WO2015182469A1 - Film pour collage temporaire, stratifié, composition pour collage temporaire, et procédé et kit de fabrication d'un dispositif - Google Patents

Film pour collage temporaire, stratifié, composition pour collage temporaire, et procédé et kit de fabrication d'un dispositif Download PDF

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Publication number
WO2015182469A1
WO2015182469A1 PCT/JP2015/064571 JP2015064571W WO2015182469A1 WO 2015182469 A1 WO2015182469 A1 WO 2015182469A1 JP 2015064571 W JP2015064571 W JP 2015064571W WO 2015182469 A1 WO2015182469 A1 WO 2015182469A1
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group
resin
temporary
region
adhesive film
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PCT/JP2015/064571
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English (en)
Japanese (ja)
Inventor
一郎 小山
悠 岩井
義貴 加持
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富士フイルム株式会社
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Priority to JP2016523446A priority Critical patent/JP6379191B2/ja
Priority to KR1020167032081A priority patent/KR101884256B1/ko
Publication of WO2015182469A1 publication Critical patent/WO2015182469A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C09J179/085—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

  • the present invention relates to a temporary adhesive film, a laminate, a temporary adhesive composition, a device manufacturing method, and a kit. More specifically, the present invention relates to a temporary adhesive film, a laminate, a temporary adhesive composition, a device manufacturing method, and a kit that can be preferably used for manufacturing various devices such as semiconductor devices.
  • a wire bonding method As an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known.
  • a device wafer In order to reduce the size of an IC chip, a device wafer is used.
  • a method is known in which a through-hole is provided in the semiconductor device and a metal plug as an external terminal is connected to an integrated circuit so as to pass through the through-hole (so-called silicon through electrode (TSV) forming method).
  • TSV silicon through electrode
  • a technique for improving the degree of integration per unit area of a device wafer by multilayering an integrated circuit in an IC chip is known.
  • the multilayered integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the members constituting the IC chip.
  • the thinning of the device wafer is being considered as a thinning of such a member, which not only leads to the miniaturization of the IC chip, but also saves the process of manufacturing the through hole of the device wafer in the production of the silicon through electrode. Because it is possible, it is considered promising.
  • thinning of semiconductor devices such as power devices and image sensors has been attempted from the viewpoint of improving the degree of integration and improving the degree of freedom of the device structure.
  • a device wafer having a thickness of about 700 to 900 ⁇ m is widely known, but in recent years, for the purpose of reducing the size of an IC chip or the like, the thickness of the device wafer can be reduced to 200 ⁇ m or less. Has been tried. However, since a device wafer having a thickness of 200 ⁇ m or less is very thin and a semiconductor device manufacturing member based on the device wafer is very thin, such a member may be further processed, or When the member is simply moved, it is difficult to support the member stably and without damage.
  • the device wafer before thinning and the support substrate (carrier substrate) are temporarily fixed (temporary bonding) with a temporary adhesive, and the back surface of the device wafer is ground and thinned.
  • a technique for removing the support substrate from the device wafer later is known.
  • a temporary fixing film including a specific polyimide resin is interposed between a support member and a device wafer, and a device wafer is temporarily fixed to the support member, and temporarily fixed to the support member.
  • a step of subjecting the device wafer to predetermined processing a step of bringing the organic solvent into contact with the temporary fixing film, dissolving a part or all of the temporary fixing film, and separating the processed device wafer from the support member; And a method of manufacturing a semiconductor device, including a step of dividing a processed device wafer into individual pieces.
  • Patent Document 2 discloses an invention related to an adhesive for fixing a semiconductor element (adhesive for die bonding) that adheres between semiconductor elements or between a semiconductor element and a support substrate.
  • an adhesive As such an adhesive, (A1) a polyimide resin having a glass transition temperature of 60 ° C. or less and a weight average molecular weight of 10,000 to 100,000, and (A2) N-methyl-2-pyrrolidone so that the resin content is 20% by mass.
  • molding the adhesive composition containing a sex component in a sheet form is disclosed.
  • the temporary adhesive film between the surface of the device wafer and the support substrate When temporarily bonding the surface of the device wafer to the support substrate, the temporary adhesive film between the surface of the device wafer and the support substrate must have a certain level of adhesive strength in order to stably support the device wafer. In addition, there is a demand for characteristics that can easily release the temporarily bonded state between the device wafer and the support substrate.
  • a film that is soluble in an organic solvent is used as a temporary fixing film, and the temporary support for the device wafer is released by bringing the organic solvent into contact with the temporary fixing film.
  • the temporary fixing film disclosed in Patent Document 1 has poor chemical resistance.
  • Various chemicals may be used in the device manufacturing process. For example, when a device wafer is thinned by a wet process, an etching solution is used. For this reason, the temporary adhesive film that may be exposed to various chemicals in the device manufacturing process is required to have improved chemical resistance.
  • Patent Document 2 is an invention related to an adhesive for fixing a semiconductor element used for bonding semiconductor elements to each other or a semiconductor element and a support substrate. It does not adhere. For this reason, the adhesive for fixing a semiconductor element disclosed in Patent Document 2 does not have a property capable of releasing the temporary adhesion between the device wafer and the support substrate.
  • the present invention has been made in view of the above background, and its object is to stably attach a device wafer temporarily and perform temporary adhesion to the device wafer when the device wafer is subjected to mechanical or chemical treatment. It is an object of the present invention to provide a temporary adhesive film, a laminate, a temporary adhesive composition, a device manufacturing method, and a kit that can be easily released.
  • the present inventors have found that the mass decrease rate at 400 ° C. when heated from 25 ° C. at 10 ° C./min is 1% by mass or less, and N-methyl at 25 ° C.
  • a temporary adhesive film having an adhesion region having a solubility in pyrrolidone of 1 g / 100 g Solvent or less and a release region on the surface of the adhesion region can stably and temporarily bond a device wafer, and easily allows temporary adhesion to a device wafer. Based on these findings, the present invention has been completed.
  • the present invention provides the following.
  • the adhesive region contains a heterocyclic-containing resin containing at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, and a polybenzoxazole resin, and a maleimide resin, according to ⁇ 1>.
  • the solubility at 25 ° C. in a heterocyclic ring-containing resin in at least one solvent selected from ⁇ -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea is 10 g /
  • ⁇ 5> The temporary adhesive film according to any one of ⁇ 1> to ⁇ 4>, wherein 50 to 100% by mass of the crosslinking component contained in the adhesion region is a maleimide resin.
  • ⁇ 6> The temporary adhesive film according to any one of ⁇ 1> to ⁇ 5>, wherein the adhesion region further contains a thermal polymerization initiator.
  • ⁇ 7> The temporary adhesive film according to ⁇ 6>, wherein the thermal polymerization initiator has a one-minute half-life temperature of 130 to 300 ° C.
  • ⁇ 8> The temporary adhesive film according to ⁇ 6> or ⁇ 7>, wherein the thermal polymerization initiator is an organic peroxide.
  • ⁇ 9> The temporary adhesive film according to any one of ⁇ 1> to ⁇ 8>, wherein the release region includes a compound containing at least one selected from a fluorine atom and a silicon atom.
  • the release region includes a compound containing at least one selected from a fluorine atom and a silicon atom.
  • the release region contains a fluorine-based silane coupling agent.
  • the heterocyclic ring-containing resin has a solubility at 25 ° C. of 10 g / in at least one solvent selected from ⁇ -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea.
  • the composition for temporary adhesion according to ⁇ 12> which is a polyimide resin of 100 g Solvent or more.
  • the thermal polymerization initiator is an organic peroxide.
  • the ⁇ 19> mold release component is a composition for temporary adhesion as described in ⁇ 18> containing the compound containing at least 1 type chosen from a fluorine atom and a silicon atom.
  • a device manufacturing method comprising a step of applying the temporary bonding composition according to any one of ⁇ 12> to ⁇ 20>.
  • ⁇ 22> A kit for forming the temporary adhesive film according to any one of ⁇ 1> to ⁇ 10>, and the temporary adhesive composition according to any one of ⁇ 12> to ⁇ 20> A release region forming composition containing a mold component and a solvent.
  • the device wafer when a mechanical or chemical treatment is performed on a device wafer, the device wafer can be stably temporarily bonded, temporary bonding to the device wafer can be easily released, and excellent in chemical resistance.
  • a temporary adhesive film can be provided.
  • FIG. 1A, FIG. 1B, and FIG. 1C are respectively a schematic cross-sectional view illustrating temporary bonding between a support substrate and a device wafer, a schematic view illustrating a device wafer temporarily bonded by a support substrate, and temporary bonding by a support substrate. It is a schematic sectional drawing which shows the state by which the made device wafer was thinned.
  • 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.
  • monomer and “monomer” are synonymous.
