマーの、２５℃から、２０℃／分で昇温した５％熱質量減少温度が２５０℃以上である請求項１～４のいずれか１項に記載の仮接着用積層体。 The laminate for temporary bonding according to any one of claims 1 to 4, wherein the 5% thermal mass reduction temperature of the polystyrene-based elastomer raised from 25 ° C at 20 ° C / min is 250 ° C or higher.
  6. 　前記離型剤が、シランカップリング剤である請求項１～５のいずれか１項に記載の仮接着用積層体。 The laminate for temporary bonding according to any one of claims 1 to 5, wherein the release agent is a silane coupling agent.
  7. 　前記フィルムの両方の表面に前記離型層を有する請求項１～６のいずれか１項に記載の仮接着用積層体。 The laminate for temporary bonding according to any one of claims 1 to 6, wherein the release layer is provided on both surfaces of the film.
  8. 　前記フィルムの片方の表面のみに前記離型層を有する請求項１～６のいずれか１項に記載の仮接着用積層体。 The laminate for temporary adhesion according to any one of claims 1 to 6, wherein the release layer is provided only on one surface of the film.
  9. 　ポリスチレン系エラストマー、ポリエステル系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマー、ポリアクリル系エラストマー、シリコーン系エラストマー、ポリイミド系エラストマー、ポリエーテルエーテルケトン、ポリフェニレンエーテルおよびポリエーテルスルホンから選ばれる少なくとも１種を含むフィルムの表面に、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する離型剤を含む離型層を形成する工程を含む、仮接着用積層体の製造方法。 At least one selected from polystyrene elastomers, polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, polyacryl elastomers, silicone elastomers, polyimide elastomers, polyether ether ketone, polyphenylene ether and polyether sulfone. The manufacturing method of the laminated body for temporary adhesion including the process of forming the mold release layer containing the mold release agent containing the at least 1 type chosen from a fluorine atom and a silicon atom on the surface of the film containing this.
  10. 　デバイスウエハと支持体との間に、請求項１～８のいずれか１項に記載の仮接着用積層体を有し、前記仮接着用積層体の一方の表面が前記デバイスウエハのデバイス面に接し、他方の表面が前記支持体の表面に接している、デバイスウエハ付き積層体。 The temporary adhesion laminate according to any one of claims 1 to 8 is provided between a device wafer and a support, and one surface of the temporary adhesion laminate is on a device surface of the device wafer. A laminated body with a device wafer in contact with the other surface of the substrate.
  11. 　前記仮接着用積層体は、フィルムの両方の表面に離型層を有する、請求項１０に記載のデバイスウエハ付き積層体。 The laminated body with a device wafer according to claim 10, wherein the laminated body for temporary bonding has a release layer on both surfaces of the film.
  12. 　前記仮接着用積層体は、フィルムの片方の表面のみに離型層を有し、前記離型層が前記デバイスウエハの表面に接している、請求項１０に記載のデバイスウエハ付き積層体。 The laminate for device wafer according to claim 10, wherein the laminate for temporary bonding has a release layer only on one surface of the film, and the release layer is in contact with the surface of the device wafer.
  13. 　前記仮接着用積層体は、フィルムの片方の表面のみに離型層を有し、前記離型層が前記支持体に接している、請求項１０に記載のデバイスウエハ付き積層体。 The laminate for device wafer according to claim 10, wherein the laminate for temporary bonding has a release layer only on one surface of the film, and the release layer is in contact with the support.
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