  • the monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymer compound in the present invention refers to a compound having a weight average molecular weight exceeding 2000.
  • the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.
  • the temporary adhesive film of the present invention has an adhesive region and a release region on the surface of the adhesive region, and the adhesive region has a mass reduction rate at 400 ° C. when the temperature is increased from 25 ° C. at 10 ° C./min.
  • the solubility in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less.
  • the temporary adhesive film of the present invention has a release region on the surface of the adhesive region, the device wafer is laminated on the surface of the release region in the temporary adhesive film, and the laminated surface of the device wafer in the temporary adhesive film
  • a support substrate on the opposite surface, the device wafer having a structure such as a bump is appropriately protected, and a temporary adhesive film is applied from the device wafer after mechanical or chemical treatment is applied to the device wafer. It can be easily peeled off by mechanical peeling.
  • the adhesion region is excellent in heat resistance, and even when subjected to a process at high temperature, The wafer can be temporarily bonded stably. Further, since the temporary adhesive film is not easily deteriorated by heat, the temporary adhesive film can be easily peeled from the device wafer by a method such as mechanical peeling even after a high temperature process.
  • the device wafer and the support substrate in the present invention can be peeled off by mechanical peeling, so that the solubility in N-methylpyrrolidone at 25 ° C. in the adhesion region can be 1 g / 100 g Solvent or less, and the chemical resistance is excellent. .
  • the device wafer can be stably temporarily bonded.
  • the temporary adhesive film of the present invention can be stably temporarily bonded to a device wafer even when various processes such as high temperature processing and chemical processing are performed, and from the device after processing. It can be easily peeled off.
  • the mass reduction rate is a value measured by the calorimeter measuring device (TGA) under the above temperature rising condition under a nitrogen stream.
  • TGA calorimeter measuring device
  • the solubility is added to a solvent in 100 g of a sample while stirring the sample, and the solubility is confirmed. If the sample is completely dissolved, the sample is further added to the solution with stirring. The amount immediately before the sample was not dissolved when finally stirred at 25 ° C. for 1 hour was defined as the solubility.
  • the temporary adhesive film of the present invention has an adhesive region and a release region on the surface of the adhesive region.
  • the mass reduction rate at 400 ° C. when the temperature is increased from 25 ° C. to 10 ° C./min in the adhesion region is 1% by mass or less, preferably 0.90% by mass or less. 8 mass% or less is more preferable, 0.7 mass% or less is more preferable, 0.6 mass% or less is especially preferable, and 0.5 mass% or less is the most preferable. Within this range, the device wafer can be stably and temporarily bonded even when a high temperature process up to 400 ° C. is performed.
  • the temporary adhesive film since the temporary adhesive film is unlikely to be thermally deteriorated, the temporary adhesive film can be easily peeled from the device wafer by a method such as mechanical peeling even after a high temperature process.
  • the solubility of the adhesive region in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less, preferably 0.8 g / 100 g Solvent or less, more preferably 0.5 g / 100 g Solvent or less, 0 .1 g / 100 g Solvent or less is more preferable.
  • the device wafer can be stably temporarily bonded even when the chemical used during the device manufacturing process comes into contact with the temporary adhesive film.
  • the adhesive region and the release region may exist as independent adhesive layers and release layers, respectively, or the boundary between the adhesive region and the release region may not be clear.
  • the boundary between the adhesive region and the release region is not clear, an aspect in which the release component is unevenly distributed in the surface layer in the temporary adhesive layer to form the release region.
  • the adhesive region may be composed of two or more types of adhesive layers, and the release region may be composed of two or more release layers.
  • the temporary adhesive film of the present invention has an adhesive region.
  • the adhesion region is for bonding the device wafer and the support substrate.
  • the bonding area has a mass reduction rate at 400 ° C. of 1% by mass or less when the temperature is raised from 25 ° C. at 10 ° C./min, and the solubility in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less. Is used.
  • the average thickness of the adhesion region is preferably 0.1 to 500 ⁇ m, preferably 0.5 to 500 ⁇ m, more preferably 0.5 to 50 ⁇ m, and particularly preferably 0.5 to 10 ⁇ m.
  • the average thickness of the adhesion region is preferably thicker than the height of the structure of the device wafer described later.
  • the average thickness of the layer forming the bonding region is 1 to 50 ⁇ m. 2 to 20 ⁇ m is more preferable.
  • the average thickness of the adhesive region is preferably 1 to 50 ⁇ m, and preferably 2 to 20 ⁇ m.
  • the average thickness of the adhesion region is defined as the average value of five points measured by ellipsometry.
  • Any adhesive region can be used as long as it can achieve the above-described mass reduction rate and solubility, but it preferably contains a resin component A and a maleimide resin described later.
  • the adhesion region includes a resin component A and a maleimide resin, which will be described later, the resin component A can be interposed between the three-dimensionally cross-linked maleimide resins, and an adhesion region excellent in heat resistance and chemical resistance can be easily obtained.
  • any resin component A that can be contained in the adhesive region can be used as long as it satisfies the mass reduction rate and solubility.
  • the resin component A does not include a maleimide resin.
  • the resin component A examples include a heterocyclic ring-containing resin (preferably, a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, a polybenzoxazole resin), a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, Hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenolic resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated Petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, indene petroleum resin, olefin copolymer (for example, methylpentene copolymer), cycloolefin copolymer (for example, norbornene copolymer, dicyclopenta
  • polyimide resin polyimide resin, polyamideimide resin, polybenzimidazole resin, polybenzoxazole resin, polycarbonate resin, polyethersulfone resin, and polyester resin are preferable, and polyimide resin, polyamideimide resin, polybenzimidazole resin, and polybenzoxazole resin are more preferable.
  • a polyimide resin or a polyamideimide resin is more preferable, and a polyimide resin is particularly preferable. Since these resins are excellent in heat resistance, it is easy to achieve the mass reduction rate.
  • the polyimide resin has a solubility at 25 ° C.
  • the adhesion region can be formed by a coating method.
  • polyimide resin a resin obtained by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method can be used.
  • Known methods include, for example, a method of dehydrating and ring-closing the polyamic acid obtained by mixing approximately equimolar amounts of tetracarboxylic dianhydride and diamine in an organic solvent and reacting at a reaction temperature of 80 ° C. or lower. It is done.
  • substantially equimolar means that the molar ratio of tetracarboxylic dianhydride and diamine is close to 1: 1.
  • the composition ratio of tetracarboxylic dianhydride and diamine is 0.5 to 2.0 mol of diamine with respect to 1.0 mol of tetracarboxylic dianhydride in total. You may adjust as follows. By adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range, the weight average molecular weight of the polyimide resin can be adjusted.
  • the tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracar
  • More than one species can be used in combination.
  • 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenone tetracarboxylic dianhydride is preferred, and 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride is more preferred.
  • the diamine is not particularly limited and includes, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3 , 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3'- Diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4
  • One or more selected from the group is preferred, and 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane is more preferred.
  • Examples of the solvent used for the reaction of the tetracarboxylic dianhydride and diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N, N-dimethylformamide.
  • a nonpolar solvent for example, toluene or xylene
  • the reaction temperature of the tetracarboxylic dianhydride and the diamine is preferably less than 100 ° C, more preferably less than 90 ° C.
  • imidation of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically a vacuum or nitrogen atmosphere).
  • the heat treatment temperature is preferably 150 ° C. or higher, more preferably 180 to 450 ° C.
  • the weight average molecular weight (Mw) of the polyimide resin is preferably 10,000 to 1,000,000, and more preferably 20,000 to 100,000.
  • the polyimide resin has a solubility at 25 ° C. of 10 g / 100 g Solvent in at least one solvent selected from ⁇ -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea.
  • solvent selected from ⁇ -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea.
  • the above polyimide resins are preferred.
  • Polyimide resins having such solubility include, for example, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride and 3- (4-aminophenyl) -1,1,3-trimethyl-5- Examples thereof include a polyimide resin obtained by reacting with aminoindane. This polyimide resin is particularly excellent in heat resistance.
  • a commercially available product may be used as the polyimide resin.
  • Durimide registered trademark
  • FUJIFILM Corporation manufactured by FUJIFILM Corporation
  • GPT-LT manufactured by Gunei Chemical Co., Ltd.
  • SOXR-S SOXR-M
  • SOXR-U SOXR-C
  • SOXR-C all of which are Nippon Advanced Paper Industries Co., Ltd.
  • polyamideimide resin for example, a resin obtained by reacting an acid component such as polycarboxylic acid or a derivative thereof with diamine or diisocyanate in a polar solvent can be used.
  • the polar solvent include N-methyl-2-pyrrolidone (NMP) and N, N′-dimethylacetamide. The above reaction can be performed by stirring while heating to a predetermined temperature (usually about 60 to 200 ° C.).
  • Acid components used in the production of polyamideimide resin include trimellitic acid, trimellitic anhydride, trimellitic acid chloride; pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid), biphenyltetra Tetracarboxylic acids such as carboxylic acid, biphenylsulfone tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, ethylene glycol bis trimellitate, propylene glycol bis trimellitate and their acid anhydrides or acid chlorides; oxalic acid, Aliphatic dicarboxylic acids such as adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), dicarboxypoly (styrene-butadiene) Alicycl
  • Aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine and their diisocyanates; alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and These diisocyanates: m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, benzidine, o-tolidine, 2,4-tolylenediamine , Aromatic diamines such as 2,6-tolylenediamine and xylylenediamine and diisocyanates thereof.
  • the number average molecular weight (Mn) of the polyamideimide resin is preferably 5,000 to 100,000. More preferably, it is 10,000 to 50,000. If the number average molecular weight (Mn) of the polyamideimide resin is 5,000 or more, the durability is good. When the number average molecular weight (Mn) of the polyamide-imide resin is 100,000 or less, the solution viscosity is low and the adhesive region is easily formed by coating.
  • a commercially available product may be used as the polyamideimide resin.
  • Durimide registered trademark
  • Viromax registered trademark
  • 13NX manufactured by Toyobo Co., Ltd.
  • Rika Coat manufactured by Nippon Nippon Chemical Co., Ltd.
  • polybenzimidazole resin for example, a resin obtained by reacting an aromatic tetraamine and a dicarboxylic acid component can be used.
  • Aromatic tetraamines include, for example, 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraamononaphthalate, 2,3,6,7-tetraaminonaphthalate, 3,3 ′, 4,4′-tetraaminodiphenylmethane, 3,3 ′, 4,4′-tetraaminodiphenylethane, 3,3 ′, 4,4′-tetraaminodiphenyl-2,2-propane, 3,3′4 Examples include 4'-tetraaminodiphenyl thioether and 3,3 ', 4,4'-tetraaminodiphenyl sulfone.
  • a preferred aromatic tetraamine is 3,3 ′, 4,4′-tetraaminobiphenyl.
  • the dicarboxylic acid component include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, diphenic acid (2,2′-biphenyldicarboxylic acid), phenylindanedicarboxylic acid, 1, Examples thereof include 6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenylthioether dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, and 4,4′-diphenylthioether dicarboxylic acid.
  • the dicarboxylic acid component is preferably introduced at a ratio of about 1 mole of dicarboxylic acid component per mole of aromatic tetraamine. Note that the optimum ratio of the reactants in the polymerization system can be easily determined by those skilled in the art.
  • polybenzimidazole resins include poly-2,2 ′-(m-phenylene) -5,5′-bibenzimidazole, poly-2,2 ′-(biphenylene-2 "2" ')-5, 5'-bibenzimidazole, poly-2,2 '-(biphenylene-4 "4"')-5,5'-bibenzimidazole, poly-2,2 '-(1 ", 1", 3 "trimethyl Indanylene-3 "5" -p-phenylene-5,5'-bibenzidiimidazole, 2,2 '-(m-phenylene) -5,5'-bibenzidiimidazole / 2,2- (1 ", 1 ", 3" -trimethylindanilene) 5 ", 3"-(p-phenylene) -5,5'-bibenzimidazole copolymer, 2,2 '-(m-phenylene) -5,5'-bi Benzimidazole / 2,2'-
  • a commercially available product may be used as the polybenzimidazole resin.
  • MRS0810H manufactured by PBI
  • PBI PBI
  • Polybenzoxazole resin a resin obtained by dissolving polyhydroxyamide synthesized from a bisaminophenol compound and a dicarboxylic acid derivative in a solvent and undergoing a dehydration ring closure reaction is used.
  • bisaminophenol compounds examples include 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 2,2-bis (4-amino- 3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 3,3′-diamino- 4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3 '-Dihydroxybiphenyl, 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene, 9,9- (4-
  • Dicarboxylic acid derivatives include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,4′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4 -Naphthalenedicarboxylic acid, 4,4'-sulfonylbisbenzoic acid, 3,4'-sulfonylbisbenzoic acid, 3,3'-sulfonylbisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,4'-oxybis Benzoic acid, 3,3′-oxybisbenzoic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) hexa Fluoropropane, 2,2-bis (3-carboxyphenyl
  • a commercially available product may be used as the polybenzoxazole resin.
  • examples thereof include CRC-8800 (manufactured by Sumitomo Bakelite Co., Ltd.).
  • the adhesion region preferably contains 1 to 99% by mass, more preferably 10 to 90% by mass, and 25 to 75% by mass of the resin component A with respect to the total solid content of the adhesion region (excluding the solvent). Is particularly preferred.
  • the temporary adhesive film preferably contains 1 to 99% by mass of resin component A with respect to the total solid content (excluding the solvent) of the temporary adhesive film, more preferably 10 to 90% by mass, and 25 Particularly preferred is ⁇ 75% by weight. Only one type of resin component A may be used, or two or more types may be used. When there are two or more types of resin components A, the total is preferably in the above range.
  • the adhesion region preferably contains a maleimide resin as a crosslinking component.
  • Any maleimide resin can be used as long as the cured product satisfies the mass reduction rate and solubility.
  • a compound having a maleimide group and a crosslinked product obtained by crosslinking such a compound are collectively referred to as maleimide resin.
  • the cross-linked product is preferably a three-dimensional cross-linked product using a compound having a maleimide group.
  • the compound having a maleimide group may be a monomer or a polymer.
  • bismaleimide resin is preferable as the maleimide resin.
  • the bismaleimide resin is more preferably at least one selected from, for example, a bismaleimide resin represented by the following general formula (III) and a novolac maleimide resin represented by the following general formula (IV).
  • R represents an aromatic ring or a divalent organic group containing a linear, branched or cyclic aliphatic hydrocarbon group.
  • R is preferably a divalent group composed of a benzene group, a toluene group, a xylene group, a naphthalene group, a linear, branched or cyclic saturated hydrocarbon group, or a combination thereof.
  • R is preferably a divalent group represented by the following formula (v), (vi) or (vii).
  • s represents an integer of 0 to 20.
  • maleimide resin those described in paragraph Nos. 0020 to 0023 of JP-A No. 2003-321608 may be used.
  • Commercially available maleimide resins include BMI-1000, 2000, 3000, 4000, 5000, 5100, 7000 (manufactured by Daiwa Kasei Kogyo, bismaleimide resin), BANI-X (manufactured by Shin-Nakamura Chemical, bismaleimide resin), BANI- M (manufactured by Shin-Nakamura Chemical Co., Ltd., bismaleimide resin).
  • the adhesion region preferably contains maleimide resin in an amount of 1 to 99% by mass, more preferably 10 to 90% by mass, and more preferably 25 to 75% by mass with respect to the total solid content of the adhesion region (excluding the solvent). Particularly preferred. If content of maleimide resin is the said range, the heat resistance of an adhesion
  • the temporary adhesive film preferably contains maleimide resin in an amount of 1 to 99% by weight, more preferably 10 to 90% by weight, more preferably 25 to 25% by weight based on the total solid content (excluding the solvent) of the temporary adhesive film. 75% by mass is particularly preferred.
  • the maleimide resin is preferably contained in an amount of 10 to 100% by mass, more preferably 20 to 100% by mass, further preferably 50 to 100% by mass, based on the total mass of the crosslinking component contained in the adhesion region, and 80 to 100% by mass. Is particularly preferred.
  • the crosslinking component is substantially composed only of maleimide resin.
  • the fact that it is substantially composed only of a maleimide resin means that the content of the crosslinking component other than the maleimide resin in the total amount of the crosslinking component is preferably, for example, 1% by mass or less, more preferably 0.5% by mass or less, 0.1 mass% or less is especially preferable. According to this aspect, the heat resistance of the adhesion region can be further improved.
  • region of this invention may contain crosslinking components (other crosslinking components) other than maleimide resin.
  • the other crosslinking component a compound having two or more polymerizable groups, which can be polymerized by the action of actinic rays, radiation, light, heat, radicals or acids, can be used.
  • the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, and the like.
  • the ethylenically unsaturated bond group a vinyl group, an acrylic group, a methacryl group, and an allyl group are preferable.
  • Examples of the compound having a group having an ethylenically unsaturated bond include a (meth) acrylamide compound having 3 to 35 carbon atoms, a (meth) acrylate compound having 4 to 35 carbon atoms, and an aromatic vinyl compound having 6 to 35 carbon atoms. And vinyl ether compounds having 3 to 20 carbon atoms.
  • Examples of the compound having an epoxy group include bisphenol A type (or AD type, S type, F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide addition.
  • a compound having an epoxy group may be contained as a cross-linking component.
  • the content of the compound having an epoxy group in 100 parts by mass of the cross-linking component is 10% by mass. % Or less, more preferably 5% by mass or less, and in particular, it may not be substantially contained.
  • substantially not containing, for example, the content of the compound having an epoxy group is preferably 1% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less, and not contained. It is particularly preferred.
  • the adhesive region of the present invention preferably further contains a thermal polymerization generator.
  • a well-known thing can be used as a thermal-polymerization initiator.
  • a thermal-polymerization initiator a compound having a one-minute half-life temperature of 130 ° C. to 300 ° C., preferably 150 ° C. to 260 ° C. can be preferably used.
  • the heat resistance of the adhesion region can be further improved.
  • the 1-minute half-life temperature of the thermal polymerization initiator is a temperature at which the thermal polymerization initiator decomposes and its residual amount (mass) becomes 1 ⁇ 2 in 1 minute.
  • the one-minute half-life temperature of the thermal polymerization initiator is, for example, prepared by adding 0.1 mol / l of the thermal polymerization initiator in benzene, and heating it at several temperatures Ti (absolute temperature). The period t 1/2, T1 is measured, lnt 1/2, T1 is plotted against 1 / Ti, and the temperature at which the half-life is 1 minute is obtained from the obtained straight line.
  • the thermal polymerization initiator is preferably a compound (thermal radical generator) that generates radicals by heat energy and initiates or accelerates the reaction of a crosslinking component such as maleimide resin.
  • Thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, an organic peroxide or an azo compound is more preferable, and an organic peroxide is particularly preferable. Specific examples of the thermal radical generator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
  • the adhesion region preferably contains the thermal polymerization initiator in an amount of 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on the total solid content of the adhesion region (excluding the solvent). 8% by mass is particularly preferred. If content of a thermal-polymerization initiator is the said range, the heat resistance of an adhesion
  • the adhesive region in the temporary adhesive film of the present invention 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 adhesion region is formed by a coating method, the liquid properties (particularly fluidity) when prepared as a coating liquid are improved, and 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.
  • 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 adhesion region has a surfactant
  • the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the total solid content of the adhesion region. 0.05 to 0.1% by mass is particularly preferable.
  • the temporary adhesive film preferably contains the surfactant in an amount of 0.001 to 1% by mass, based on the total solid content of the temporary adhesive film (excluding the solvent), and 0.01 to 0.5% by mass. % Is more preferable, and 0.05 to 0.1% by mass is particularly preferable. Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
  • the adhesion region in the temporary adhesion film of the present invention may contain an antioxidant from the viewpoint of preventing the adhesion region from being lowered in molecular weight or gelled by oxidation during heating.
  • an antioxidant a phenol-based antioxidant, a sulfur-based antioxidant, a quinone-based antioxidant, a nitrogen-based antioxidant, and the like can be used.
  • phenolic antioxidant examples include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, “Irganox 1010”, “Irganox 1330”, “Irganox 3114”, “Irganox 1035” manufactured by BASF Corporation, Examples thereof include “Sumilizer MDP-S” and “Sumilizer GA-80” manufactured by Sumitomo Chemical Co., Ltd.
  • sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, “Sumilizer TPM”, “Sumilizer TPS”, “Sumilizer TP-D” manufactured by Sumitomo Chemical Co., Ltd., and the like.
  • Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
  • Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
  • Irganox 1010, Irganox 1330, and 3,3′-thiodipropionate distearyl are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.
  • 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 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the adhesion region. 1 to 1% by mass is particularly preferable.
  • the temporary adhesive film preferably contains the antioxidant in an amount of 0.001 to 10% by mass, and 0.01 to 5% by mass relative to the total solid content (excluding the solvent) of the temporary adhesive film. More preferred is 0.1 to 1% by mass.
  • One type of antioxidant may be sufficient and two or more types may be sufficient. When there are two or more kinds of antioxidants, the total is preferably within the above range.
  • the temporary adhesive film of the present invention has a release region on the surface of the adhesive region.
  • the release region is used for the purpose of adjusting the adhesive force between the device wafer and the bonding region, and facilitating peeling of the temporary adhesive film from the device wafer.
  • the average thickness of the release region is preferably 0.001 to 1 ⁇ m, and more preferably 0.01 to 0.5 ⁇ m. If it is the said range, while a temporary adhesive film has moderate adhesive force and adhesiveness with a device wafer is favorable, a temporary adhesive film can be easily peeled from a device wafer.
  • the average thickness of the layer forming the release region is 0.001. ⁇ 1 ⁇ m is preferable, and 0.01 to 0.5 ⁇ m is more preferable.
  • the average thickness of the release region is preferably 0.001 to 1 ⁇ m, More preferably, it is 0.01 to 0.5 ⁇ m.
  • the average thickness of the release region is defined as the average value of points measured by ellipsometry at five points.
  • the release region in the temporary adhesive film of the present invention preferably contains a compound containing at least one selected from fluorine atoms and silicon atoms, and more preferably contains a fluorine-based silane coupling agent.
  • the fluorine content in the release region is preferably 30 to 80% by mass, more preferably 40 to 76% by mass, and particularly preferably 60 to 75% by mass.
  • the fluorine content is defined by “ ⁇ (number of fluorine atoms in one molecule ⁇ mass of fluorine atoms) / mass of all atoms in one molecule ⁇ ⁇ 100”.
  • the release region preferably contains 10 to 100% by mass, preferably 50 to 100% by mass, of a compound containing at least one selected from fluorine atoms and silicon atoms, based on the total solid content of the release region. Is more preferable.
  • the temporary adhesive film is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content of the temporary adhesive film, of a compound containing at least one selected from fluorine atoms and silicon atoms. .
  • region contains the three-dimensional crosslinked material containing a fluorine atom from a heat resistant viewpoint.
  • a three-dimensional crosslinked product of a fluorine-containing polyfunctional monomer / oligomer or a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is preferable, and a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is particularly preferable.
  • a fluorine-containing silane coupling agent a non-halogen silane coupling agent having a low risk to human body and low metal corrosivity is preferable, and fluorine-containing alkoxysilane is particularly preferable.
  • Commercially available products include OPTOOL DAC-HP and OPTOOL DSX manufactured by Daikin Industries, Ltd.
  • the halogen-based silane coupling agent include a fluorinated chlorosilane compound.
  • the release region can contain a polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom.
  • the non-three-dimensional crosslinked structure means that the compound does not contain a crosslinked structure or the ratio of the crosslinked structure forming the three-dimensional crosslinked structure to the total crosslinked structure in the compound is 5% or less. % Or less is preferable. It is preferable that it is contained substantially.
  • the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used.
  • tetrafluoroethylene hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester.
  • Homopolymers of one or more fluorine-containing monofunctional monomers or copolymers of these monomers copolymers of one or more fluorine-containing monofunctional monomers with ethylene, fluorine-containing monofunctional monomers And at least one fluorine-containing resin selected from a copolymer of one or more of these and chlorotrifluoroethylene.
  • the polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure 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 has a repeating unit represented by the following formula (102).
  • R 101 , R 102 , R 103 , Y 101 , and Rf are each synonymous with General Formula (101), and preferred embodiments are also synonymous.
  • a copolymer component can be selected in addition to the perfluoroalkyl group-containing (meth) acrylic acid ester from the viewpoint of peelability.
  • the radical polymerizable compound capable of forming a copolymer component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, and acrylonitriles. And radical polymerizable compounds selected from methacrylonitriles and the like.
  • acrylate esters such as alkyl acrylate (alkyl group preferably has 1 to 20 carbon atoms), such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid Butyl, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol Monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg phenyl Methacrylic acid esters (eg, methyl methacrylate, ethyl)
  • (meth) acrylic acid esters having a hydrocarbon group having 1 to 24 carbon atoms are particularly preferred, for example, methyl (meth) acrylate, butyl , 2-ethylhexyl, lauryl, steer Le, include such glycidyl ester, 2-ethylhexyl, lauryl, higher alcohol (meth) acrylate stearyl, especially acrylate.
  • a commercially available product may be used.
  • Teflon registered trademark
  • DuPont Teflon
  • Tefzel DuPont
  • Fullon Asahi Glass
  • Halar SolvaySolexis
  • Heiler SolvaySolexis
  • Lumiflon Alignment
  • Afras Alignment
  • Cytop Alignment
  • Cefral Soft Central Glass Co., Ltd.
  • Cefral Coat Central Glass Co., Ltd.
  • Dionine Dionine
  • fluoro oils including perfluoropolyether oils such as fluoro rubber, Krytox (DuPont), Fomblin (Daitotech), Demnam (D
  • the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) of the non-three-dimensional crosslinked polymer compound having a fluorine atom is preferably 100000 to 2000, more preferably 50000 to 2000, and 10,000 to Most preferred is 2000.
  • the content of the non-three-dimensional crosslinked polymer compound having fluorine atoms in the release region is preferably 1 to 99% by mass with respect to the total solid content of the release region, from the viewpoint of good releasability. More preferably, it is preferably -95% by mass, more preferably 5-90% by mass.
  • the ratio (mass ratio) of the three-dimensional crosslinked product containing fluorine atoms to the polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms is preferably 5:95 to 50:50, and 10:90 to 40:60 is more preferable, and 15:85 to 30:70 is still more preferable.
  • the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom may be only one kind or two or more kinds. In the case of two or more types, the total is preferably in the above range.
  • the temporary bonding composition of the present invention includes a heterocyclic ring-containing resin containing at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, and a polybenzoxazole resin, and a crosslink containing 50 to 100% by mass of a maleimide resin. Contains ingredients and solvent.
  • heterocyclic ring-containing resin one or more selected from polyimide resins, polyamideimide resins, polybenzimidazole resins, and polybenzoxazole resins are used. As these specific examples, those described in the section of the adhesion region are preferably used. Of these, polyimide resin is preferable.
  • the polyimide resin is a polyimide having a solubility at 25 ° C.
  • the content of the heterocyclic ring-containing resin is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and more preferably 25 to 75% by mass with respect to the total solid content (excluding the solvent) of the temporary bonding composition. Is particularly preferred.
  • Crosslinking component one containing 50 to 100% by mass of maleimide resin is used.
  • the maleimide resin is preferably a bismaleimide resin.
  • specific examples of the maleimide resin those described in the section of the adhesion region are preferably used.
  • the crosslinking component preferably has a maleimide resin content of 80 to 100% by mass of the total crosslinking component.
  • the crosslinking component is substantially composed only of maleimide resin.
  • it is substantially comprised only with maleimide resin that content of crosslinking components other than maleimide resin is, for example, preferably 1% by mass or less, more preferably 0.5% by mass or less, and 0.1% by mass or less. Is particularly preferred.
  • the crosslinking component other than the maleimide resin those described in the section of other crosslinking components in the adhesion region are preferably used.
  • the content of the maleimide resin is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass with respect to the total solid content (excluding the solvent) of the temporary bonding composition. preferable.
  • a known solvent can be used without limitation.
  • anisole N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 2-butanone, methyl amyl ketone, limonene, mesitylene, methyl ethyl ketone, PGMEA (1-methoxy-2-propyl acetate) and the like are preferable.
  • Methyl-2-pyrrolidone, N, N-dimethylacetamide, methyl amyl ketone and limonene are preferred.
  • These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface.
  • the solvent content is preferably used such that the solid content concentration of the temporary bonding composition is 5 to 60% by mass.
  • One type of solvent may be sufficient and two or more types may be sufficient. When there are two or more solvents, the total is preferably in the above range.
  • the temporary bonding composition further contains a thermal polymerization initiator.
  • a thermal polymerization initiator By containing a thermal polymerization initiator, a temporary adhesive film having more excellent heat resistance and chemical resistance can be formed.
  • the thermal polymerization initiator those described in the section of the adhesion region are preferably used, and the preferred range is also the same.
  • the content of the thermal polymerization initiator is preferably 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, based on the total solid content (excluding the solvent) of the temporary bonding composition. 0.05 to 0.1% by mass is particularly preferable.
  • the temporary bonding composition further contains a release component.
  • a release component By including a release component, when the temporary bonding composition is applied in the form of a film, the release component is unevenly distributed on the surface layer, and the release region is unevenly distributed on the surface layer of the bonded region Can be formed.
  • the release component is preferably a material containing at least one selected from fluorine atoms and silicon atoms. Examples of the material containing at least one selected from a fluorine atom and a silicon atom include polymerizable monomers having a fluorine atom or a silicon atom. A fluorine-based silane coupling agent is more preferable.
  • the polymerizable monomer having a fluorine atom or a silicon atom is preferably a radical polymerizable monomer or oligomer in which one or more fluorine atoms or silicon atoms are contained in one molecule, and two or more fluorine atoms are contained in one molecule.
  • Particularly preferred is a polymerizable monomer having a group generally called a perfluoro group.
  • the radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom has a radically polymerizable functional group, and the radically polymerizable functional group is not particularly limited, but is an unsaturated group (such as an ethylenically unsaturated bond group). ) Is preferred.
  • the radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom preferably has two or more radically polymerizable functional groups, whereby the device wafer after undergoing a process at a high temperature in the device manufacturing process.
  • the peelability from can be further improved.
  • the polymerizable monomer having a fluorine atom can be selected from known monomers, preferably a monomer having a polymerizable group, and more preferably a fluorine-based silane coupling agent.
  • Examples of the polymerizable group include a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) acryloyl group, allyl group, Vinyloxy groups, etc.), ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, mercapto groups, ⁇ -ketoester groups, Hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like.
  • a silyl group having a hydroxyl group or a hydrolyzable group for example
  • the radically polymerizable monomer having a fluorine atom is preferably a compound represented by the following general formula (1).
  • Formula (I): Rf ⁇ -LY ⁇ n (In the formula, Rf represents a chain or cyclic n-valent group containing at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom, and n represents an integer of 2 or more.
  • L represents a single bond or a divalent linking group, and Y represents a polymerizable group.)
  • Y is a polymerizable group, for example, a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), a reactive unsaturated double bond.
  • Y represents a radical polymerizable group, and more preferably a group having a reactive unsaturated double bond.
  • T is preferably a radical polymerizable functional group represented by the following general formula (9).
  • R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • the dotted line represents a bond to a group linked to L.
  • alkyl group examples are preferably alkyl groups having 1 to 8 carbon atoms.
  • the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
  • L represents a single bond or a divalent linking group.
  • the divalent linking group a divalent aliphatic group, a divalent aromatic group, —O—, —S—, —CO—, —N (R) —, or a combination of two or more thereof can be obtained.
  • R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Rf represents a chain or cyclic n-valent group that contains at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom.
  • Rf may be a linear or branched polymer structure having a repeating unit having a fluorine atom.
  • the radically polymerizable monomer having a fluorine atom may be at least one selected from compounds represented by the following structural formulas (1), (2), (3), (4) and (5). preferable.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents —C p H 2p —, —C (C p H 2p + 1 ) H—, —CH 2 C ( C p H 2p + 1 ) H— or —CH 2 CH 2 O—, where R f is —C n F 2n + 1 , — (CF 2 ) n H, —C n F 2n + 1 —CF 3, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, or, -N (C p H 2p + 1) represents the SO 2 C n F 2n + 1 .
  • p is an integer of 1 ⁇ 10
  • n is an integer of 1 ⁇ 16
  • CF 2 CFOR g.
  • Structural formula (2) (In the structural formula (2), R g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
  • R 3 and R 4 represent a hydrogen atom or a methyl group.
  • R 5 and R 6 represent —C q H 2q —, —C (C q H 2q + 1 ) H— , —CH 2 C (C q H 2q + 1 ) H— or —CH 2 CH 2 O—,
  • R j represents —C t F 2t , q is an integer of 1 to 10, and t is 1 to 16 Is an integer.
  • radical polymerizable monomer or oligomer having a fluorine atom an oligomer having a repeating unit having a fluorine atom and a repeating unit having a radical polymerizable functional group can also be preferably used.
  • the repeating unit having a fluorine atom is preferably selected from at least one repeating unit represented by the following formulas (6), (7) and (10).
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, and R 1 , R 2 , R 3 , At least one of R 4 is a fluorine atom or a monovalent organic group having a fluorine atom.
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group
  • Y 1 represents a single bond, —CO—, — It represents a divalent linking group selected from the group consisting of O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.
  • R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group
  • Y 2 and Y 3 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
  • Rf represents a divalent organic group having a fluorine atom.
  • the monovalent organic group having a fluorine atom in formula (6) and formula (7) is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
  • a fluorine-containing alkyl group having 1 to 15 carbon atoms is particularly preferred.
  • This fluorine-containing alkyl group is a straight chain (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.
  • branched structures for example, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like, and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these).
  • An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , — CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
  • the divalent organic group having a fluorine atom in the formula (10) is not particularly limited, but is preferably a fluorine-containing alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Fifteen fluorine-containing alkylene groups are particularly preferred.
  • This fluorine-containing alkylene group is a straight chain (for example, —CF 2 CF 2 —, —CH 2 (CF 2 ) 4 —, —CH 2 (CF 2 ) 8 CF 2 —, —CH 2 CH 2 (CF 2 ) 4 -, Etc.), branched structures (eg, —CH (CF 3 ) CF 2 —, —CH 2 CF (CF 3 ) CF 2 —, —CH (CH 3 ) CF 2 CF 2 —, —CH (CH 3 ) (CF 2 ) 5 CF 2- and the like) and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl, perfluorocyclopentyl, or substituted therewith A linking group having an alkyl group, etc.) or an ether bond (for example, —CH 2 OCH 2 CF 2 CF 2 —, —CH 2 CH 2 OCH 2 C 4 F 8 —,
  • the monovalent organic group in the formulas (6), (7), and (10) is preferably an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms. At least one or more selected from atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms Examples include organic groups composed of elements. More specific examples include organic groups composed of the following structures singly or in combination. The monovalent organic group may further have a substituent.
  • substituents that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group.
  • the organic group may contain an ether bond, an ester bond, or a ureido bond.
  • the monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
  • the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
  • a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-ethylhexyl group, A methylhexyl group, a cyclopentyl group, etc. are mentioned.
  • alkenyl group and an alkenyl group having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group.
  • the alkynyl group is preferably an alkynyl group having 3 to 10 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethylsilylethynyl group.
  • the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.
  • an alkyl group or an aryl group is preferable.
  • the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms.
  • the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
  • the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
  • an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
  • the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
  • the content of the repeating unit having a fluorine atom is preferably 2 mol% to 98 mol%, preferably 10 mol% to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. Is more preferable.
  • repeating unit having a radical polymerizable functional group a repeating unit represented by the following formula (8) is preferable.
  • R 801 to R 803 each independently represents a hydrogen atom, an alkyl group, or a halogen atom.
  • Y 8 represents a single bond, or —CO—, —O—, — NH— represents a divalent linking group selected from the group consisting of a divalent aliphatic group, a divalent aromatic group, and combinations thereof, and T represents a structure having a radical polymerizable functional group.
  • the alkyl group as R 801 to R 803 is preferably an alkyl group having 1 to 6 carbon atoms.
  • T preferably represents a radical polymerizable functional group represented by the general formula (9).
  • R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • the dotted line represents a bond to a group linked to Y 8.
  • alkyl group examples are preferably alkyl groups having 1 to 8 carbon atoms.
  • the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
  • Y 8 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. To express. Specific examples of comprising the combination Y 8 below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the formula (9).
  • the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
  • an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
  • the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
  • substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
  • Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
  • Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
  • the content of the repeating unit having a radical polymerizable functional group is preferably 2 to 98 mol%, preferably 10 to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. More preferred.
  • the weight average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a fluorine atom as measured by gel permeation chromatography (GPC) is preferably 2000 to 20000, more preferably 2000 to 15000, and more preferably 2000 to 10,000. Most preferred.
  • the weight average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a fluorine atom as measured by gel permeation chromatography (GPC) method is preferably 2000 to 10,000, more preferably 8000 to 2000, and preferably 6000 to 2000. Most preferred.
  • the content of the radically polymerizable monomer or oligomer having a fluorine atom is not particularly limited, and is preferably a release region.
  • the content is preferably 0.01 to 15% by mass with respect to the total solid content of the forming composition. If it is 0.01 mass% or more, sufficient peelability is obtained. If it is 15 mass% or less, sufficient adhesive force will be obtained.
  • the radically polymerizable monomer or oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer.
  • at least one terminal of a polydimethylsiloxane bond is an ethylenically unsaturated group such as a (meth) acryloyl group and a styryl group.
  • a compound having a (meth) acryloyl group is preferable.
  • the number average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a silicon atom as measured by gel permeation chromatography is preferably 1,000 to 10,000.
  • the number average molecular weight in terms of polystyrene by a gel permeation chromatography method of a radically polymerizable oligomer having a silicon atom is less than 1,000 or 10,000 or more, properties such as releasability due to a silicon atom are hardly expressed.
  • radical polymerizable monomer having a silicon atom a compound represented by the general formula (11) or (12) is preferable.
  • R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group.
  • Z 11 , Z 12 , and Z 13 each independently represents a radically polymerizable group,
  • L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group, and
  • n and m each independently represents 0 or more. Represents an integer.
  • R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group.
  • the alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, n-propyl group. Group, isopropyl group and the like.
  • An alkoxy group means —OR 20 , wherein R 20 represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group And a butoxy group.
  • An alkoxycarbonyl group means —C ( ⁇ O) R 21 , where R 21 represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specifically includes methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl.
  • R 21 represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specifically includes methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl.
  • the aryl group include a phenyl group, a tolyl group, and a naphthyl group, which may have a substituent, such as phenylmethyl (benzyl) group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl. Groups and the like.
  • L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group.
  • the divalent linking group represents a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. .
  • N and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, and more preferably an integer of 0 to 50.
  • Z 11 , Z 12 , and Z 13 each independently represent a radical polymerizable group, and a functional group represented by any one of the following general formulas (i) to (iii) is particularly preferable.
  • R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group.
  • X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —, R 104 represents a hydrogen atom or a monovalent organic group.
  • R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group.
  • R 101 preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity.
  • R 102 and R 103 are each independently preferably a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, or optionally substituted alkyl.
  • aryl group which may have a substituent alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent Represents an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, among which a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.
  • X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —
  • R 104 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include an alkyl group which may have a substituent.
  • R 104 is preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.
  • substituents examples include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, A nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.
  • R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group.
  • Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —.
  • R 206 represents a hydrogen atom or a monovalent organic group.
  • R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group.
  • R 201 to R 205 each independently represents a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent.
  • An aryl group that may have, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent It is preferably a good arylamino group, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group, having a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent. It is more preferably an alkyl group which may be substituted or an aryl group which may have a substituent.
  • Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —.
  • R 206 has the same meaning as R 104 in formula (i), and preferred examples thereof are also the same.
  • R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group.
  • Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or a substituent.
  • R 304 has the same meaning as R 104 in formula (i).
  • R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group.
  • R 301 is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group because of high radical reactivity.
  • R 302 and R 303 are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent.
  • An alkyl group that may have a substituent or an aryl group that may have a substituent is more preferable because of high radical reactivity.
  • Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or an optionally substituted phenylene group.
  • R 304 has the same meaning as R 104 in the general formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and An isopropyl group is preferable because of high radical reactivity.
  • the release region forming composition 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 based on the total solid content of the release region forming composition. 0.01 to 15% by mass is preferable. If it is 0.01 mass% or more, sufficient peelability is obtained. If it is 15 mass% or less, sufficient adhesive force will be obtained.
  • 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 Co., Ltd., TEGORad2700, manufactured by Degussa, and UV-3500B (manufactured by BYK).
  • the content of the release component is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content (excluding the solvent) of the temporary bonding composition. 1 to 1% by mass is particularly preferred.
  • the temporary bonding composition preferably further contains a surfactant.
  • a surfactant those described in the section of the adhesion region are preferably used, and the preferable range is also the same.
  • the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the total solid content (excluding the solvent) of the temporary bonding composition. 0.05 to 0.1% by mass is particularly preferable. Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
  • the temporary bonding composition preferably further contains an antioxidant.
  • an antioxidant those described in the section of the adhesion region are preferably used, and the preferred range is also the same.
  • the content of the antioxidant is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content (excluding the solvent) of the temporary bonding composition. 1 to 1% by mass is particularly 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.
  • the temporary bonding composition preferably contains a plasticizer in order to enhance the deformability at high temperature and improve the adhesion flatness.
  • a plasticizer phthalic acid esters, fatty acid esters, aromatic polycarboxylic acid esters, polyesters, and the like can be used.
  • phthalic acid esters examples include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (above, manufactured by Daihachi Chemical), PL-200, DOIP (above, made by CG Esther), Sunsizer DUP (new) Nippon Rika).
  • fatty acid esters examples include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panaceto 800B, Panaceto 875, Panaceto 810 (above, NOF Corporation), DBA, DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (manufactured by Daihachi Chemical Co., Ltd.), and the like.
  • aromatic polycarboxylic acid ester examples include TOTM (manufactured by Daihachi Chemical), monosizer W-705 (manufactured by Daihachi Chemical), UL-80, UL-100 (manufactured by ADEKA), and the like.
  • polyester examples include Polycizer TD-1720, Polycizer S-2002, Polycizer S-2010 (above, manufactured by DIC), BAA-15 (produced by Daihachi Chemical).
  • plasticizers DIDP, DIDA, TOTM, Unistar M-2222SL and Polycizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable. Only one type of plasticizer may be used, or two or more types may be combined.
  • the molecular weight of the plasticizer is preferably 250 ° C. or higher when the weight is reduced by 1% by mass when measured under a nitrogen stream under a constant rate of temperature increase at 20 ° C./min. 270 ° C. or higher is more preferable, and 300 ° C. or higher is particularly preferable.
  • the upper limit is not particularly defined, but can be, for example, 500 ° C. or less.
  • the content of the plasticizer is preferably 1 to 50.0% by mass and more preferably 5 to 20.0% by mass with respect to the total mass of the temporary bonding composition. Only one type of plasticizer may be used, or two or more types may be used. When two or more plasticizers are used, the total is preferably within the above range.
  • composition for temporary bonding in the present invention is blended with various additives such as a curing agent, a curing catalyst, a filler, an ultraviolet absorber, an anti-aggregation agent, etc. can do.
  • blending these additives it is preferable that the total compounding quantity shall be 3 mass% or less of solid content of the composition for temporary adhesion
  • the adhesion region in the temporary adhesive film of the present invention supports the above-described temporary adhesion composition using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. It can be formed by coating on a substrate and then drying.
  • the spin coat method, the spray method, and the screen printing method are preferable, the spin coat method and the spray method are more preferable, and the spin coat method is particularly preferable.
  • the composition for forming a release region preferably contains a release component and a solvent.
  • the release component is preferably a material containing at least one selected from fluorine atoms and silicon atoms.
  • the material containing at least one selected from a fluorine atom and a silicon atom include polymerizable monomers having a fluorine atom or a silicon atom.
  • a fluorine-based silane coupling agent is more preferable. With the fluorine-based silane coupling agent, the release region layer can be firmly formed on the surface of the adhesion region. For this reason, it becomes difficult for a solvent to permeate into the interface between the layer in the adhesion region and the layer in the release region, and a temporary adhesive film having excellent chemical resistance can be formed.
  • the content of the mold release component is preferably 5 to 100% by mass, more preferably 50 to 100% by mass, more preferably 90 to 90% by mass with respect to the total solid content of the mold release region forming composition, from the viewpoint of good releasability. 100 mass% is more preferable.
  • a known solvent can be used without limitation, and the same solvent as the solvent in the temporary bonding composition described above can be used.
  • Perfluoroalkanes can also be used. Among them, N-methyl-2-pyrrolidone, 2-butanone, methyl amyl ketone, limonene, 1-methoxy-2-propyl acetate, perfluoroalkane, and methyl ethyl ketone are preferable. N-methyl-2-pyrrolidone, 2-butanone, methyl More preferred are amyl ketone, limonene and 1-methoxy-2-propyl acetate. These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface.
  • the release region-forming composition can contain various compounds depending on the purpose within a range that does not impair 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.
  • those described above with reference to the temporary bonding composition can be used.
  • the solid content concentration of the release region forming composition is preferably 3 to 40% by mass, and more preferably 5 to 40% by mass.
  • the above-described composition for forming a release region is applied onto a supporting substrate using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. And then dried.
  • a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like is preferable, the spin coat method and the spray method are more preferable, and the spin coat method is particularly preferable.
  • the kit of this invention contains the composition for temporary adhesion mentioned above, and the composition for mold release area
  • the temporary adhesive film of the present invention can be produced by sequentially applying the temporary bonding composition and the release region forming composition onto the support substrate.
  • the temporary adhesive film of the present invention can also be produced by sequentially applying a release region forming composition and a temporary bonding composition to a device wafer.
  • the respective compositions and preferred ranges of the temporary bonding composition and the release region forming composition are the same as those described above.
  • the laminate of the present invention is obtained by laminating a device wafer on the surface of the release region of the temporary adhesive film of the present invention described above.
  • 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 temporary adhesive film of the present invention can be stably temporarily bonded even to a device wafer having a structure on the surface, and can be easily released from temporary bonding to the device wafer.
  • the height of the structure is not particularly limited, but is preferably 5 to 100 ⁇ m, for example.
  • 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 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.
  • a support substrate is disposed on the surface of the temporary adhesive film on the side opposite to the laminated surface of the device wafer.
  • the material of the support substrate is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate.
  • it may be a silicon substrate.
  • the thickness of the support substrate is not particularly limited, but is preferably 300 ⁇ m to 5 mm, for example.
  • the method for producing a device of the present invention includes a step of applying the above-described temporary bonding composition of the present invention.
  • the device manufacturing method of the present invention will be described in more detail.
  • a support substrate-temporary adhesive film-device wafer laminate (hereinafter also referred to as a laminate) can be produced by any of the following methods (1) to (4).
  • the temporary adhesion composition of the present invention is applied to a support substrate and heated (baked) to form a layer of an adhesion region.
  • Examples of the method for applying the temporary bonding composition include conventionally known methods such as spin coating, spraying, roller coating, flow coating, doctor coating, and dipping.
  • the release region forming composition described above is applied on the layer of the adhesive region, and heated (baked) to form a layer of the release region, thereby forming the temporary adhesive film of the present invention.
  • the application method of the release region forming composition include conventionally known methods such as spin coating, spraying, roller coating, flow coating, doctor coating, and dipping.
  • the device wafer is pressure-bonded to the surface opposite to the surface on which the support substrate of the temporary adhesive film is disposed (that is, the surface of the temporary adhesive film on the release region side) to manufacture a laminate.
  • 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.
  • release region forming composition is applied to a device wafer and heated (baked) to form a release region layer.
  • the temporary adhesion composition of the present invention is applied on the release area layer, and heated (baked) to form the adhesion area layer, thereby forming the temporary adhesion film of the present invention.
  • the surface opposite to the surface on which the device wafer of the temporary adhesive film is disposed is pressure-bonded to the support substrate to produce a laminate.
  • the pressure bonding conditions are preferably the above-described conditions.
  • the temporary bonding composition of the present invention containing a release component is applied to the surface of either the support substrate or the device wafer, and heated (baked), so that the release area is unevenly distributed on the surface layer of the adhesive area.
  • a temporary adhesive film is formed.
  • a support substrate or a device wafer is pressure-bonded to the surface of the temporary adhesive film to produce a laminate.
  • the pressure bonding conditions are preferably the above-described conditions.
  • the mold release region forming composition described above is applied to a device wafer and heated (baked) to form a mold release layer layer on the device wafer.
  • the above-described temporary adhesion composition of the present invention is applied to a support substrate and heated (baked) to form a layer of an adhesion region on the support substrate.
  • the release area on the device wafer and the adhesion area on the support substrate are pressure-bonded to form a temporary adhesion film, and a laminate is manufactured.
  • the pressure bonding conditions are preferably the above-described conditions.
  • FIG. 1A, FIG. 1B, and FIG. 1C are respectively a schematic cross-sectional view illustrating temporary bonding between a support substrate and a device wafer, a schematic view illustrating a device wafer temporarily bonded by a support substrate, and temporary bonding by a support substrate. It is a schematic sectional drawing which shows the state by which the made device wafer was thinned.
  • the device wafer 60 is formed by providing a plurality of device chips 62 on a surface 61a of a silicon substrate 61. Further, a release region 71 is provided on the surface of the device wafer 60 on the structure 62 side.
  • the device wafer 60 preferably has an average film thickness of 500 ⁇ m or more.
  • the structure 62 is called a device chip or a bump, and the average height is preferably in the range of 5 to 100 ⁇ m.
  • an adhesive support 100 in which an adhesive region 11 is provided on a support substrate 12 is prepared.
  • the adhesive support 100 is formed on the support substrate 12 using the conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. It can be formed by applying to and then drying.
  • the surface of the release area 71 provided on the device wafer is pressed against the adhesion area 11 of the adhesive support 100. Thereby, as shown in FIG. 1B, the release region 71 and the adhesion region 11 are bonded to each other, and a temporary adhesive film 80 having the release region 71 and the adhesion region 11 is formed.
  • the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (not particularly limited, for example, thinning treatment such as gliding or chemical mechanical polishing (CMP), high temperature / vacuum such as CVD or PVD. Treatment with chemicals such as organic solvent, acidic treatment solution or basic treatment solution, plating treatment, actinic ray irradiation, heating / cooling treatment, etc.), as shown in FIG.
  • the thickness of 61 is reduced (for example, the average thickness is preferably less than 500 ⁇ m, more preferably 1 to 200 ⁇ m) to obtain a thin device wafer 60a.
  • a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61c 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 maximum temperature reached in the heat treatment is set to a temperature lower than the softening point of the adhesion region.
  • 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 temporary adhesive film 80 is peeled from the surface 61a of the thin device wafer 60a.
  • the temporary adhesive film 80 is preferably peeled off by a physical action such as peeling. That is, it is preferable to slide the thin device wafer 60 a against the adhesive support 100 or peel the thin device wafer 60 a from the adhesive support 100.
  • the temporary adhesive film 80 can be peeled from the surface 61a of the thin device wafer 60a.
  • the surface 61a of the thin device wafer 60a may be treated with a stripping solution or the like as necessary.
  • a stripping solution for example, stripping solutions described in paragraph numbers 0203 to 0212 of JP-A-2014-80570 can be used.
  • the temporary adhesive film 80 of the present invention does not necessarily require treatment with a stripping solution or the like.
  • the temporary adhesive film 80 can be removed from the surface 61a of the thin device wafer 60a only by mechanical peeling and without causing peeling residue.
  • the release layer has a single layer structure, but the release layer may have a multilayer structure.
  • the silicon substrate is exemplified as the member to be processed.
  • the present invention is not limited to this, and any member that can be subjected to mechanical or chemical treatment in the device manufacturing method is used. 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 silicon substrate thinning process and the silicon through electrode forming process are exemplified as the mechanical or chemical process for the silicon substrate supported by the support substrate.
  • the present invention is not limited thereto. Any processing required in the device manufacturing method 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.
  • Example 1 ⁇ Formation of adhesion area> After applying the adhesive region forming composition 1 having the composition shown in Table 1 to a 4-inch Si wafer with a spin coater (Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa), 120 ° C. for 3 minutes, 250 ° C. for 3 minutes. Baking was performed to form a wafer 1 provided with an adhesive region having a thickness of 5 ⁇ m.
  • a spin coater Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa
  • ⁇ Formation of release area> After applying the release region forming composition 1 having the composition shown in Table 2 to the adhesion region of the wafer 1 using a spin coater (Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa) at 120 ° C. on a hot plate. Then, the wafer 1 was baked at 190 ° C. for 3 minutes to form a release region having a thickness of 0.1 ⁇ m on the adhesion region, and a wafer 1 provided with a temporary adhesion film was formed.
  • a spin coater Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa
  • test piece was prepared by thermocompression bonding of wafer 1 and a 4-inch Si wafer (wafer 2) having nothing applied to the surface.
  • Wafer 2 a 4-inch Si wafer
  • the surface of the wafer 1 having the temporary adhesive film and the surface of the wafer 2 on which nothing was applied were overlapped and pressure-bonded at 190 ° C. and 0.20 MPa for 3 minutes.
  • pressure bonding After pressure bonding, it was heated at 280 ° C. for 30 minutes.
  • Example 1 (Examples 2 to 32, 35) In Example 1, the adhesive region forming composition and the release region forming composition were formed in the combinations shown in Table 3 to form the adhesive region and the release region, respectively. The provided test piece was produced.
  • Example 33 A composition prepared by mixing 99% by mass of the adhesive region forming composition 19 and 1% by mass of the release region forming composition 1 was mixed with a spin coater (Opticaat MS-A100 manufactured by Mikasa) on a 4-inch Si wafer. And then baked at 120 ° C. for 3 minutes and at 250 ° C. for 3 minutes to form a wafer 1 having a 5 ⁇ m-thick adhesive region, and a temporary adhesive film is provided according to Example 1. The obtained test piece was produced.
  • a spin coater Opticaat MS-A100 manufactured by Mikasa
  • Example 34 A composition prepared by mixing 99% by mass of the adhesive region forming composition 19 and 1% by mass of the release region forming composition 2 was mixed with a spin coater (Opticaat MS-A100 made by Mikasa) on a 4-inch Si wafer. And then baked at 120 ° C. for 3 minutes and at 250 ° C. for 3 minutes to form a wafer 1 having a 5 ⁇ m-thick adhesive region, and a temporary adhesive film is provided according to Example 1. The obtained test piece was produced.
  • a spin coater Opticaat MS-A100 made by Mikasa
  • Example 1 a test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that the release region forming composition 1 was not used.
  • Example 2 In Example 1, a test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that the composition 1 for forming an adhesive region was not used.
  • Comparative Examples 3 to 7 A test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that Comparative Compositions 1 to 7 were used in place of the adhesive region forming composition 1.
  • Adhesive force of 80N or more 4 Adhesive force of 60N or more and less than 80N 3: Adhesive force of 40N or more and less than 60N 2: Adhesive force of 20N or more and less than 40N 1: Adhesive force of less than 20N
  • ⁇ Chemical resistance> The prepared test piece is put in a glass container filled with N-methyl-2-pyrrolidone at 25 ° C., and the sample after applying ultrasonic waves for 15 minutes using an ultrasonic cleaner is observed. evaluated. In the following evaluation criteria, 2 to 5 is practical, and 3 to 5 is preferable. 5: There is no peeling of the wafer, and the surface of the temporary adhesive film after peeling is not affected by the solvent. 4: Although there is no peeling of the wafer, a range of less than 1 mm from the side surface in contact with the solvent of the temporary adhesive film after peeling is affected by the solvent.
  • ⁇ Void> When the wafer 1 is formed, there is no change except that a 4-inch glass wafer is used instead of the 4-inch Si wafer, and the temporary adhesive layers of Examples 1 to 35 and Comparative Examples 1 to 9 are formed, and the 4-inch Si is formed. Bonded to the wafer.
  • the obtained sample was heated in an oven at 400 ° C. for 3 hours under a nitrogen atmosphere. Thereafter, the temporary adhesive layer was visually observed from the glass wafer side of the sample and evaluated according to the following criteria. In the following evaluation criteria, 2 to 5 is practical, and 3 to 5 is preferable.
  • the void is a void generated at the interface between the temporary adhesive layer and the glass. 5: Void was not seen at all. 4: Less than 5 voids were observed. 3: 5 or more and less than 10 voids were observed. 2: 10 or more and less than 15 voids were observed. 1: 15 or more voids were observed.
  • Comparative compositions 1 to 8 in Table 1 were prepared by the following method.
  • Comparative composition 1 A composition of Example 1 of JP-A-2014-29999 was prepared.
  • Comparative composition 2 The composition of Example 2 of JP-A-2014-29999 was prepared.
  • Comparative composition 3 A composition of Example 3 of JP-A-2014-29999 was prepared.
  • Comparative composition 4 A composition of Example 4 of JP-A-2014-29999 was prepared.
  • Comparative composition 5 A composition of Example 5 of JP 2014-29999 A was prepared.
  • Comparative composition 6 A composition of Example 6 of JP-A-2014-29999 was prepared.
  • Comparative composition 7 The temporary bonding composition 1 did not contain the crosslinking component C-1.
  • decrease rate in Table 1 was measured with the following method. ⁇ 400 ° C mass reduction rate> Using a thermogravimetric analyzer Q500 (TA), a 2-3 mg sample was heated on an aluminum pan under a nitrogen stream of 60 mL / min to an initial temperature of 25 ° C. to 400 ° C. under a constant temperature increase condition of 10 ° C./min. The residual mass when reaching 400 ° C. was measured.
  • TA thermogravimetric analyzer Q500
  • the solubility in Table 1 was measured by the following method. ⁇ Solubility> A fixed amount of the sample was added to 100 g of N-methyl-2-pyrrolidone while stirring to confirm the solubility. When the sample was completely dissolved, the operation of adding a certain amount of the sample while stirring was repeated, and the amount immediately before the sample was not dissolved when finally stirred at 25 ° C. for 1 hour was defined as the solubility.
  • A-1 OPTOOL DSX (Daikin Kogyo Co., Ltd., fluorine-based silane coupling agent)
  • A-2 RS-72-K (DIC Corporation, fluorine compound)
  • A-3 RS-76-E (DIC Corporation, fluorine compound)
  • A-4 UV-3500B (manufactured by BYK, silicon-based compound)
  • A-5 (Heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane (manufactured by TCI)
  • A-7 TEFLON (registered trademark) AF (made by Mitsui DuPont Fluorochemical Co., Ltd., fluorine-based compound)
  • A-8 CYTOP (A

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Abstract

Cette invention concerne : un film pour collage temporaire qui permet le collage temporaire stable d'une plaquette de semi-conducteur de dispositif quand ladite plaquette de semi-conducteur de dispositif est soumise à un traitement mécanique ou chimique, et qui permet également de mettre facilement fin au collage temporaire à la plaquette de semi-conducteur de dispositif, tout en présentant une excellente résistance aux produits chimiques ; un stratifié ; une composition pour collage temporaire ; et un procédé et un kit de fabrication d'un dispositif. Ce film de collage temporaire comporte une région de collage et une région anti-adhésive sur la surface de la région de collage. La région de collage présente un taux de réduction en poids à 400°C de 1 % en poids ou moins si elle est chauffée à partir de 25°C à une vitesse de chauffage de 10°C/minute, tout en ayant une solubilité dans la N-méthylpyrrolidone à 25°C de 1 g/100 g de solvant ou moins.
PCT/JP2015/064571 2014-05-30 2015-05-21 Film pour collage temporaire, stratifié, composition pour collage temporaire, et procédé et kit de fabrication d'un dispositif WO2015182469A1 (fr)

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JP7134291B2 (ja) 2019-08-08 2022-09-09 達興材料股▲ふん▼有限公司 仮貼組成物、仮貼膜、複合膜、及び、半導体ウエハーパッケージ
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TWI663239B (zh) 2019-06-21
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JPWO2015182469A1 (ja) 2017-04-27
JP6379191B2 (ja) 2018-08-22

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